Microenvironment Evolution at Triple-phase Interface on the CO2RR Process of Hydrophobic Oxide-derived Copper

Microenvironment Evolution at Triple-phase Interface on the CO2RR Process of Hydrophobic Oxide-derived Copper | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Microenvironment Evolution at Triple-phase Interface on the CO2RR Process of Hydrophobic Oxide-derived Copper Jinli YU, Zezhong Xie, Hao Yang, Qiushi Wang, Jian Chen, Shu-qin Song, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3812973/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The local microenvironment of electricity-powered CO 2 electroreduction reaction (CO 2 RR) surrounding the catalyst-electrolyte-gas triple-phase interface plays a crucial role in catalytic activity and selectivity as it affects reaction pathways and species transport. However, it still needs to be explored and understood regarding the impact of microenvironment evolution on the CO 2 RR performance. We report here a hydrophobic oxide-derived copper foam with villous nanowires on the surface that demonstrates significant suppressed HER and enhanced C 2+ selectivity in H-type cell. In-situ 3D Raman mapping and in-situ Raman spectra investigation on micro-environmental species reveal that high local pH and fast CO 2 mass transfer were simultaneously allowed in the microenvironment of the triple-phase interface because of the special hydrophobic structure. On this mechanism, the material reaches a minimum H 2 Faradaic efficiency (FE) of 6.6% and maximum C 2+ FE of 74.4% at the current density of 300 mA cm -2 in a flow cell under acidic conditions (pH=4) without an additional gas-diffusion layer (GDL). This study not only highlighted the importance of the microenvironment but also provided an effective method for tuning the triple-phase interface of CO 2 RR and demonstrated a promising application of the pure metal foam-based GDEs. Physical sciences/Engineering/Chemical engineering Physical sciences/Chemistry/Catalysis/Electrocatalysis CO2RR Copper hydrophobicity triple-phase interface microenvironment Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction The renewable electricity-powered CO 2 electro-reduction (CO 2 RR) offers a promising route to simultaneously achieve renewable energy storage and effectively address the challenge of climate change. 1–4 In this context, the value-added multi-carbon (C 2+ ) products from CO 2 RR like ethylene, ethanol, and propanol, are particularly desired due to their substantial energy density and economic returns. 4–8 Accordingly, extensive efforts have been dedicated to developing potent electrocatalysts, such as Cu-based catalysts, for efficient conversion of CO 2 to C 2+ products. 9–11 Besides seeking for novel catalysts, it is also critical to understand the reaction microenvironment, 11, 12 which can influence reaction pathways through the affecting mass transfer and local concentration of reaction species. 11, 13 Significantly, the reaction microenvironment involves the local environment surrounding the reaction interface between the catalyst, 14 reactants, 15, 16 , and electrolyte 17 , which decides both the kinetics and thermodynamics during reactions. 11, 18, 19 For example, the electrolyte's local pH, species, and buffer capacity, etc., have significant effects on the local reaction conditions and the product distribution of the electrochemical reactions, and the hydrophilicity and hydrophobicity of electrode/catalysts can affect the mass transfer of interfacial water thereby modulating the process of the reactions. 17,20 As for the electrochemical CO 2 RR process, the structure and properties of the catalyst-electrolyte-gas triple-phase interface, which interacts with the reaction microenvironment, play a crucial role in the catalytic activity and selectivity. 21 As a typical work, Warkerley et al. introduced a hydrophobic Cu dendrite catalyst with a triple-phase interface, which can trap gas under hydrophobic hairs in water like a spider to modulate the reaction process. 22 In this catalyst-electrolyte-gas system, the CO 2 RR process only evolved near the triple-phase boundary with CO 2 diffusion, and the microenvironment like the local ion and gas transfer was significantly changed, which led to the suppressed hydrogen evolution reaction (HER) with a Faradaic efficiency (FE) below 10% and induced high C 2+ product selectivity. 22 Recently, the cells with gas-diffusion electrodes (GDE) were developed and upgraded to enhance the mass transfer of reactants, which can achieve high current density at an industrial scale because the limitation of CO 2 mass transfer was alleviated. 11, 23, 24 For example, Dinh et al. achieved enhanced operational stability of constant ethylene selectivity for an initial 150 operating hours though the Polytetrafluoroethylene (PTFE)-based gas diffusion layer, which sandwiches the reaction interface between separate hydrophobic and conductive carbon layer. 24 It was emphasized that the stability of the CO 2 RR in gas-type reactors was significantly affected by the durability of the triple-phase interface, which was successfully kept with the additional carbon materials on the electrode. 21, 24 These studies have demonstrated the substantial influence of the catalyst-electrolyte-gas triple-phase interface and its microenvironment in gas-involved electrochemical reactions. 11, 25 However, most of the reported electrode is either carbon-based or PTFE derived GDE, metal foam based GDE without GDL is rarely reported. And there is still need to be explored and understood regarding that the impact of catalyst microenvironment and reaction interfaces on the mass transport and kinetics of metal foam-based GDE, which was conducive to further design of the effective CO 2 RR system with an optimal microenvironment at the catalyst-electrolyte-gas interfaces. In this context, our work aimed at constructing an intuitive and conveniently researchable catalyst-electrolyte-gas triple-phase interface, deepening the understanding of the triple-phase interface microenvironment and guiding the design of the efficient CO 2 RR system. We prepared the oxide-derived copper with villous nanowire structure (OBC) 26 base on the porous copper foam framework, and then on its basis synthesized the corresponding hydrophobic materials (OBC-OT) with the treatment of 1-octadecanethiol. CO 2 RR performance in H-type cell showed that the HER of OBC-OT was effectively suppressed to 12.6%, and the C 2+ /C 1 selectivity of OBC-OT was improved to 3.3 compared to the 1.4 of OBC. The weak CO adsorption in TPD results showed that the surface active site variation caused by the 1-octadecanethiol adsorption was not the deep reason for elevated C 2+ selectivity. The in-situ 3D Raman mapping was used to visually observe the catalyst-electrolyte-gas triple-phase interface and demonstrated the significant increase of reactants and local current density at the triple-phase interface. The in-situ Raman spectra further verified the high local current density under different applied potentials and revealed the changes from C 1 products favored to C 2+ products along with the applied potential negative shifted or current density increase. Additionally, combining the measurements with simulations of micro-environmental species, it is found that high local pH and fast CO 2 mass transfer can be simultaneously allowed in the microenvironment of the triple-phase interface as a result of the special hydrophobic structure of OBC-OT, which led to the high C 2+ selectivity and suppressed HER. Leveraging this mechanism and the porous hydrophobic structure, the OBC-OT was further applied in the flow cell under acidic conditions (pH = 4) and displayed a low H 2 FE of 6.6% and high C 2+ FE of 74.4% at the current density of 300 mA cm − 2 without additional gas-diffusion layer (GDL). Results Catalyst Synthesis and Characterization. Catalyst-electrolyte-gas triple-phase interface and its microenvironment play a crucial role in the CO 2 RR performance. Therefore, we prepared the hydrophobic and porous OBC-OT based on Cu foam as the catalysts, which can intuitively observe the interface and conveniently research the microenvironment. Firstly, we synthesized a layer of Cu(OH) 2 nanowires on the surface of Cu foam with the alkaline solution according to the previous report 26–28 , and the blue Cu(OH) 2 layer was turned to CuO layer after the annealing process. After that, the OBC materials were then obtained as the CuO layer was electro-reduced to oxide-derived Cu with a villous nanowire structure 8, 26 . Based on OBC, the OBC-OT materials were prepared with the hydrophobic treatment of 1-octadecanethiol (Fig. 1 a and Figure S1 ). The scanning electron microscopy (SEM) images of the OBC-OT showed that the villous and twisted nanowires were grown on the surface of Cu foam and a large amount of dense and interlaced channels can be formed based on this structure (Fig. 1 b). The typical transmission electron microscopy (TEM) images in Fig. 1 c further demonstrated certain rough surfaces belong to the oxide-derived Cu. Additionally, the corresponding energy dispersive spectroscopy (EDS) mapping in Fig. 1 c also showed that the oxide-derived Cu was different from the pure metallic and there are still some O remained after the electro-reduction, which was in accord with the previous report. 26 The 1-octadecanethiol was verified to be successfully absorbed with the thickness of ~ 1.5 nm (Fig. 1 d) on the nanowires based on the EDS images of C and S element (Fig. 1 c) and the S 2p spectra in X-ray photoelectron spectroscopy (XPS) result (Figure S7). The BET results showed that there was no obvious pore blinding after the processing of 1-octadecanethiol as the surface area even increased (Figure S9). The CuO, OBC, and OBC-OT were also characterized by the Raman and infrared absorption (IR) spectra in Figure S8a-b. Although there was no obvious Raman peak of 1-octadecanethiol detected in OBC-OT because of the low content and Raman scattering area, the weak IR peak of 1-octadecanethiol was detected in OBC-OT. High-resolution transmission electron microscopy (HRTEM) indicated that the lattice space of oxide-derived Cu (1.90, 2.17, 2.21, and 3.55 Å) differs from the pure Cu, CuO, or Cu 2 O, which can be designed as the CuO x (Fig. 1 d and Figure S2). The X-ray diffraction (XRD) results of OBC with different electrochemical reduction time (Figure S4a-b) further confirmed that this phenomenon was not resulted from the incomplete reduction of CuO. The CuO x on OBC was formed in 10 min and can be stable with the potential of -1.0 V vs. RHE applied for 10 h. The in-situ Raman spectra (Figure S5) monitored the process of this conversion process from CuO to OBC at -1.0 V vs. RHE and the peak of 616 cm − 1 (Cu-O) was gradually weakened. When the 1-octadecanethiol directly adsorbed on CuO nanowires (CuO-OT), a thick layer (~ 15 nm) of 1-octadecanethiol was averse to the exposure of reaction sites, which confirmed the necessity of the electrochemical reduction process (Figure S6). The XPS was conducted to reveal the valence and chemical bonding information of the catalysts (Fig. 1 e and Figure S7). The Cu LMM spectra showed that the proportion of Cu(0) increased as the 1-octadecanethiol adsorbed on OBC, which was in accord with the previous report. 22 While, the proportion of Cu(Ⅰ) decreased concomitantly. Combining the S-Cu(Ⅰ) existed on OBC-OT in Figure S7a, 22, 29, 30 it can be speculated that the decrease in the signal strength of Cu (I) can be attributed to the coverage of long-chain 1-octadecanethiol on Cu(Ⅰ). 31, 32 The weakened peak intensity of OBC-OT compared to OBC in the O 1s spectra further verified the increased content of Cu(0) on the surface. The comparison of XPS data between OBC-OT and the OBC-OT-tested (after testing at -1.57 V vs. RHE for 1 h) demonstrated the considerable adsorption stability of the 1-octadecanethiol on OBC-OT as there was a small variation between them. The hydrophobic property of the OBC and OBC-OT was investigated via the contact angle result and photography water immersion test. After the hydrophobic treatment, the contact angle of OBC-OT was turned to 129° compared to the 17° of OBC (Fig. 1 f), and it remained 127° after testing at -1.57 V vs. RHE for 1 h (Figure S11), which illustrated the stability of the hydrophobic layer as well. As the OBC-OT was immersed in the water (Figure S3), the white surface liquid film appeared because of the high contact and refractive index difference between liquid and gas. Additionally, the plucked OBC-OT can keep dry from visual observation although it had been completely submerged in water. The electrochemical double-layer capacitance (C dl ) was calculated to evaluate the electrochemical active surface area (ECSA) in Fig. 1 g. The OBC-OT showed a C dl of 0.021 mF cm − 2 , which was well below the 4.60 mF cm − 2 of OBC, which indicated the great reduction of the catalyst-electrolyte contact area due to the hydrophobic property. Furthermore, the C dl of polished plate Cu was 0.067 mF cm − 2 according to a previous study 28 , higher than that of OBC-OT, which further verified the hollow space as the OBC-OT was immersed in the electrolyte. CO 2 RR Performances in H-type cell. The CO 2 RR properties of the OBC and OBC-OT catalysts were evaluated in the H-type cell setup with the CO 2 -saturated 0.1 M KHCO 3 (pH ∼ 6.8) solution as the electrolyte, the prepared catalysts as the working electrode, the Pt mesh as the counter electrode, and the saturated Ag/AgCl as the reference electrode. The FE of CO 2 -reduction products was calculated by nuclear magnetic resonance (NMR) spectroscopy (Figure S13-14) and gas chromatography (GC, Figure S15). The voltage drop from solution resistance was compensated. The solution resistance was measured by the electrochemical impedance spectroscopy (EIS) in Figure S12. The linear sweep voltammetry (LSV) was conducted in the CO 2 -saturated and N 2 -saturated 0.1 M KHCO 3 solution to estimate the CO 2 RR and competitive HER activity (Fig. 2 a) of OBC and OBC-OT. The general current density of OBC-OT was lower than that of OBC owing to the hydrophobic property of OBC-OT. The OBC in CO 2 -saturated electrolyte showed an approximate current density with that in N 2 -saturated electrolyte, indicating a high competitive HER on the OBC. However, the OBC-OT showed higher current density in the presence of CO 2 than that of N 2 , which reflected its preferable CO 2 RR activity. The CO 2 RR selectivity results (Fig. 2 b-c and Figure S16a-c) also showed that the HER was effectively suppressed on OBC-OT. The OBC exhibited a high FE H2 of about 40%, while the FE H2 of OBC-OT can reach a small value of 12.6% at the testing potential (Figure S16a). Besides, the OBC-OT showed a higher C 2 H 4 FE (~ 36.5%) and C 2+ FE (~ 67.9%) than the OBC that exhibited the C 2 H 4 FE and C 2+ FE of ~ 17.0% and 33.8%, respectively (Figure S16b-c). The C 2+ , C 1 , and H 2 selectivity of OBC and OBC-OT were arranged in Fig. 2 d and it intuitively indicated the improvement of CO 2 RR performance via the hydrophobic processing of OBC. Additionally, to ensure that the improved C 2+ FE was not simply resulted from the decreased HER, the FE ratio of C 2+ /C 1 of OBC and OBC-OT was presented in Fig. 2 d. The C 2+ /C 1 selectivity of OBC-OT was significantly elevated to 3.3 compared to the 1.4 of OBC, which meant that the C 2+ selectivity was indeed improved even disregarding the HER factor. However, it should be noted that the CO FE was significantly increased (reached ~ 21.3%) with the hydrophobic processing when the applied potential was not too negative (-1.2 V to -1.4 V). While, as the applied potential became more negative, the CO FE rapidly declined to ~ 4.5%. Similarly, the C 1 product of HCOOH showed the same variation trend as the applied potential changed. Therefore, combining the analysis of the opposite trend of C 2 H 4 or C 2 H 5 OH in Fig. 2 c, it can be concluded that the C 2+ selectivity of OBC-OT under the low applied potential was not ideal enough (similar to the OBC) and the C 2+ selectivity can be elevated with more negative potential and higher current density applied. The long-term CO 2 RR stability of OBC and OBC-OT regarding the C 2 H 4 FE and C 2+ FE retention over a 6-hour operation period in H-type cell were investigated (Figure S17). After the 6 h operation period, the C 2 H 4 FE and C 2+ FE of OBC-OT were stable and can be held at 34.2% and 61.2%, respectively. Furthermore, the SEM and EDS of OBC-OT with 10 h of CO 2 RR test (Figure S10) also demonstrated that the absorbed hydrophobic layer was durable, which was consistent with the high CO 2 RR stability of OBC-OT. In addition, the influence of the 1-octadecanethiol adsorption quantity on OBC was investigated. We prepared the OBC-sOT which contained a slight content of 1-octadecanethiol molecules on the surface (Figure S18). Unlike the OBC-OT that possessed strong HER suppression capacity, OBC-sOT exhibited a higher H 2 evolution. However, the HER was still lower than the untreated OBC, which indicated the certain effect of 1-octadecanethiol. The LSV curves of OBC-sOT in CO 2 -saturated and N 2 -saturated 0.1 M KHCO 3 solution indicated the not strong enough HER suppression as well (Figure S18c). Besides, the CO FE on OBC-sOT was higher than that on OBC-OT, which demonstrated the preferable C 1 selectivity when the adsorption quantity of 1-octadecanethiol was not enough. The ECSA results of OBC-sOT showed that certain hydrophobic property was achieved and the C dl was also significantly reduced with slight 1-octadecanethiol absorbed (Figure S18b). The partial current density of C 2+ products on OBC and OBC-OT was normalized 33 (Figure S16d) with the value of 0.067 mF cm − 2 was used as the C dl of polished Cu from the previous report 8 . The C dl of OBC-OT was small and the electrocatalytic reaction was conducted on a small solid-liquid contact area. It emphasized the high local current density at the solid-liquid-gas interface, which may lead the microenvironment variation with such mass transfer occurred at the interface. Surface properties and catalyst-electrolyte-gas triple-phase interfaces. To gain insight into the mechanism of CO 2 RR performance improvement, we studied the surface properties and the difference between OBC and OBC-OT. The kelvin probe force microscope (KPFM) was applied to further explore the origin of CO2RR performance difference with the analysis of surface potential. Figure 3 a-b displayed the KPFM images and the corresponding height and potential difference of OBC and OBC-OT. The OBC-OT showed a higher potential difference of − 34.2 mV ( vs. silicon substrate) compared with − 6.2 mV ( vs. silicon substrate) of OBC, which implied the lower local work function of OBC-OT. The lower local work function indicated the faster charge separation and transfer, thereby contributing to spontaneous polarization and enhanced energetics for CO 2 RR, 34, 35 which was consistent with the weak HER and strong CO 2 RR of OBC-OT. As displayed in Fig. 3 c, the temperature-programmed desorption (TPD) of CO and H 2 was carried out to evaluate the CO and H 2 desorption on catalysts 36, 37 . The similar H 2 -TPD curves of OBC and OBC-OT implied the similar H 2 adsorption on the catalysts. However, comparing to the OBC, the OBC-OT presented a CO desorption peak with obviously lower temperature in the CO-TPD spectra, indicating that the CO was not easy to adsorbed on the OBC-OT surface 36 . The weak adsorption of CO on OBC-OT was not beneficial to the CO coupling and high C 2+ selectivity 38–40 , which was inconsistent with the elevated C 2+ selectivity of OBC-OT. The surface-active site variation caused by the 1-octadecanethiol adsorption was not the root cause of elevated C 2+ selectivity. However, it was noteworthy that the TPD was not tested under operating conditions for CO 2 RR as no additional potential was applied in the TPD measurement. Besides, the TPD result of OBC-OT was in accord with the high C 1 selectivity at less negative potential owing to the similar microenvironment when no potential or low potential was applied. The microenvironment could be changed with the different potential applied to the catalysts, which also affect the product's selectivity. The catalyst-electrolyte-gas triple-phase interface of the OBC-OT, where the CO 2 RR mainly occurred, was primarily investigated via the in-situ 3D Raman mapping technique. Firstly, the 3D Raman mapping (based on the peak intensity of surface CuO x in 615 cm − 1 ) 41 of OBC-OT at air atmosphere (Fig. 3 d and Figure S20a) showed the clear structure of the foam framework, indicating the feasibility of the measurement method for the materials. In addition, the corresponding 2D Raman mapping represented high consistency with the white light imaging as for the OBC-OT (Fig. 3 g). Figure 3 e demonstrated the in-situ 3D Raman mappings (based on the peak intensity of CuO x in 615 cm − 1 and HCO 3 − in 1070 cm − 1 ) 41 of OBC-OT at -0.2 V vs. RHE. Combining with the analysis of the corresponding white light imaging and the sliced mapping along depth (Figure S20b), it can be easily concluded that the gas chamber and solid-liquid-gas triple-phase reaction interface caused by hydrophobicity were presented in the immersed OBC-OT. Additionally, the white liquid film formed on the surface of immersed OBC-OT owing to the high contact angle and the refractivity difference of the electrolyte and gas (Fig. 3 h). Below the white liquid film, the obvious CuO x peak was presented and there was no HCO 3 − peak being detected even though the frame of OBC-OT can be seen in the white light imaging, which further verified the existence of gas chamber and the catalyst-electrolyte-gas triple-phase interface. Different from the OBC-OT, the peak of CuO x vanished and only the HCO 3 − peak was shown in the in-situ 3D Raman mapping because of the O atoms detachment from OBC under the negative potential (Fig. 3 f and Figure S20c). The corresponding outer surface white light imaging and 2D Raman mapping showed that there was no gas chamber in the immersed OBC (Fig. 3 i). On the other hand, noteworthy that the peak intensity of HCO 3 − on the outer side was higher than that on the inner side of the foam, which can be attributed to the higher solution IR drop on the inner side. Comparing the peak intensity of HCO 3 − absorbed on the surface of catalysts (Fig. 3 h-i), it can be revealed that the peak intensity of HCO 3 − on OBC-OT was nearly ten times that on OBC, which meant that the large amount of HCO 3 − was gathered around the triple-phase interface of OBC-OT. The high local current density resulted in high local mass transfer, including the transfer of HCO 3 − and the CO 2 RR reactants. Based on the data above, it can be speculated that the reaction microenvironment changed by the accumulation of local reactants and intermediates at the solid-liquid gas triple-phase interface with high negative potentials applied, led to the variation in the catalytic reaction pathway and the significant increase in C 2+ selectivity. In-situ Raman spectroscopy characterization. To elucidate the origin of the promoted C 2+ selectivity on OBC-OT, we conducted an extensive set of investigations via the in-situ Raman spectra and mapping. The intermediates and adsorbates on the OBC-OT with an elevated potential applied were displayed in the in-situ Raman spectra for the triple-phase interface of the OBC-OT catalysts (Fig. 4 a-b). When the weak negative potential was applied, the strong peak of HCO 3 − (1070 cm − 1 ) appeared and the peak of CuO x (1581 cm − 1 ) was weakened due to the HCO 3 − adsorption and O detachment in the lattice under the negative potential 41 . Additionally, the COOH* peak of 1581 cm − 1 was detected as the applied potential was not too negative, which was consistent with the result of CO-TPD and the preferable C 1 selectivity of OBC-OT at weak negative potential. 42 Furthermore, the *CO peak of 2000–2100 cm − 1 was also studied with the applied potential shifted negatively. The *CO peak is an important index to judge the C 2+ selectivity of catalysts, as the CO 2 RR to multi-carbon products undergo a critical CO dimerization step. 43 However, there was no obvious *CO peak until the applied potential was negatively shifted to -1.1 V vs. RHE, which was in accord with the C 2+ FE variation trend with the potential change. Besides the *CO peak, the peaks around 1296 cm − 1 and 704 cm − 1 , which can be assigned to the adsorbed C-O bonds of CO 2 and the in-plane δCO 2 − , 41, 44 respectively, were also obviously raised with the potential applied from − 1.1 V vs. RHE to -1.8 V vs. RHE, indicating the improved activation of CO 2 . In addition, owing to the high local current density and reaction, the peaks of C-C stretching (1103 cm − 1 ), symmetrical CH 3 deformation (1132 cm − 1 ), C-H vibration of hydrogenated intermediates after C-C coupling (1332 cm − 1 ), and COO stretching vibration of CH 3 COOH (1437 cm − 1 ) from the CO 2 RR intermediates and reactants were clearly presented, demonstrated the hydrocarbons were generated during the CO 2 RR process. 42, 45, 46 It was noteworthy that the HCO 3 − peak declined with the peak of C-C stretching and symmetrical CH 3 deformation raised, which implied the competition between HCO 3 − and multi-carbons on the surface of catalysts. The HCO 3 − was gradually replaced by the multi-carbon intermediates, reflecting the strong C 2+ production accordingly. The bands related to symmetric -CH 2 (ν s CH 2 ) and -CH 3 (ν s CH 3 ) stretching gradually appeared around 2854 and 2930 cm − 1 in Fig. 4 b, which further indicated the hydrocarbons generation and consistency with the elevated C 2+ selectivity in highly negative potential. 47 However, Fig. 4 c showed the weak peaks of intermediates and adsorbates on the OBC and the *CO peak nearly vanished as the applied potential was negative than − 0.9 V vs. RHE, which was agreed to its low C 2+ selectivity. The weak *CO and HCO 3 − signal can be detected with weak negative potential applied, but they disappeared because of the active site occupation from strong HER. The in-situ 2D Raman mapping of OBC-OT and OBC (Fig. 4 d-e) further verified that the reaction intermediates accumulated at the solid-liquid-gas triple-phase interface, and the Raman signal on OBC-OT was stronger than that on OBC. Under the weak negative potential, the intermediate of OBC-OT was mainly the *COOH with strong peak, while intermediates of OBC mainly consisted of CH 3 COOH, *COOH and *CO with weak peaks. The intermediates are disorderly distributed on the immersed OBC through the 2D Raman mapping (based on the peak intensity of CH 3 COOH, *COOH and *CO) in Fig. 4 e. However, the 2D Raman mapping (based on the peak intensity of *COOH) in Fig. 4 d showed the relatively clear shape of the immersed OBC-OT as the *COOH can not be detected in the area below the liquid film. Combining the analysis of the in-situ Raman measurement and ECSA normalized partial current density of C 2+ products, it can be confirmed that the high local current density and high mass transfer prevail at the triple-phase interface on OBC-OT. The in-situ Raman further verified that the changes from C 1 products favored to C 2+ products favored with the applied potential negative shift, which was in accord with the CO 2 RR performance in H-type cell. From another perspective, it meant that properly increasing the applied current density can further improve the C 2+ selectivity for OBC-OT. Microenvironment evolution. According to the previous report, 4 the local pH, which impacted the C 2+ selectivity on catalysts, was significantly affected by the current density. Therefore, it can be reasonably hypothesized that the improved C-C coupling and generation of C 2+ products at the triple-phase interface originated from the large consumption of local protons and local pH increase. To further verify this supposition, we simulated local pH changes along the catalyst surface (plate electrode) at various applied current densities (Fig. 5 a). The local pH was gradually elevated and reached pH13 with the applied current density was improved to 10 mA cm − 2 . Besides the local pH, the local reactant CO 2 concentration was also an important factor in the HER suppression and C 2+ FE. The modeled local CO 2 concentration profiles in Fig. 5 b showed that the local CO 2 concentration was nearly zero at the current density of 15 mA cm − 2 . Due to the limitation of CO 2 mass transfer in typical H-type cells, the excessive current density was not beneficial for CO 2 RR performance, although the high local pH was produced. However, according to the previous report 22, 48 , this kind of hydrophobic microscale and nanoscale surface can trap gas under hydrophobic hairs in water like a spider, which means that the CO 2 mass transfer of OBC-OT can be effectively improved based on its special hydrophobic structure. In addition, the injected CO 2 can be stored in the internal pore of the foam structure and diffuse to the triple-phase interface for the CO 2 RR reaction. During the CO 2 RR test, the CO 2 will be constantly supplied from both the electrolyte and gas chamber of OBC-OT, which is different from the individual CO 2 supply from electrolytes like OBC. Therefore, the special hydrophobic structure of OBC-OT can allow high local CO 2 concentration and high current density for high local pH. On the other side, it should be emphasized that the practical local current density was influenced by the structure of catalysts, which differed from the current density modeled by the plate electrode or valued from the area of the macroscopic catalyst. Based on the above ECSA and in-situ Raman result, the obviously higher practical local current density was conducted on OBC-OT than that on OBC. Accordingly, the local pH was directly measured by surface-enhanced Raman spectroscopy (SERS) with pH-sensitive molecules (4-MBA) and further verified the local pH difference with the same applied current density of 5 mA cm − 2 (Fig. 5 c). The pH at 10 µm of distance to the catalyst surface for OBC-OT reached pH ~ 11, higher than the pH ~ 10 for OBC, which indicated the higher local pH induced by the higher practical local current density. As shown in Fig. 5 d, during the process of CO 2 RR on OBC-OT, the reaction only occurred in the area that contacted the electrolyte (catalyst-electrolyte-gas triple-phase interface), and the inside pores of foam were filled with CO 2 . The reaction microenvironment of CO 2 RR evolved to the favored C 2+ products and suppressed HER (Fig. 5 e). The high local pH was generated with high practical local current density, and simultaneously the CO 2 mass transfer can be efficiently improved by CO 2 supply from both the electrolyte and gas chamber because of its special hydrophobic structure. Application in flow cells. According to previous reports 49–53 , the massive CO 2 assumption caused by the carbonate formation, and the liquid product crossover owing to the anion exchange membrane, reflects a major obstacle of the traditional alkaline or neutral pH electrolytes system for the economical CO 2 RR catalysis. The acid electrolyte and accordingly used Nafion membrane can effectively address the challenges, however, are not beneficial for the multi-carbon production and HER suppression. 4, 54, 55 Therefore, we artfully applied the OBC-OT in flow cells with the acid electrolyte for high C 2+ selectivity and strong HER suppression, as high local pH can be achieved at the thee-phase interface of OBC-OT based on our investigation above (Figure S23a). Based on the villous hydrophobic structure of porous foam, the OBC-OT was directly applied in the flow cells as the cathode without an additional gas-diffusion layer (GDL) as the brief flow-cell configuration showed in Fig. 6 a. The acid electrolyte of 0.5 M K 2 SO 4 (pH = 4) was employed according to the previous report. 4 The gas diffusion scheme of the CO 2 RR process on OBC-OT with the local pH variation was demonstrated in Fig. 6 b. The CO 2 diffused through the porous foam frame and then further diffused across the villous nanowires on OBC-OT, participated in the reaction and led to local pH variation at the triple-phase interface. The OBC-OT exhibited a high C 2+ FE of 74.4% and low H 2 FE of 6.6% with the current density of 300 mA cm − 2 (Fig. 6 d and Figure S22), which further verified the proposed mechanism that the local pH can be elevated for improved C 2+ selectivity and suppress HER even in the acid electrolyte. For comparison, the Cu foam adsorbed with 1-octadecanethiol (Cu-OT) was also investigated in the flow cell (Figure S23b-c). The strong and obvious cathode flooding suggested the necessity of the villous hydrophobic structure on OBC-OT. In addition, the H 2 FE and C 2+ FE on OBC-OT with the current density of 300 mA cm − 2 applied were relatively stable and can be held at 13.5% and 59.5% after the 10 h operation, respectively, which further demonstrated the application prospect of OBC-OT. Discussion In summary, a hydrophobic oxide-derived copper foam with villous nanowires on the surface has been constructed, representing significant improvement on HER suppression and C 2+ selectivity for the CO 2 RR performance in H-type cell. The in-situ 3D Raman mapping was adopted to probe the catalyst-electrolyte-gas triple-phase interface and indicated the significant increase of reactants and local current density at the triple-phase interface. Besides, the in-situ Raman spectra further verified the variations from C 1 preferred to C 2+ preferred with the applied potential negative shifted or current density increased, which was consistent with the CO 2 RR performance and TPD results. Combining the measurements and simulations of micro-environmental species, high local pH and CO 2 mass transfer can be simultaneously allowed in the microenvironment of the triple-phase interface based on the special hydrophobic structure, being the internal mechanism of the high C 2+ selectivity and HER suppression. Therefore, on this mechanism, both the low HER of 6.6% and high C 2+ selectivity of 74.4% were achieved in the flow cell under acidic conditions at the current density of 300 mA cm − 2 without an additional gas-diffusion layer (GDL). This work provides valuable theoretical insights for the design of catalysts and catalytic devices and opens up promising opportunities for the application of metal foam-based GDEs without fragility. Methods Chemicals Copper foam (0.3 mm, > 99.99%), copper foil (0.3 mm, > 99.99%), sodium hydroxide (NaOH, Aladdin, ≥ 99%), ammonium persulfate ((NH 4 ) 2 S 2 O 8 , Aladdin, ≥ 99%), 1-octadecanethiol (C 18 H 38 S, Macklin, ≥ 99%), potassium bicarbonate (KHCO 3 , Macklin, ≥ 99.5%), ethanol (C 2 H 5 OH, Sinoreagent, AR), carbon dioxide (CO 2 , 99.99%), argon (Ar, 99.999%), nitrogen (N 2 , 99.999%), 4-mercaptobenzoic acid (4-MBA, Aladdin, ≥ 99%), silver nitrate (AgNO 3 , Aladdin, ≥ 99.9%). chloroauric acid (HAuCl 4 , Aladdin, ≥ 99.9%), sodium citrate (Aladdin, ≥ 99.9%), ascorbic acid (Aladdin, ≥ 99.9%). Catalyst Preparation Synthesis of OBC materials The CuO nanowires were synthesized by annealing method from Cu(OH) 2 nanowires according to a previously reported procedure. 56 In a typical synthesis, the Cu foam (1 mm×0.5 mm) was cleaned by hydrochloric acid solution (1 M), acetone, ethanol and distilled water in sequence, then the cleaned Cu foam was immediately soaked into the mixture solution with 4.8g NaOH, 2.28g (NH 4 ) 2 S 2 O 8 and distilled water (100 mL) at 3℃ for 30 min. After that, the Cu foam turned to blue and a layer of Cu(OH) 2 nanowires was obtained on the surface after it was thoroughly rinsed with distilled water and dried in 60℃. The black CuO MPNWs were prepared after the Cu foam with a layer of Cu(OH) 2 nanowires was annealed in air at a preset temperature of 180°C for 1 h. The CuO MPNWs were used as the pre-catalysts and they were reduced to dark-red OBC materials in the 0.1M KHCO 3 aqueous solution with the potential of -1.0 V (vs. RHE) for 10 min before the CO 2 reduction test. Synthesis of OBC-OT/OBC-sOT materials The OBC-OT materials were synthesized by the functionalization of OBC materials with 1-octadecanethiol. The OBC materials were soaked in the Ar-saturated ethyl acetate solution with 10 wt% (0.01wt%) 1-octadecanethiol at room temperature for 30 min (2 min). The processed OBC materials were removed to ethyl acetate to clean the residual 1-octadecanethiol molecules which were not strongly absorbed on the OBC materials, and dried with nitrogen to obtain the OBC-OT (OBC-sOT) materials. Materials Characterization SEM and EDS measurements were performed on a scanning electron microscope (G500). The HRTEM data were obtained on a Field Emission Transmission Electron Microscope (Tecnai F30). The Raman spectroscopy was tested by a Laser confocal Raman Spectrometer (Renishaw). The X-ray photoelectron spectroscopy (XPS) was measured by the instrument ESCALAB and the X-ray diffraction (XRD) measurement was conducted by an X-ray diffractometer (SmartLab). A Kelvin probe force microscopy (KPFM, Bruker) was used to study the morphology and surface potential properties variation of the catalyst. The quantification of solution-phase and gas-phase products was carried out by nuclear magnetic resonance (NMR) spectroscopy (Figure S14) and gas chromatography (GC) (Figure S15), respectively. In-situ Raman spectra tests The in-situ Raman spectra were measured via a homemade electrolytic cell with CO 2 -saturated 0.1 M KHCO3 aqueous solution flowing inside. This electrolytic cell was connected to the electrochemical station with a triple-electrode system, and the prepared electrode with catalysts, Ag/AgCl electrode, and Pt wire were used as work electrode, reference electrode, and counter electrode, respectively. The reduction process of the CuO MPNWs to OBC materials was monitored at the excitation laser source of 532 nm. The reaction intermediates of the CO 2 RR process were monitored at the excitation laser source of 785 nm. 57 The measured potentials were converted to V versus RHE (E RHE = E Ag/AgCl + 0.197 V + 0.0591 V × pH) without the iR s compensation. Electrochemical measurements Electrochemical properties and CO 2 RR performance in H-type electrochemical cell were measured with three electrode system. The prepared electrode, Ag/AgCl electrode, and platinum nets electrode were used as the working, reference, and counter electrodes, respectively. The CO 2 -saturated 0.1 M KHCO 3 aqueous solution (pH∼6.8) was used as the electrolyte and the cathode and anode chamber of the H-type electrochemical cell were separated by an anion exchange membrane (FAA-3-50). The measured potentials were converted to V versus RHE (E RHE = E Ag/AgCl + 0.197 V + 0.0591 V × pH ‒ iR s ). 58 The R s was the resistance of the electrolyte solution between the working and reference electrode, which was measured by the impedance method. Flow cell application test The application of materials in the flow cell (Figure S23) was conducted with the acid electrolyte of 0.5 M K 2 SO 4 (pH = 4) solution. Three pieces of OBC-OT were stacked to avoid the cathode flooding and used as the working electrode without any other gas diffusion attachment because of its hydrophobic and porous properties. The Ag/AgCl electrode and platinum nets electrode were used as the reference and counter electrodes, respectively. The cathode and anode chambers were separated with the Nafion membrane (N211) in between. The liquid flow rate in the cathode and anode chamber was 3 mL min − 1 and 40 mL min − 1 , respectively. The CO 2 flow rate was set as 30 mL min − 1 . ECSA measurements The Electrochemical Active Surface area (ECSA) was evaluated by the double-layer capacitance (C dl ). The CV curves were taken over a range of scan rates (20, 40, 60, 80, and 100 mV/s), and the potential range was 0.15 V to 0.25 V vs. RHE. GC analysis The gas products were quantified by a gas chromatography (GC9790plus, FULI INSTRUMENTS) connecting to the cathode chamber of the electrochemical cell, which can automatically sample at the set time. The gas chromatography used Argon as the carrier gas, and it was calibrated by the standard curves obtained from a series of concentrations of the standard gas mixture. The CO 2 was sparged into the cathode chamber by a mass flow controller (Sevenstar) and the electrolyte was stirred (600 rpm). With the online measurement system, the gas products were typically sampled at 15, 35 and 55 min. 1 H NMR spectroscopy The liquid components were analyzed by 1 H NMR spectroscopy undertaken with a Bruker Avance III 400 MHz spectrometer. During the NMR test, the mixture solution containing 500 µL electrolyte after the CO 2 RR test, 100 µL D 2 O, and 100 µL DMSO aqueous solution (10 ppm, volume/volume) was added to the NMR tube for quantification. A Pre-SAT180 water suppression method was used to diminish the effect of the excessively strong water peak of each spectrum. The standard curve of each liquid product was fitted to quantify the concentration of liquid production before the CO 2 RR tests. Faradaic Efficiency calculation : The Faradaic Efficiency of different gas components was calculated by the following method: FE j = (nFV g νp 0 )/(RT 0 I total ), where n is the electron transfer number from the CO 2 to its reduced gas product; F means the Faraday Constant (96485 C/mol); V g is the flow rate of CO 2 ; ν is the gas component concentration quantified by the gas chromatography; R is the universal gas constant (8.314 J/mol·K); the p 0 and T 0 mean the pressure and temperature during the electrochemical catalytic reduction process; I total is the averaged current over the whole test period. The Faradaic Efficiency of different liquid products was calculated by the following method: FE j =nFVC/Q, where n means electron transfer number from the CO 2 to its reduced liquid product; F is the Faraday constant (96485 C/mol); V means the volume of the electrolyte for cathode; C is the liquid component concentration calculated from the standard curve; Q means the total passed charge (C) during the whole electrochemical catalytic test period. In-situ local pH measurement The in-situ local pH was tested via Raman signal of the pH-sensitive molecules (4-MBA) on the prepared SERS substrates (Figure S21a). The electrode was separated with the SERS substrate through a very thin insulating layer. As the potential was applied to the electrode, the local pH was varied and the peaks of 1372 cm − 1 (νCOO − ) and 1633 cm − 1 (νC = O) were sensed (Figure S21b). Before the pH detection, we made the standard curve based on the peak area ratio of 1372 cm − 1 and 1633 cm − 1 (Figure S21c). The laser was 532 nm and the line image mode was used for local pH detection. The pH-sensitive SERS substrates were prepared according to previous reports. 59, 60 The 1.28 mL sodium citrate solution (1 wt%) was rapidly added to the boiling mixture of 31.6 mL distilled water and 390.4 µL HAuCl 4 (1 wt%), and then the Au seeds were obtained after the 30 min heating reflux. The Au@Ag soliquid was synthesized via the dropwise addition of the 2.5 mL AgNO 3 solution to the mixture of 32 mL distilled water, 2 mL sodium citrate (1 wt%), 630 µL ascorbic acid (0.1 M), and 930 µL Au seeds solution for 30 min. A piece of gold-plated silicon wafer was immerged in the 4-MBA solution (ethanol, 10 mM) for 24 h and then washed with massive ethanol to get the 4-MBA adsorbed gold-plated silicon wafer. Then the Au@Ag soliquid (concentrated 20 times) was dropped on the 4-MBA adsorbed gold-plated silicon wafer and dried for 12 h naturally. The obtained sample was immerged in the 4-MBA solution (ethanol, 10 mM) for 24 h, and then cleaned the dissociative 4-MBA with ethanol to gain the pH-sensitive SERS substrate. COMSOL simulation The local pH and CO 2 concentration profiles were simulated with COMSOL (COMSOL Multiphysics v5.6, Stockholm, Se) based on previous publications 4, 24 . Two-dimensional (2D) domain (20 µm*100 µm) including the electrode surface in the left boundary (x = 0 µm) and the bulk solution in the right boundary (100 µm) was used for simulation. The zero flux of aqueous species was set in the top and bottom boundaries. The model considered the acid-base equilibria (equations 1–5) of CO 2 hydrolysis reactions: where j meant the current density applied; F was the Faraday’s constant; \({F}_{{CO}_{2}RR}\) and \({F}_{HER}\) meant the Faradaic efficiencies of the CO 2 RR and HER, respectively, which were set as 70% and 30%, respectively; \({n}_{{CO}_{2}RR}\) and \({n}_{HER}\) was the number of electrons required for the reduction reaction. The “eps” was added to the code to avoid zero or negative concentration. The model parameters are listed in Table S1 . Declarations Data Availability Statement The data that support the findings of this study are available from the corresponding author upon reasonable request. Acknowledgments This work was financially supported by the National Natural Science Foundation of China (22172196, 21902188), the Guangxi Science and Technology Program (AD21220067), Natural Science Foundation of Guangxi Province (2022GXNSFAA035467). Author contributions Y. T. and K.W. supervised this this project. Z. X., J. Y and H. Yperformed most of the experiments and analyzed the experimental data. Q. W. and J. C helped with the physical characterization and data analysis. S. S., C. M., and K.W. helped with visualization. Z. X., J. Y and K.W. wrote and revised the manuscript. All authors discussed the results and assisted during manuscript preparation. Competing Interest The authors declare no competing financial interest. References Obama, B., The irreversible momentum of clean energy. Science 2017, 355 (6321), 126-129. Birdja, Y. Y.; Pérez-Gallent, E.; Figueiredo, M. C.; Göttle, A. J.; Calle-Vallejo, F.; Koper, M. T. M., Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels. Nature Energy 2019, 4 (9), 732-745. Wang, G.; Chen, J.; Ding, Y.; Cai, P.; Yi, L.; Li, Y.; Tu, C.; Hou, Y.; Wen, Z.; Dai, L., Electrocatalysis for CO 2 conversion: from fundamentals to value-added products. Chemical Society Reviews 2021, 50 (8), 4993-5061. Xie, Y.; Ou, P.; Wang, X.; Xu, Z.; Li, Y. C.; Wang, Z.; Huang, J. E.; Wicks, J.; McCallum, C.; Wang, N.; Wang, Y.; Chen, T.; Lo, B. T. W.; Sinton, D.; Yu, J. C.; Wang, Y.; Sargent, E. H., High carbon utilization in CO 2 reduction to multi-carbon products in acidic media. Nature Catalysis 2022, 5 (6), 564-570. Li, F.; Li, Y. C.; Wang, Z.; Li, J.; Nam, D.-H.; Lum, Y.; Luo, M.; Wang, X.; Ozden, A.; Hung, S.-F.; Chen, B.; Wang, Y.; Wicks, J.; Xu, Y.; Li, Y.; Gabardo, C. M.; Dinh, C.-T.; Wang, Y.; Zhuang, T.-T.; Sinton, D.; Sargent, E. H., Cooperative CO 2 -to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces. Nature Catalysis 2020, 3 (1), 75-82. Pang, Y.; Li, J.; Wang, Z.; Tan, C.-S.; Hsieh, P.-L.; Zhuang, T.-T.; Liang, Z.-Q.; Zou, C.; Wang, X.; De Luna, P.; Edwards, J. P.; Xu, Y.; Li, F.; Dinh, C.-T.; Zhong, M.; Lou, Y.; Wu, D.; Chen, L.-J.; Sargent, E. H.; Sinton, D., Efficient electrocatalytic conversion of carbon monoxide to propanol using fragmented copper. Nature Catalysis 2019, 2 (3), 251-258. Wang, X.; Wang, Z.; Zhuang, T.-T.; Dinh, C.-T.; Li, J.; Nam, D.-H.; Li, F.; Huang, C.-W.; Tan, C.-S.; Chen, Z.; Chi, M.; Gabardo, C. M.; Seifitokaldani, A.; Todorović, P.; Proppe, A.; Pang, Y.; Kirmani, A. R.; Wang, Y.; Ip, A. H.; Richter, L. J.; Scheffel, B.; Xu, A.; Lo, S.-C.; Kelley, S. O.; Sinton, D.; Sargent, E. H., Efficient upgrading of CO to C 3 fuel using asymmetric C-C coupling active sites. Nature Communications 2019, 10 (1), 5186. Wu, Z. Z.; Zhang, X. L.; Niu, Z. Z.; Gao, F. Y.; Yang, P. P.; Chi, L. P.; Shi, L.; Wei, W. S.; Liu, R.; Chen, Z.; Hu, S.; Zheng, X.; Gao, M. R., Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO 2 Electroreduction. Journal of the American Chemical Society 2022, 144 (1), 259-269. Garza, A. J.; Bell, A. T.; Head-Gordon, M., Mechanism of CO 2 Reduction at Copper Surfaces: Pathways to C 2 Products. ACS Catalysis 2018, 8 (2), 1490-1499. Kim, C.; Cho, K. M.; Park, K.; Kim, J. Y.; Yun, G. T.; Toma, F. M.; Gereige, I.; Jung, H. T., Cu/Cu 2 O interconnected porous aerogel catalyst for highly productive electrosynthesis of ethanol from CO 2 . Advanced Functional Materials 2021, 31 (32), 2102142. Xing, Z.; Hu, L.; Ripatti, D. S.; Hu, X.; Feng, X., Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment. Nature Communications 2021, 12 (1), 136. Garg, S.; Li, M.; Weber, A. Z.; Ge, L.; Li, L.; Rudolph, V.; Wang, G.; Rufford, T. E., Advances and challenges in electrochemical CO 2 reduction processes: an engineering and design perspective looking beyond new catalyst materials. Journal of Materials Chemistry A 2020, 8 (4), 1511-1544. Tan, Y. C.; Lee, K. B.; Song, H.; Oh, J., Modulating Local CO 2 Concentration as a General Strategy for Enhancing C−C Coupling in CO 2 Electroreduction. Joule 2020, 4 (5), 1104-1120. Higgins, D.; Hahn, C.; Xiang, C.; Jaramillo, T. F.; Weber, A. Z., Gas-Diffusion Electrodes for Carbon Dioxide Reduction: A New Paradigm. ACS Energy Letters 2019, 4 (1), 317-324. Nam, D.-H.; De Luna, P.; Rosas-Hernández, A.; Thevenon, A.; Li, F.; Agapie, T.; Peters, J. C.; Shekhah, O.; Eddaoudi, M.; Sargent, E. H., Molecular enhancement of heterogeneous CO 2 reduction. Nature Materials 2020, 19 (3), 266-276. Li, R.; Xiang, K.; Peng, Z.; Zou, Y.; Wang, S., Recent Advances on Electrolysis for Simultaneous Generation of Valuable Chemicals at both Anode and Cathode. Advanced Energy Materials 2021, 11 (46), 2102292. König, M.; Vaes, J.; Klemm, E.; Pant, D., Solvents and Supporting Electrolytes in the Electrocatalytic Reduction of CO 2 . iScience 2019, 19 , 135-160. Tao, Z.; Rooney, C. L.; Liang, Y.; Wang, H., Accessing Organonitrogen Compounds via C–N Coupling in Electrocatalytic CO 2 Reduction. Journal of the American Chemical Society 2021, 143 (47), 19630-19642. Xing, Z.; Hu, X.; Feng, X., Tuning the Microenvironment in Gas-Diffusion Electrodes Enables High-Rate CO 2 Electrolysis to Formate. ACS Energy Letters 2021, 6 (5), 1694-1702. Zhang, F.; Co, A. C., Direct Evidence of Local pH Change and the Role of Alkali Cation during CO2 Electroreduction in Aqueous Media. Angewandte Chemie International Edition 2020, 59 (4), 1674-1681. Sa, Y. J.; Lee, C. W.; Lee, S. Y.; Na, J.; Lee, U.; Hwang, Y. J., Catalyst–electrolyte interface chemistry for electrochemical CO 2 reduction. Chemical Society Reviews 2020, 49 (18), 6632-6665. Wakerley, D.; Lamaison, S.; Ozanam, F.; Menguy, N.; Mercier, D.; Marcus, P.; Fontecave, M.; Mougel, V., Bio-inspired hydrophobicity promotes CO 2 reduction on a Cu surface. Nature Materials 2019, 18 (11), 1222-1227. García de Arquer, F. P.; Dinh, C.-T.; Ozden, A.; Wicks, J.; McCallum, C.; Kirmani, A. R.; Nam, D.-H.; Gabardo, C.; Seifitokaldani, A.; Wang, X.; Li, Y. C.; Li, F.; Edwards, J.; Richter, L. J.; Thorpe, S. J.; Sinton, D.; Sargent, E. H., CO 2 electrolysis to multicarbon products at activities greater than 1 A cm −2 . Science 2020, 367 (6478), 661-666. Dinh, C.-T.; Burdyny, T.; Kibria, M. G.; Seifitokaldani, A.; Gabardo, C. M.; García de Arquer, F. P.; Kiani, A.; Edwards, J. P.; De Luna, P.; Bushuyev, O. S.; Zou, C.; Quintero-Bermudez, R.; Pang, Y.; Sinton, D.; Sargent, E. H., CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 2018, 360 (6390), 783-787. Wang, Y.; Zou, Y.; Tao, L.; Wang, Y.; Huang, G.; Du, S.; Wang, S., Rational design of three-phase interfaces for electrocatalysis. Nano Research 2019, 12 (9), 2055-2066. Zhang, W.; Huang, C.; Xiao, Q.; Yu, L.; Shuai, L.; An, P.; Zhang, J.; Qiu, M.; Ren, Z.; Yu, Y., Atypical Oxygen-Bearing Copper Boosts Ethylene Selectivity toward Electrocatalytic CO 2 Reduction. Journal of the American Chemical Society 2020, 142 (26), 11417-11427. Yu, L.; Zhou, H.; Sun, J.; Qin, F.; Yu, F.; Bao, J.; Yu, Y.; Chen, S.; Ren, Z., Cu nanowires shelled with NiFe layered double hydroxide nanosheets as bifunctional electrocatalysts for overall water splitting. Energy & Environmental Science 2017, 10 (8), 1820-1827. Zhong, D.; Zhao, Z.-J.; Zhao, Q.; Cheng, D.; Liu, B.; Zhang, G.; Deng, W.; Dong, H.; Zhang, L.; Li, J.; Li, J.; Gong, J., Coupling of Cu(100) and (110) Facets Promotes Carbon Dioxide Conversion to Hydrocarbons and Alcohols. Angewandte Chemie International Edition 2021, 133 (9), 4929-4935. Dilimon, V. S.; Denayer, J.; Delhalle, J.; Mekhalif, Z., Electrochemical and Spectroscopic Study of the Self-Assembling Mechanism of Normal and Chelating Alkanethiols on Copper. Langmuir 2012, 28 (17), 6857-6865. Wang, Y.; Im, J.; Soares, J. W.; Steeves, D. M.; Whitten, J. E., Thiol Adsorption on and Reduction of Copper Oxide Particles and Surfaces. Langmuir 2016, 32 (16), 3848-3857. Li, H.; Liu, T.; Wei, P.; Lin, L.; Gao, D.; Wang, G.; Bao, X., High-Rate CO 2 Electroreduction to C 2+ Products over a Copper-Copper Iodide Catalyst. Angewandte Chemie International Edition 2021, 60 (26), 14329-14333. Yang, Y.; Zhang, X.; Kanchanakungwankul, S.; Lu, Z.; Noh, H.; Syed, Z. H.; Farha, O. K.; Truhlar, D. G.; Hupp, J. T., Unexpected “Spontaneous” Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles. Journal of the American Chemical Society 2020, 142 (50), 21169-21177. Scholten, F.; Nguyen, K.-L. C.; Bruce, J. P.; Heyde, M.; Roldan Cuenya, B., Identifying Structure–Selectivity Correlations in the Electrochemical Reduction of CO 2 : A Comparison of Well-Ordered Atomically Clean and Chemically Etched Copper Single-Crystal Surfaces. Angewandte Chemie International Edition 2021, 60 (35), 19169-19175. Jia, Y.; Zhang, L.; Zhuang, L.; Liu, H.; Yan, X.; Wang, X.; Liu, J.; Wang, J.; Zheng, Y.; Xiao, Z.; Taran, E.; Chen, J.; Yang, D.; Zhu, Z.; Wang, S.; Dai, L.; Yao, X., Identification of active sites for acidic oxygen reduction on carbon catalysts with and without nitrogen doping. Nature Catalysis 2019, 2 (8), 688-695. Kim, J.-H.; Hwang, J. H.; Suh, J.; Tongay, S.; Kwon, S.; Hwang, C. C.; Wu, J.; Young Park, J., Work function engineering of single layer graphene by irradiation-induced defects. Applied Physics Letters 2013, 103 (17), 171604. Lin, L.; Li, H.; Wang, Y.; Li, H.; Wei, P.; Nan, B.; Si, R.; Wang, G.; Bao, X., Temperature-Dependent CO 2 Electroreduction over Fe-N-C and Ni-N-C Single-Atom Catalysts. Angewandte Chemie International Edition 2021, 60 (51), 26582-26586. Wang, Q.; Liu, K.; Fu, J.; Cai, C.; Li, H.; Long, Y.; Chen, S.; Liu, B.; Li, H.; Li, W.; Qiu, X.; Zhang, N.; Hu, J.; Pan, H.; Liu, M., Atomically Dispersed s-Block Magnesium Sites for Electroreduction of CO 2 to CO. Angewandte Chemie International Edition 2021, 60 (48), 25241-25245. Bagger, A.; Ju, W.; Varela, A. S.; Strasser, P.; Rossmeisl, J., Electrochemical CO 2 Reduction: Classifying Cu Facets. ACS Catalysis 2019, 9 (9), 7894-7899. Feng, J.; Zhang, L.; Liu, S.; Xu, L.; Ma, X.; Tan, X.; Wu, L.; Qian, Q.; Wu, T.; Zhang, J.; Sun, X.; Han, B., Modulating adsorbed hydrogen drives electrochemical CO 2 -to-C 2 products. Nature Communications 2023, 14 (1), 4615. Zhou, Y.; Che, F.; Liu, M.; Zou, C.; Liang, Z.; De Luna, P.; Yuan, H.; Li, J.; Wang, Z.; Xie, H.; Li, H.; Chen, P.; Bladt, E.; Quintero-Bermudez, R.; Sham, T.-K.; Bals, S.; Hofkens, J.; Sinton, D.; Chen, G.; Sargent, E. H., Dopant-induced electron localization drives CO 2 reduction to C 2 hydrocarbons. Nature Chemistry 2018, 10 (9), 974-980. Zhao, Y.; Zhang, X.-G.; Bodappa, N.; Yang, W.-M.; Liang, Q.; Radjenovica, P. M.; Wang, Y.-H.; Zhang, Y.-J.; Dong, J.-C.; Tian, Z.-Q.; Li, J.-F., Elucidating electrochemical CO 2 reduction reaction processes on Cu(hkl) single-crystal surfaces by in situ Raman spectroscopy. Energy & Environmental Science 2022, 15 (9), 3968-3977. Gong, S.; Niu, Y.; Liu, X.; Xu, C.; Chen, C.; Meyer, T. J.; Chen, Z., Selective CO 2 Photoreduction to Acetate at Asymmetric Ternary Bridging Sites. ACS Nano 2023, 17 (5), 4922-4932. Gao, D.; Arán-Ais, R. M.; Jeon, H. S.; Roldan Cuenya, B., Rational catalyst and electrolyte design for CO 2 electroreduction towards multicarbon products. Nature Catalysis 2019, 2 (3), 198-210. Zhang, X.-G.; Zhao, Y.; Chen, S.; Xing, S.-M.; Dong, J.-C.; Li, J.-F., Electrolyte effect for carbon dioxide reduction reaction on copper electrode interface: A DFT prediction. The Journal of Chemical Physics 2023, 158 (9), 094704. Li, J.; Li, C.; Hou, J.; Gao, W.; Chang, X.; Lu, Q.; Xu, B., Intercepting Elusive Intermediates in Cu-Mediated CO Electrochemical Reduction with Alkyl Species. Journal of the American Chemical Society 2022, 144 (44), 20495-20506. Wang, C.; Chen, Y.; Su, D.; Man, W.-L.; Lau, K.-C.; Han, L.; Zhao, L.; Zhan, D.; Zhu, X., In situ Electropolymerized 3D Microporous Cobalt-Porphyrin Nanofilm for Highly Effective Molecular Electrocatalytic Reduction of Carbon Dioxide. Advanced Materials 2023 , 2303179. Vasileff, A.; Zhu, Y.; Zhi, X.; Zhao, Y.; Ge, L.; Chen, H. M.; Zheng, Y.; Qiao, S.-Z., Electrochemical Reduction of CO 2 to Ethane through Stabilization of an Ethoxy Intermediate. Angewandte Chemie International Edition 2020, 59 (44), 19649-19653. Hokmabad, B. V.; Ghaemi, S., Effect of Flow and Particle-Plastron Collision on the Longevity of Superhydrophobicity. Scientific Reports 2017, 7 (1), 41448. Dinh, C.-T.; Li, Y. C.; Sargent, E. H., Boosting the Single-Pass Conversion for Renewable Chemical Electrosynthesis. Joule 2019, 3 (1), 13-15. Kibria Nabil, S.; McCoy, S.; Kibria, M. G., Comparative life cycle assessment of electrochemical upgrading of CO 2 to fuels and feedstocks. Green Chemistry 2021, 23 (2), 867-880. Ma, M.; Clark, E. L.; Therkildsen, K. T.; Dalsgaard, S.; Chorkendorff, I.; Seger, B., Insights into the carbon balance for CO 2 electroreduction on Cu using gas diffusion electrode reactor designs. Energy & Environmental Science 2020, 13 (3), 977-985. Zhang, J.; Luo, W.; Züttel, A., Crossover of liquid products from electrochemical CO 2 reduction through gas diffusion electrode and anion exchange membrane. Journal of Catalysis 2020, 385 , 140-145. Salvatore, D. A.; Gabardo, C. M.; Reyes, A.; O’Brien, C. P.; Holdcroft, S.; Pintauro, P.; Bahar, B.; Hickner, M.; Bae, C.; Sinton, D.; Sargent, E. H.; Berlinguette, C. P., Designing anion exchange membranes for CO 2 electrolysers. Nature Energy 2021, 6 (4), 339-348. Goyal, A.; Marcandalli, G.; Mints, V. A.; Koper, M. T. M., Competition between CO 2 Reduction and Hydrogen Evolution on a Gold Electrode under Well-Defined Mass Transport Conditions. Journal of the American Chemical Society 2020, 142 (9), 4154-4161. Zhang, Y.-J.; Sethuraman, V.; Michalsky, R.; Peterson, A. A., Competition between CO 2 Reduction and H 2 Evolution on Transition-Metal Electrocatalysts. ACS Catalysis 2014, 4 (10), 3742-3748. Mikkelsen, M.; Jørgensen, M.; Krebs, F., Energy Environ. Sci. 2010, 3, 43.(b) Riduan, SN; Zhang, Y. Dalton Trans 2010, 39 , 3347. Zhong, D.; Zhao, Z.; Zhao, Q.; Cheng, D.; Liu, B.; Zhang, G.; Deng, W.; Dong, H.; Zhang, L.; Li, J.; Li, J.; Gong, J., Coupling of Cu(100) and (110) Facets Promotes Carbon Dioxide Conversion to Hydrocarbons and Alcohols. Angewandte Chemie international edtion 2021, 133 (9), 4929-4935. Liu, G.; Zheng, F.; Li, J.; Zeng, G.; Ye, Y.; Larson, D. M.; Yano, J.; Crumlin, E. J.; Ager, J. W.; Wang, L.; Toma, F. M., Investigation and mitigation of degradation mechanisms in Cu 2 O photoelectrodes for CO 2 reduction to ethylene. Nature Energy 2021 . Hu, S.; Liu, B.-J.; Feng, J.-M.; Zong, C.; Lin, K.-Q.; Wang, X.; Wu, D.-Y.; Ren, B., Quantifying Surface Temperature of Thermoplasmonic Nanostructures. Journal of the American Chemical Society 2018, 140 (42), 13680-13686. Xu, M.; Ma, X.; Wei, T.; Lu, Z.-X.; Ren, B., In Situ Imaging of Live-Cell Extracellular pH during Cell Apoptosis with Surface-Enhanced Raman Spectroscopy. Analytical Chemistry 2018, 90 (23), 13922-13928. Additional Declarations There is NO Competing Interest. Supplementary Files SupportingInformation.docx Supportting information Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3812973","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":266451926,"identity":"bfe897da-7795-49a5-b8da-33075a7c3dba","order_by":0,"name":"Jinli YU","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABEklEQVRIie2RMUvEMBTH/7HQLq/q2EHOr5BDUES4fpUcB96icNPhZkHoLYqrg19CBOdI1ljXExdv6eTgItygYJIKXZrTUTC/IZBHfnn/xwMCgT8IOwOTAugBkbQFauoxwMmrwCo75pVwCv2kWOzvwwLE0bZZoUSzVMpFqViR6PdbwmArz4443qYKeyQ9wdaFHJYqAh3fPRNGREZhV5XC/kXhUYhbJc7nqVWkU6K0VOCPvvEbhZBR3Sqfv1Ayo8StwqzysCKYqMYcdLj7dM3NLLqe3J9XY+K6e/z+pe4vltOD0yJR9fz1ZJAns9HNi6n0uBbdim3O4uay5lazKdymvIvcdufHd8qlPTe68wQCgcD/5QtQWFrIStJmkwAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0002-2353-8773","institution":"City university of Hong Kong","correspondingAuthor":true,"prefix":"","firstName":"Jinli","middleName":"","lastName":"YU","suffix":""},{"id":266451927,"identity":"d0f0fadd-929c-4cde-84a7-ec4081aea5e2","order_by":1,"name":"Zezhong Xie","email":"","orcid":"","institution":"Sun Yat-sen University","correspondingAuthor":false,"prefix":"","firstName":"Zezhong","middleName":"","lastName":"Xie","suffix":""},{"id":266451928,"identity":"4398e419-cdfb-4f29-b56b-4c47ea42248a","order_by":2,"name":"Hao Yang","email":"","orcid":"","institution":"Guangxi University","correspondingAuthor":false,"prefix":"","firstName":"Hao","middleName":"","lastName":"Yang","suffix":""},{"id":266451929,"identity":"8a053caa-da14-4f08-8b72-b579a49675aa","order_by":3,"name":"Qiushi Wang","email":"","orcid":"","institution":"Dalian Minzu University","correspondingAuthor":false,"prefix":"","firstName":"Qiushi","middleName":"","lastName":"Wang","suffix":""},{"id":266451930,"identity":"29eec147-e6e0-4da1-93fd-9f96d98ecc93","order_by":4,"name":"Jian Chen","email":"","orcid":"","institution":"Sun Yat-sen University","correspondingAuthor":false,"prefix":"","firstName":"Jian","middleName":"","lastName":"Chen","suffix":""},{"id":266451931,"identity":"c45211ef-6997-4e57-aad8-7b1252bd6af0","order_by":5,"name":"Shu-qin Song","email":"","orcid":"","institution":"Sun Yat-sen University","correspondingAuthor":false,"prefix":"","firstName":"Shu-qin","middleName":"","lastName":"Song","suffix":""},{"id":266451932,"identity":"a996942f-8142-4c7e-8595-846b7189efc9","order_by":6,"name":"Changgong Meng","email":"","orcid":"","institution":"Dalian University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Changgong","middleName":"","lastName":"Meng","suffix":""},{"id":266451933,"identity":"232abf6a-b206-4737-a850-83acdebd2072","order_by":7,"name":"Kun Wang","email":"","orcid":"","institution":"Sun Yat-sen University","correspondingAuthor":false,"prefix":"","firstName":"Kun","middleName":"","lastName":"Wang","suffix":""},{"id":266451934,"identity":"5b033c30-2bb4-4ed6-b26d-e8e9501c8254","order_by":8,"name":"Yexiang Tong","email":"","orcid":"https://orcid.org/0000-0003-4344-443X","institution":"Sun Yat-sen University","correspondingAuthor":false,"prefix":"","firstName":"Yexiang","middleName":"","lastName":"Tong","suffix":""}],"badges":[],"createdAt":"2023-12-27 16:00:09","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3812973/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3812973/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":49505129,"identity":"3d9ad95e-a367-4d5e-9daa-e8846320034b","added_by":"auto","created_at":"2024-01-12 03:09:40","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":634052,"visible":true,"origin":"","legend":"\u003cp\u003eSurface structure characterization of the catalysts. (a) Schematic illustration of the preparation of OBC and OBC-OT materials. (b) SEM images of the OBC-OT, the insert is the enlarged image. (c) Typical TEM image, EDS mapping, and (d) HRTEM image of the nanowire on the surface of OBC-OT. (e) Cu LMM spectra of the OBC, OBC-OT, and OBC-OT-tested (after testing at -1.57 V vs. RHE for 1 h). (f) Contact angle of OBC (left) and OBC-OT (right). (g) The ECSA difference of OBC and OBC-OT.\u003c/p\u003e","description":"","filename":"Onlinefloatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-3812973/v1/dd42ee08829888e096ca275b.png"},{"id":49505621,"identity":"1a8920c5-ad9d-465c-99d9-b2870ee26ebc","added_by":"auto","created_at":"2024-01-12 03:17:40","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":90953,"visible":true,"origin":"","legend":"\u003cp\u003eCO\u003csub\u003e2\u003c/sub\u003eRR performance in H-type cell. (a) LSV curves of OBC and OBC-OT in the CO\u003csub\u003e2\u003c/sub\u003e-saturated and N\u003csub\u003e2\u003c/sub\u003e-saturated KHCO\u003csub\u003e3\u003c/sub\u003e solution (0.1 M). FE of the main products on (b) OBC and (c) OBC-OT catalysts. (d) H\u003csub\u003e2\u003c/sub\u003e, C\u003csub\u003e2+\u003c/sub\u003e, C\u003csub\u003e1\u003c/sub\u003e FE, and C\u003csub\u003e2+\u003c/sub\u003e/C\u003csub\u003e1\u003c/sub\u003e selectivity on the OBC, OBC-OT catalysts.\u003c/p\u003e","description":"","filename":"Onlinefloatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-3812973/v1/a69f8edb35185cc4f545b43c.png"},{"id":49505620,"identity":"c5dcf637-a013-451c-9a79-5d289a87b9cc","added_by":"auto","created_at":"2024-01-12 03:17:40","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":408804,"visible":true,"origin":"","legend":"\u003cp\u003eSurface CO adsorption and the catalyst-electrolyte-gas triple-phase interface. (a) KPFM results and (b) corresponding height and potential difference of OBC and OBC-OT. (c) CO-TPD and H\u003csub\u003e2\u003c/sub\u003e-TPD profiles over OBC and OBC-OT catalysts. (d) 3D Raman mapping, (g) the corresponding outer surface white light imaging (top-left), 2D Raman mapping (top-right), and dash lines represented Raman spectra (bottom) for the OBC-OT. (e) \u003cem\u003eIn-situ \u003c/em\u003e3D Raman mapping, (h) the corresponding outer surface white light imaging (top-left), 2D Raman mapping (top-right), and dash lines represented Raman spectra (bottom) for the OBC-OT with potential of -0.2 V vs. RHE was applied. (f) \u003cem\u003eIn-situ \u003c/em\u003e3D Raman mapping, (i) the corresponding outer surface white light imaging (top-left), 2D Raman mapping (top-right), and dash lines represented Raman spectra (bottom) for the OBC with potential of -0.2 V vs. RHE was applied. The yellow and rainbow of Raman mapping meant the peak intensity of CuO\u003csub\u003ex\u003c/sub\u003e and HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e, respectively.\u0026nbsp;\u003c/p\u003e","description":"","filename":"Onlinefloatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-3812973/v1/f4ab45c26d2493c3d7c845ad.png"},{"id":49505133,"identity":"704ffa80-cd0f-429a-b501-775ce43870ce","added_by":"auto","created_at":"2024-01-12 03:09:40","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":252857,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003eIn-situ\u003c/em\u003e Raman spectra of the catalysts. (a-b) \u003cem\u003eIn-situ\u003c/em\u003e Raman spectra for the triple-phase interface of the OBC-OT catalysts. (c) \u003cem\u003eIn-situ\u003c/em\u003e Raman spectra for the OBC catalysts. (d) Outer surface 2D Raman mapping of CO\u003csub\u003e2\u003c/sub\u003eRR intermediate (top-right), corresponding white light imaging (top-left), and dash lines represented Raman spectra (bottom) for the OBC-OT with potential of -0.2 V vs. RHE was applied. (e) Outer surface 2D Raman mapping of CO\u003csub\u003e2\u003c/sub\u003eRR intermediate (top-right), corresponding white light imaging (top-left), and dash lines represented Raman spectra (bottom) for the OBC with potential of -0.2 V vs. RHE was applied. The magenta, red, and rainbow of Raman mapping meant the peak intensity of *COOH, CH\u003csub\u003e3\u003c/sub\u003eCOOH, and *CO, respectively.\u003c/p\u003e","description":"","filename":"Onlinefloatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-3812973/v1/e5742efc06864889e6018d29.png"},{"id":49505131,"identity":"bd7aa5e3-0626-46be-88cf-55c54a708ca6","added_by":"auto","created_at":"2024-01-12 03:09:40","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":256932,"visible":true,"origin":"","legend":"\u003cp\u003eSimulations and measurements of micro-environmental species. (a) Modeled local pH and (b) CO\u003csub\u003e2\u003c/sub\u003e concentration profiles along the catalyst surface at various applied current densities. (c) Experimental local pH profiles measured by the surface-enhanced Raman spectroscopy (SERS) with pH-sensitive molecules. (d) Schematic illustration of the CO\u003csub\u003e2\u003c/sub\u003eRR process on OBC-OT material. (e) Microenvironment evolution at the triple-phase interface on the CO\u003csub\u003e2\u003c/sub\u003eRR process of OBC-OT. The electrolyte was CO\u003csub\u003e2\u003c/sub\u003e-saturated 0.1 M KHCO\u003csub\u003e3\u003c/sub\u003e solution.\u003c/p\u003e","description":"","filename":"Onlinefloatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-3812973/v1/a00d542e4b132e4c52511867.png"},{"id":49505134,"identity":"daf4445a-5d87-454e-8437-21e6912c2508","added_by":"auto","created_at":"2024-01-12 03:09:40","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":153333,"visible":true,"origin":"","legend":"\u003cp\u003eApplication in flow cell system with acid electrolyte. (a) Flow-cell configuration. Cathode:\u003c/p\u003e\n\u003cp\u003eOBC-OT (without additional gas diffusion electrode); Reference electrode: Ag/AgCl; Membrane: Nafion N211; anode: Pt net; Electrolyte: acid 0.5 M K\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e (pH=4, H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e adjusted). (b) The gas diffusion scheme and the SEM images of the OBC-OT (insert is the enlarged image of hydrophobic nanowires on OBC-OT). (c) H\u003csub\u003e2\u003c/sub\u003e, C\u003csub\u003e2+\u003c/sub\u003e, and C\u003csub\u003e1\u003c/sub\u003e FE on the OBC-OT under different current densities. (d) Long-term CO\u003csub\u003e2\u003c/sub\u003eRR stability of the OBC-OT catalysts with the current density of 300 mA cm\u003csup\u003e-2 \u003c/sup\u003eapplied.\u003c/p\u003e","description":"","filename":"Onlinefloatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-3812973/v1/28a6a273d574f365ae88f59d.png"},{"id":50995324,"identity":"19e24272-87a6-417c-a08b-5c39e9e5922b","added_by":"auto","created_at":"2024-02-12 11:33:21","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4126414,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3812973/v1/443bf422-25cd-4b30-8a68-184c9f8224ee.pdf"},{"id":49505135,"identity":"921cfaa2-a90f-47fe-9e41-0f820102cc3c","added_by":"auto","created_at":"2024-01-12 03:09:40","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":36663724,"visible":true,"origin":"","legend":"Supportting information","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-3812973/v1/e3dbd1cd4bb0060ff74d11f4.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Microenvironment Evolution at Triple-phase Interface on the CO2RR Process of Hydrophobic Oxide-derived Copper","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe renewable electricity-powered CO\u003csub\u003e2\u003c/sub\u003e electro-reduction (CO\u003csub\u003e2\u003c/sub\u003eRR) offers a promising route to simultaneously achieve renewable energy storage and effectively address the challenge of climate change.\u003csup\u003e1\u0026ndash;4\u003c/sup\u003e In this context, the value-added multi-carbon (C\u003csub\u003e2+\u003c/sub\u003e) products from CO\u003csub\u003e2\u003c/sub\u003eRR like ethylene, ethanol, and propanol, are particularly desired due to their substantial energy density and economic returns.\u003csup\u003e4\u0026ndash;8\u003c/sup\u003e Accordingly, extensive efforts have been dedicated to developing potent electrocatalysts, such as Cu-based catalysts, for efficient conversion of CO\u003csub\u003e2\u003c/sub\u003e to C\u003csub\u003e2+\u003c/sub\u003e products.\u003csup\u003e9\u0026ndash;11\u003c/sup\u003e Besides seeking for novel catalysts, it is also critical to understand the reaction microenvironment,\u003csup\u003e11, 12\u003c/sup\u003e which can influence reaction pathways through the affecting mass transfer and local concentration of reaction species. \u003csup\u003e11, 13\u003c/sup\u003e Significantly, the reaction microenvironment involves the local environment surrounding the reaction interface between the catalyst,\u003csup\u003e14\u003c/sup\u003e reactants,\u003csup\u003e15, 16\u003c/sup\u003e, and electrolyte\u003csup\u003e17\u003c/sup\u003e, which decides both the kinetics and thermodynamics during reactions.\u003csup\u003e11, 18, 19\u003c/sup\u003e For example, the electrolyte's local pH, species, and buffer capacity, etc., have significant effects on the local reaction conditions and the product distribution of the electrochemical reactions, and the hydrophilicity and hydrophobicity of electrode/catalysts can affect the mass transfer of interfacial water thereby modulating the process of the reactions.\u003csup\u003e17,20\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eAs for the electrochemical CO\u003csub\u003e2\u003c/sub\u003eRR process, the structure and properties of the catalyst-electrolyte-gas triple-phase interface, which interacts with the reaction microenvironment, play a crucial role in the catalytic activity and selectivity.\u003csup\u003e21\u003c/sup\u003e As a typical work, Warkerley et al. introduced a hydrophobic Cu dendrite catalyst with a triple-phase interface, which can trap gas under hydrophobic hairs in water like a spider to modulate the reaction process.\u003csup\u003e22\u003c/sup\u003e In this catalyst-electrolyte-gas system, the CO\u003csub\u003e2\u003c/sub\u003eRR process only evolved near the triple-phase boundary with CO\u003csub\u003e2\u003c/sub\u003e diffusion, and the microenvironment like the local ion and gas transfer was significantly changed, which led to the suppressed hydrogen evolution reaction (HER) with a Faradaic efficiency (FE) below 10% and induced high C\u003csub\u003e2+\u003c/sub\u003e product selectivity.\u003csup\u003e22\u003c/sup\u003e Recently, the cells with gas-diffusion electrodes (GDE) were developed and upgraded to enhance the mass transfer of reactants, which can achieve high current density at an industrial scale because the limitation of CO\u003csub\u003e2\u003c/sub\u003e mass transfer was alleviated.\u003csup\u003e11, 23, 24\u003c/sup\u003e For example, Dinh et al. achieved enhanced operational stability of constant ethylene selectivity for an initial 150 operating hours though the Polytetrafluoroethylene (PTFE)-based gas diffusion layer, which sandwiches the reaction interface between separate hydrophobic and conductive carbon layer.\u003csup\u003e24\u003c/sup\u003e It was emphasized that the stability of the CO\u003csub\u003e2\u003c/sub\u003eRR in gas-type reactors was significantly affected by the durability of the triple-phase interface, which was successfully kept with the additional carbon materials on the electrode.\u003csup\u003e21, 24\u003c/sup\u003e These studies have demonstrated the substantial influence of the catalyst-electrolyte-gas triple-phase interface and its microenvironment in gas-involved electrochemical reactions.\u003csup\u003e11, 25\u003c/sup\u003e However, most of the reported electrode is either carbon-based or PTFE derived GDE, metal foam based GDE without GDL is rarely reported. And there is still need to be explored and understood regarding that the impact of catalyst microenvironment and reaction interfaces on the mass transport and kinetics of metal foam-based GDE, which was conducive to further design of the effective CO\u003csub\u003e2\u003c/sub\u003eRR system with an optimal microenvironment at the catalyst-electrolyte-gas interfaces.\u003c/p\u003e \u003cp\u003eIn this context, our work aimed at constructing an intuitive and conveniently researchable catalyst-electrolyte-gas triple-phase interface, deepening the understanding of the triple-phase interface microenvironment and guiding the design of the efficient CO\u003csub\u003e2\u003c/sub\u003eRR system. We prepared the oxide-derived copper with villous nanowire structure (OBC)\u003csup\u003e26\u003c/sup\u003e base on the porous copper foam framework, and then on its basis synthesized the corresponding hydrophobic materials (OBC-OT) with the treatment of 1-octadecanethiol. CO\u003csub\u003e2\u003c/sub\u003eRR performance in H-type cell showed that the HER of OBC-OT was effectively suppressed to 12.6%, and the C\u003csub\u003e2+\u003c/sub\u003e/C\u003csub\u003e1\u003c/sub\u003e selectivity of OBC-OT was improved to 3.3 compared to the 1.4 of OBC. The weak CO adsorption in TPD results showed that the surface active site variation caused by the 1-octadecanethiol adsorption was not the deep reason for elevated C\u003csub\u003e2+\u003c/sub\u003e selectivity. The \u003cem\u003ein-situ\u003c/em\u003e 3D Raman mapping was used to visually observe the catalyst-electrolyte-gas triple-phase interface and demonstrated the significant increase of reactants and local current density at the triple-phase interface. The \u003cem\u003ein-situ\u003c/em\u003e Raman spectra further verified the high local current density under different applied potentials and revealed the changes from C\u003csub\u003e1\u003c/sub\u003e products favored to C\u003csub\u003e2+\u003c/sub\u003e products along with the applied potential negative shifted or current density increase. Additionally, combining the measurements with simulations of micro-environmental species, it is found that high local pH and fast CO\u003csub\u003e2\u003c/sub\u003e mass transfer can be simultaneously allowed in the microenvironment of the triple-phase interface as a result of the special hydrophobic structure of OBC-OT, which led to the high C\u003csub\u003e2+\u003c/sub\u003e selectivity and suppressed HER. Leveraging this mechanism and the porous hydrophobic structure, the OBC-OT was further applied in the flow cell under acidic conditions (pH\u0026thinsp;=\u0026thinsp;4) and displayed a low H\u003csub\u003e2\u003c/sub\u003e FE of 6.6% and high C\u003csub\u003e2+\u003c/sub\u003e FE of 74.4% at the current density of 300 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e without additional gas-diffusion layer (GDL).\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e\u003cstrong\u003eCatalyst Synthesis and Characterization.\u003c/strong\u003e Catalyst-electrolyte-gas triple-phase interface and its microenvironment play a crucial role in the CO\u003csub\u003e2\u003c/sub\u003eRR performance. Therefore, we prepared the hydrophobic and porous OBC-OT based on Cu foam as the catalysts, which can intuitively observe the interface and conveniently research the microenvironment. Firstly, we synthesized a layer of Cu(OH)\u003csub\u003e2\u003c/sub\u003e nanowires on the surface of Cu foam with the alkaline solution according to the previous report\u003csup\u003e26\u0026ndash;28\u003c/sup\u003e, and the blue Cu(OH)\u003csub\u003e2\u003c/sub\u003e layer was turned to CuO layer after the annealing process. After that, the OBC materials were then obtained as the CuO layer was electro-reduced to oxide-derived Cu with a villous nanowire structure\u003csup\u003e8, 26\u003c/sup\u003e. Based on OBC, the OBC-OT materials were prepared with the hydrophobic treatment of 1-octadecanethiol (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ea and Figure \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e).\u003c/p\u003e\n\u003cp\u003eThe scanning electron microscopy (SEM) images of the OBC-OT showed that the villous and twisted nanowires were grown on the surface of Cu foam and a large amount of dense and interlaced channels can be formed based on this structure (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003eb). The typical transmission electron microscopy (TEM) images in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ec further demonstrated certain rough surfaces belong to the oxide-derived Cu. Additionally, the corresponding energy dispersive spectroscopy (EDS) mapping in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ec also showed that the oxide-derived Cu was different from the pure metallic and there are still some O remained after the electro-reduction, which was in accord with the previous report.\u003csup\u003e26\u003c/sup\u003e The 1-octadecanethiol was verified to be successfully absorbed with the thickness of ~\u0026thinsp;1.5 nm (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ed) on the nanowires based on the EDS images of C and S element (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ec) and the S 2p spectra in X-ray photoelectron spectroscopy (XPS) result (Figure S7). The BET results showed that there was no obvious pore blinding after the processing of 1-octadecanethiol as the surface area even increased (Figure S9). The CuO, OBC, and OBC-OT were also characterized by the Raman and infrared absorption (IR) spectra in Figure S8a-b. Although there was no obvious Raman peak of 1-octadecanethiol detected in OBC-OT because of the low content and Raman scattering area, the weak IR peak of 1-octadecanethiol was detected in OBC-OT.\u003c/p\u003e\n\u003cp\u003eHigh-resolution transmission electron microscopy (HRTEM) indicated that the lattice space of oxide-derived Cu (1.90, 2.17, 2.21, and 3.55 \u0026Aring;) differs from the pure Cu, CuO, or Cu\u003csub\u003e2\u003c/sub\u003eO, which can be designed as the CuO\u003csub\u003ex\u003c/sub\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ed and Figure S2). The X-ray diffraction (XRD) results of OBC with different electrochemical reduction time (Figure S4a-b) further confirmed that this phenomenon was not resulted from the incomplete reduction of CuO. The CuO\u003csub\u003ex\u003c/sub\u003e on OBC was formed in 10 min and can be stable with the potential of -1.0 V vs. RHE applied for 10 h. The \u003cem\u003ein-situ\u003c/em\u003e Raman spectra (Figure S5) monitored the process of this conversion process from CuO to OBC at -1.0 V vs. RHE and the peak of 616 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Cu-O) was gradually weakened. When the 1-octadecanethiol directly adsorbed on CuO nanowires (CuO-OT), a thick layer (~\u0026thinsp;15 nm) of 1-octadecanethiol was averse to the exposure of reaction sites, which confirmed the necessity of the electrochemical reduction process (Figure S6).\u003c/p\u003e\n\u003cp\u003eThe XPS was conducted to reveal the valence and chemical bonding information of the catalysts (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ee and Figure S7). The Cu LMM spectra showed that the proportion of Cu(0) increased as the 1-octadecanethiol adsorbed on OBC, which was in accord with the previous report.\u003csup\u003e22\u003c/sup\u003e While, the proportion of Cu(Ⅰ) decreased concomitantly. Combining the S-Cu(Ⅰ) existed on OBC-OT in Figure S7a,\u003csup\u003e22, 29, 30\u003c/sup\u003e it can be speculated that the decrease in the signal strength of Cu (I) can be attributed to the coverage of long-chain 1-octadecanethiol on Cu(Ⅰ).\u003csup\u003e31, 32\u003c/sup\u003e The weakened peak intensity of OBC-OT compared to OBC in the O 1s spectra further verified the increased content of Cu(0) on the surface. The comparison of XPS data between OBC-OT and the OBC-OT-tested (after testing at -1.57 V vs. RHE for 1 h) demonstrated the considerable adsorption stability of the 1-octadecanethiol on OBC-OT as there was a small variation between them.\u003c/p\u003e\n\u003cp\u003eThe hydrophobic property of the OBC and OBC-OT was investigated via the contact angle result and photography water immersion test. After the hydrophobic treatment, the contact angle of OBC-OT was turned to 129\u0026deg; compared to the 17\u0026deg; of OBC (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ef), and it remained 127\u0026deg; after testing at -1.57 V vs. RHE for 1 h (Figure S11), which illustrated the stability of the hydrophobic layer as well. As the OBC-OT was immersed in the water (Figure S3), the white surface liquid film appeared because of the high contact and refractive index difference between liquid and gas. Additionally, the plucked OBC-OT can keep dry from visual observation although it had been completely submerged in water.\u003c/p\u003e\n\u003cp\u003eThe electrochemical double-layer capacitance (C\u003csub\u003edl\u003c/sub\u003e) was calculated to evaluate the electrochemical active surface area (ECSA) in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003eg. The OBC-OT showed a C\u003csub\u003edl\u003c/sub\u003e of 0.021 mF cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, which was well below the 4.60 mF cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e of OBC, which indicated the great reduction of the catalyst-electrolyte contact area due to the hydrophobic property. Furthermore, the C\u003csub\u003edl\u003c/sub\u003e of polished plate Cu was 0.067 mF cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e according to a previous study\u003csup\u003e28\u003c/sup\u003e, higher than that of OBC-OT, which further verified the hollow space as the OBC-OT was immersed in the electrolyte.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u0026nbsp;\u003c/sub\u003e \u003cstrong\u003eRR Performances in H-type cell.\u003c/strong\u003e The CO\u003csub\u003e2\u003c/sub\u003eRR properties of the OBC and OBC-OT catalysts were evaluated in the H-type cell setup with the CO\u003csub\u003e2\u003c/sub\u003e-saturated 0.1 M KHCO\u003csub\u003e3\u003c/sub\u003e (pH \u0026sim; 6.8) solution as the electrolyte, the prepared catalysts as the working electrode, the Pt mesh as the counter electrode, and the saturated Ag/AgCl as the reference electrode. The FE of CO\u003csub\u003e2\u003c/sub\u003e-reduction products was calculated by nuclear magnetic resonance (NMR) spectroscopy (Figure S13-14) and gas chromatography (GC, Figure S15). The voltage drop from solution resistance was compensated. The solution resistance was measured by the electrochemical impedance spectroscopy (EIS) in Figure S12.\u003c/p\u003e\n\u003cp\u003eThe linear sweep voltammetry (LSV) was conducted in the CO\u003csub\u003e2\u003c/sub\u003e-saturated and N\u003csub\u003e2\u003c/sub\u003e-saturated 0.1 M KHCO\u003csub\u003e3\u003c/sub\u003e solution to estimate the CO\u003csub\u003e2\u003c/sub\u003eRR and competitive HER activity (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea) of OBC and OBC-OT. The general current density of OBC-OT was lower than that of OBC owing to the hydrophobic property of OBC-OT. The OBC in CO\u003csub\u003e2\u003c/sub\u003e-saturated electrolyte showed an approximate current density with that in N\u003csub\u003e2\u003c/sub\u003e-saturated electrolyte, indicating a high competitive HER on the OBC. However, the OBC-OT showed higher current density in the presence of CO\u003csub\u003e2\u003c/sub\u003e than that of N\u003csub\u003e2\u003c/sub\u003e, which reflected its preferable CO\u003csub\u003e2\u003c/sub\u003eRR activity.\u003c/p\u003e\n\u003cp\u003eThe CO\u003csub\u003e2\u003c/sub\u003eRR selectivity results (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb-c and Figure S16a-c) also showed that the HER was effectively suppressed on OBC-OT. The OBC exhibited a high FE\u003csub\u003eH2\u003c/sub\u003e of about 40%, while the FE\u003csub\u003eH2\u003c/sub\u003e of OBC-OT can reach a small value of 12.6% at the testing potential (Figure S16a). Besides, the OBC-OT showed a higher C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e FE (~\u0026thinsp;36.5%) and C\u003csub\u003e2+\u003c/sub\u003e FE (~\u0026thinsp;67.9%) than the OBC that exhibited the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e FE and C\u003csub\u003e2+\u003c/sub\u003e FE of ~\u0026thinsp;17.0% and 33.8%, respectively (Figure S16b-c). The C\u003csub\u003e2+\u003c/sub\u003e, C\u003csub\u003e1\u003c/sub\u003e, and H\u003csub\u003e2\u003c/sub\u003e selectivity of OBC and OBC-OT were arranged in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed and it intuitively indicated the improvement of CO\u003csub\u003e2\u003c/sub\u003eRR performance via the hydrophobic processing of OBC. Additionally, to ensure that the improved C\u003csub\u003e2+\u003c/sub\u003e FE was not simply resulted from the decreased HER, the FE ratio of C\u003csub\u003e2+\u003c/sub\u003e/C\u003csub\u003e1\u003c/sub\u003e of OBC and OBC-OT was presented in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed. The C\u003csub\u003e2+\u003c/sub\u003e/C\u003csub\u003e1\u003c/sub\u003e selectivity of OBC-OT was significantly elevated to 3.3 compared to the 1.4 of OBC, which meant that the C\u003csub\u003e2+\u003c/sub\u003e selectivity was indeed improved even disregarding the HER factor.\u003c/p\u003e\n\u003cp\u003eHowever, it should be noted that the CO FE was significantly increased (reached\u0026thinsp;~\u0026thinsp;21.3%) with the hydrophobic processing when the applied potential was not too negative (-1.2 V to -1.4 V). While, as the applied potential became more negative, the CO FE rapidly declined to ~\u0026thinsp;4.5%. Similarly, the C\u003csub\u003e1\u003c/sub\u003e product of HCOOH showed the same variation trend as the applied potential changed. Therefore, combining the analysis of the opposite trend of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e or C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eOH in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec, it can be concluded that the C\u003csub\u003e2+\u003c/sub\u003e selectivity of OBC-OT under the low applied potential was not ideal enough (similar to the OBC) and the C\u003csub\u003e2+\u003c/sub\u003e selectivity can be elevated with more negative potential and higher current density applied.\u003c/p\u003e\n\u003cp\u003eThe long-term CO\u003csub\u003e2\u003c/sub\u003eRR stability of OBC and OBC-OT regarding the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e FE and C\u003csub\u003e2+\u003c/sub\u003e FE retention over a 6-hour operation period in H-type cell were investigated (Figure S17). After the 6 h operation period, the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e FE and C\u003csub\u003e2+\u003c/sub\u003e FE of OBC-OT were stable and can be held at 34.2% and 61.2%, respectively. Furthermore, the SEM and EDS of OBC-OT with 10 h of CO\u003csub\u003e2\u003c/sub\u003eRR test (Figure S10) also demonstrated that the absorbed hydrophobic layer was durable, which was consistent with the high CO\u003csub\u003e2\u003c/sub\u003eRR stability of OBC-OT.\u003c/p\u003e\n\u003cp\u003eIn addition, the influence of the 1-octadecanethiol adsorption quantity on OBC was investigated. We prepared the OBC-sOT which contained a slight content of 1-octadecanethiol molecules on the surface (Figure S18). Unlike the OBC-OT that possessed strong HER suppression capacity, OBC-sOT exhibited a higher H\u003csub\u003e2\u003c/sub\u003e evolution. However, the HER was still lower than the untreated OBC, which indicated the certain effect of 1-octadecanethiol. The LSV curves of OBC-sOT in CO\u003csub\u003e2\u003c/sub\u003e-saturated and N\u003csub\u003e2\u003c/sub\u003e-saturated 0.1 M KHCO\u003csub\u003e3\u003c/sub\u003e solution indicated the not strong enough HER suppression as well (Figure S18c). Besides, the CO FE on OBC-sOT was higher than that on OBC-OT, which demonstrated the preferable C\u003csub\u003e1\u003c/sub\u003e selectivity when the adsorption quantity of 1-octadecanethiol was not enough. The ECSA results of OBC-sOT showed that certain hydrophobic property was achieved and the C\u003csub\u003edl\u003c/sub\u003e was also significantly reduced with slight 1-octadecanethiol absorbed (Figure S18b).\u003c/p\u003e\n\u003cp\u003eThe partial current density of C\u003csub\u003e2+\u003c/sub\u003e products on OBC and OBC-OT was normalized\u003csup\u003e33\u003c/sup\u003e (Figure S16d) with the value of 0.067 mF cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e was used as the C\u003csub\u003edl\u003c/sub\u003e of polished Cu from the previous report\u003csup\u003e8\u003c/sup\u003e. The C\u003csub\u003edl\u003c/sub\u003e of OBC-OT was small and the electrocatalytic reaction was conducted on a small solid-liquid contact area. It emphasized the high local current density at the solid-liquid-gas interface, which may lead the microenvironment variation with such mass transfer occurred at the interface.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSurface properties and catalyst-electrolyte-gas triple-phase interfaces.\u003c/strong\u003e To gain insight into the mechanism of CO\u003csub\u003e2\u003c/sub\u003eRR performance improvement, we studied the surface properties and the difference between OBC and OBC-OT. The kelvin probe force microscope (KPFM) was applied to further explore the origin of CO2RR performance difference with the analysis of surface potential. Figure \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea-b displayed the KPFM images and the corresponding height and potential difference of OBC and OBC-OT. The OBC-OT showed a higher potential difference of \u0026minus;\u0026thinsp;34.2 mV (\u003cem\u003evs.\u003c/em\u003e silicon substrate) compared with \u0026minus;\u0026thinsp;6.2 mV (\u003cem\u003evs.\u003c/em\u003e silicon substrate) of OBC, which implied the lower local work function of OBC-OT. The lower local work function indicated the faster charge separation and transfer, thereby contributing to spontaneous polarization and enhanced energetics for CO\u003csub\u003e2\u003c/sub\u003eRR,\u003csup\u003e34, 35\u003c/sup\u003e which was consistent with the weak HER and strong CO\u003csub\u003e2\u003c/sub\u003eRR of OBC-OT.\u003c/p\u003e\n\u003cp\u003eAs displayed in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ec, the temperature-programmed desorption (TPD) of CO and H\u003csub\u003e2\u003c/sub\u003e was carried out to evaluate the CO and H\u003csub\u003e2\u003c/sub\u003e desorption on catalysts\u003csup\u003e36, 37\u003c/sup\u003e. The similar H\u003csub\u003e2\u003c/sub\u003e-TPD curves of OBC and OBC-OT implied the similar H\u003csub\u003e2\u003c/sub\u003e adsorption on the catalysts. However, comparing to the OBC, the OBC-OT presented a CO desorption peak with obviously lower temperature in the CO-TPD spectra, indicating that the CO was not easy to adsorbed on the OBC-OT surface\u003csup\u003e36\u003c/sup\u003e. The weak adsorption of CO on OBC-OT was not beneficial to the CO coupling and high C\u003csub\u003e2+\u003c/sub\u003e selectivity\u003csup\u003e38\u0026ndash;40\u003c/sup\u003e, which was inconsistent with the elevated C\u003csub\u003e2+\u003c/sub\u003e selectivity of OBC-OT. The surface-active site variation caused by the 1-octadecanethiol adsorption was not the root cause of elevated C\u003csub\u003e2+\u003c/sub\u003e selectivity. However, it was noteworthy that the TPD was not tested under operating conditions for CO\u003csub\u003e2\u003c/sub\u003eRR as no additional potential was applied in the TPD measurement. Besides, the TPD result of OBC-OT was in accord with the high C\u003csub\u003e1\u003c/sub\u003e selectivity at less negative potential owing to the similar microenvironment when no potential or low potential was applied. The microenvironment could be changed with the different potential applied to the catalysts, which also affect the product\u0026apos;s selectivity.\u003c/p\u003e\n\u003cp\u003eThe catalyst-electrolyte-gas triple-phase interface of the OBC-OT, where the CO\u003csub\u003e2\u003c/sub\u003eRR mainly occurred, was primarily investigated via the \u003cem\u003ein-situ\u003c/em\u003e 3D Raman mapping technique. Firstly, the 3D Raman mapping (based on the peak intensity of surface CuO\u003csub\u003ex\u003c/sub\u003e in 615 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003csup\u003e41\u003c/sup\u003e of OBC-OT at air atmosphere (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ed and Figure S20a) showed the clear structure of the foam framework, indicating the feasibility of the measurement method for the materials. In addition, the corresponding 2D Raman mapping represented high consistency with the white light imaging as for the OBC-OT (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eg).\u003c/p\u003e\n\u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ee demonstrated the \u003cem\u003ein-situ\u003c/em\u003e 3D Raman mappings (based on the peak intensity of CuO\u003csub\u003ex\u003c/sub\u003e in 615 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e in 1070 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003csup\u003e41\u003c/sup\u003e of OBC-OT at -0.2 V vs. RHE. Combining with the analysis of the corresponding white light imaging and the sliced mapping along depth (Figure S20b), it can be easily concluded that the gas chamber and solid-liquid-gas triple-phase reaction interface caused by hydrophobicity were presented in the immersed OBC-OT. Additionally, the white liquid film formed on the surface of immersed OBC-OT owing to the high contact angle and the refractivity difference of the electrolyte and gas (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eh). Below the white liquid film, the obvious CuO\u003csub\u003ex\u003c/sub\u003e peak was presented and there was no HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e peak being detected even though the frame of OBC-OT can be seen in the white light imaging, which further verified the existence of gas chamber and the catalyst-electrolyte-gas triple-phase interface.\u003c/p\u003e\n\u003cp\u003eDifferent from the OBC-OT, the peak of CuO\u003csub\u003ex\u003c/sub\u003e vanished and only the HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e peak was shown in the \u003cem\u003ein-situ\u003c/em\u003e 3D Raman mapping because of the O atoms detachment from OBC under the negative potential (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ef and Figure S20c). The corresponding outer surface white light imaging and 2D Raman mapping showed that there was no gas chamber in the immersed OBC (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ei). On the other hand, noteworthy that the peak intensity of HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e on the outer side was higher than that on the inner side of the foam, which can be attributed to the higher solution IR drop on the inner side.\u003c/p\u003e\n\u003cp\u003eComparing the peak intensity of HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e absorbed on the surface of catalysts (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eh-i), it can be revealed that the peak intensity of HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e on OBC-OT was nearly ten times that on OBC, which meant that the large amount of HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e was gathered around the triple-phase interface of OBC-OT. The high local current density resulted in high local mass transfer, including the transfer of HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e and the CO\u003csub\u003e2\u003c/sub\u003eRR reactants. Based on the data above, it can be speculated that the reaction microenvironment changed by the accumulation of local reactants and intermediates at the solid-liquid gas triple-phase interface with high negative potentials applied, led to the variation in the catalytic reaction pathway and the significant increase in C\u003csub\u003e2+\u003c/sub\u003e selectivity.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eIn-situ\u003c/strong\u003e \u003cstrong\u003eRaman spectroscopy characterization.\u003c/strong\u003e To elucidate the origin of the promoted C\u003csub\u003e2+\u003c/sub\u003e selectivity on OBC-OT, we conducted an extensive set of investigations via the \u003cem\u003ein-situ\u003c/em\u003e Raman spectra and mapping. The intermediates and adsorbates on the OBC-OT with an elevated potential applied were displayed in the \u003cem\u003ein-situ\u003c/em\u003e Raman spectra for the triple-phase interface of the OBC-OT catalysts (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea-b). When the weak negative potential was applied, the strong peak of HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e (1070 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) appeared and the peak of CuO\u003csub\u003ex\u003c/sub\u003e (1581 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) was weakened due to the HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e adsorption and O detachment in the lattice under the negative potential\u003csup\u003e41\u003c/sup\u003e. Additionally, the COOH* peak of 1581 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was detected as the applied potential was not too negative, which was consistent with the result of CO-TPD and the preferable C\u003csub\u003e1\u003c/sub\u003e selectivity of OBC-OT at weak negative potential.\u003csup\u003e42\u003c/sup\u003e Furthermore, the *CO peak of 2000\u0026ndash;2100 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was also studied with the applied potential shifted negatively. The *CO peak is an important index to judge the C\u003csub\u003e2+\u003c/sub\u003e selectivity of catalysts, as the CO\u003csub\u003e2\u003c/sub\u003eRR to multi-carbon products undergo a critical CO dimerization step.\u003csup\u003e43\u003c/sup\u003e However, there was no obvious *CO peak until the applied potential was negatively shifted to -1.1 V vs. RHE, which was in accord with the C\u003csub\u003e2+\u003c/sub\u003e FE variation trend with the potential change.\u003c/p\u003e\n\u003cp\u003eBesides the *CO peak, the peaks around 1296 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 704 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which can be assigned to the adsorbed C-O bonds of CO\u003csub\u003e2\u003c/sub\u003e and the in-plane \u0026delta;CO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e,\u003csup\u003e41, 44\u003c/sup\u003e respectively, were also obviously raised with the potential applied from \u0026minus;\u0026thinsp;1.1 V vs. RHE to -1.8 V vs. RHE, indicating the improved activation of CO\u003csub\u003e2\u003c/sub\u003e. In addition, owing to the high local current density and reaction, the peaks of C-C stretching (1103 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), symmetrical CH\u003csub\u003e3\u003c/sub\u003e deformation (1132 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), C-H vibration of hydrogenated intermediates after C-C coupling (1332 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), and COO stretching vibration of CH\u003csub\u003e3\u003c/sub\u003eCOOH (1437 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) from the CO\u003csub\u003e2\u003c/sub\u003eRR intermediates and reactants were clearly presented, demonstrated the hydrocarbons were generated during the CO\u003csub\u003e2\u003c/sub\u003eRR process.\u003csup\u003e42, 45, 46\u003c/sup\u003e It was noteworthy that the HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e peak declined with the peak of C-C stretching and symmetrical CH\u003csub\u003e3\u003c/sub\u003e deformation raised, which implied the competition between HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e and multi-carbons on the surface of catalysts. The HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e was gradually replaced by the multi-carbon intermediates, reflecting the strong C\u003csub\u003e2+\u003c/sub\u003e production accordingly. The bands related to symmetric -CH\u003csub\u003e2\u003c/sub\u003e (\u0026nu;\u003csub\u003es\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003e) and -CH\u003csub\u003e3\u003c/sub\u003e (\u0026nu;\u003csub\u003es\u003c/sub\u003eCH\u003csub\u003e3\u003c/sub\u003e) stretching gradually appeared around 2854 and 2930 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb, which further indicated the hydrocarbons generation and consistency with the elevated C\u003csub\u003e2+\u003c/sub\u003e selectivity in highly negative potential.\u003csup\u003e47\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eHowever, Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec showed the weak peaks of intermediates and adsorbates on the OBC and the *CO peak nearly vanished as the applied potential was negative than \u0026minus;\u0026thinsp;0.9 V vs. RHE, which was agreed to its low C\u003csub\u003e2+\u003c/sub\u003e selectivity. The weak *CO and HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e signal can be detected with weak negative potential applied, but they disappeared because of the active site occupation from strong HER.\u003c/p\u003e\n\u003cp\u003eThe \u003cem\u003ein-situ\u003c/em\u003e 2D Raman mapping of OBC-OT and OBC (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed-e) further verified that the reaction intermediates accumulated at the solid-liquid-gas triple-phase interface, and the Raman signal on OBC-OT was stronger than that on OBC. Under the weak negative potential, the intermediate of OBC-OT was mainly the *COOH with strong peak, while intermediates of OBC mainly consisted of CH\u003csub\u003e3\u003c/sub\u003eCOOH, *COOH and *CO with weak peaks. The intermediates are disorderly distributed on the immersed OBC through the 2D Raman mapping (based on the peak intensity of CH\u003csub\u003e3\u003c/sub\u003eCOOH, *COOH and *CO) in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ee. However, the 2D Raman mapping (based on the peak intensity of *COOH) in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed showed the relatively clear shape of the immersed OBC-OT as the *COOH can not be detected in the area below the liquid film.\u003c/p\u003e\n\u003cp\u003eCombining the analysis of the \u003cem\u003ein-situ\u003c/em\u003e Raman measurement and ECSA normalized partial current density of C\u003csub\u003e2+\u003c/sub\u003e products, it can be confirmed that the high local current density and high mass transfer prevail at the triple-phase interface on OBC-OT. The \u003cem\u003ein-situ\u003c/em\u003e Raman further verified that the changes from C\u003csub\u003e1\u003c/sub\u003e products favored to C\u003csub\u003e2+\u003c/sub\u003e products favored with the applied potential negative shift, which was in accord with the CO\u003csub\u003e2\u003c/sub\u003eRR performance in H-type cell. From another perspective, it meant that properly increasing the applied current density can further improve the C\u003csub\u003e2+\u003c/sub\u003e selectivity for OBC-OT.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMicroenvironment evolution.\u003c/strong\u003e According to the previous report,\u003csup\u003e4\u003c/sup\u003e the local pH, which impacted the C\u003csub\u003e2+\u003c/sub\u003e selectivity on catalysts, was significantly affected by the current density. Therefore, it can be reasonably hypothesized that the improved C-C coupling and generation of C\u003csub\u003e2+\u003c/sub\u003e products at the triple-phase interface originated from the large consumption of local protons and local pH increase. To further verify this supposition, we simulated local pH changes along the catalyst surface (plate electrode) at various applied current densities (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ea). The local pH was gradually elevated and reached pH13 with the applied current density was improved to 10 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e. Besides the local pH, the local reactant CO\u003csub\u003e2\u003c/sub\u003e concentration was also an important factor in the HER suppression and C\u003csub\u003e2+\u003c/sub\u003e FE. The modeled local CO\u003csub\u003e2\u003c/sub\u003e concentration profiles in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003eb showed that the local CO\u003csub\u003e2\u003c/sub\u003e concentration was nearly zero at the current density of 15 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e. Due to the limitation of CO\u003csub\u003e2\u003c/sub\u003e mass transfer in typical H-type cells, the excessive current density was not beneficial for CO\u003csub\u003e2\u003c/sub\u003eRR performance, although the high local pH was produced. However, according to the previous report\u003csup\u003e22, 48\u003c/sup\u003e, this kind of hydrophobic microscale and nanoscale surface can trap gas under hydrophobic hairs in water like a spider, which means that the CO\u003csub\u003e2\u003c/sub\u003e mass transfer of OBC-OT can be effectively improved based on its special hydrophobic structure. In addition, the injected CO\u003csub\u003e2\u003c/sub\u003e can be stored in the internal pore of the foam structure and diffuse to the triple-phase interface for the CO\u003csub\u003e2\u003c/sub\u003eRR reaction. During the CO\u003csub\u003e2\u003c/sub\u003eRR test, the CO\u003csub\u003e2\u003c/sub\u003e will be constantly supplied from both the electrolyte and gas chamber of OBC-OT, which is different from the individual CO\u003csub\u003e2\u003c/sub\u003e supply from electrolytes like OBC. Therefore, the special hydrophobic structure of OBC-OT can allow high local CO\u003csub\u003e2\u003c/sub\u003e concentration and high current density for high local pH.\u003c/p\u003e\n\u003cp\u003eOn the other side, it should be emphasized that the practical local current density was influenced by the structure of catalysts, which differed from the current density modeled by the plate electrode or valued from the area of the macroscopic catalyst. Based on the above ECSA and \u003cem\u003ein-situ\u003c/em\u003e Raman result, the obviously higher practical local current density was conducted on OBC-OT than that on OBC. Accordingly, the local pH was directly measured by surface-enhanced Raman spectroscopy (SERS) with pH-sensitive molecules (4-MBA) and further verified the local pH difference with the same applied current density of 5 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ec). The pH at 10 \u0026micro;m of distance to the catalyst surface for OBC-OT reached pH\u0026thinsp;~\u0026thinsp;11, higher than the pH\u0026thinsp;~\u0026thinsp;10 for OBC, which indicated the higher local pH induced by the higher practical local current density.\u003c/p\u003e\n\u003cp\u003eAs shown in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ed, during the process of CO\u003csub\u003e2\u003c/sub\u003eRR on OBC-OT, the reaction only occurred in the area that contacted the electrolyte (catalyst-electrolyte-gas triple-phase interface), and the inside pores of foam were filled with CO\u003csub\u003e2\u003c/sub\u003e. The reaction microenvironment of CO\u003csub\u003e2\u003c/sub\u003eRR evolved to the favored C\u003csub\u003e2+\u003c/sub\u003e products and suppressed HER (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ee). The high local pH was generated with high practical local current density, and simultaneously the CO\u003csub\u003e2\u003c/sub\u003e mass transfer can be efficiently improved by CO\u003csub\u003e2\u003c/sub\u003e supply from both the electrolyte and gas chamber because of its special hydrophobic structure.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eApplication in flow cells.\u003c/strong\u003e According to previous reports\u003csup\u003e49\u0026ndash;53\u003c/sup\u003e, the massive CO\u003csub\u003e2\u003c/sub\u003e assumption caused by the carbonate formation, and the liquid product crossover owing to the anion exchange membrane, reflects a major obstacle of the traditional alkaline or neutral pH electrolytes system for the economical CO\u003csub\u003e2\u003c/sub\u003eRR catalysis. The acid electrolyte and accordingly used Nafion membrane can effectively address the challenges, however, are not beneficial for the multi-carbon production and HER suppression.\u003csup\u003e4, 54, 55\u003c/sup\u003e Therefore, we artfully applied the OBC-OT in flow cells with the acid electrolyte for high C\u003csub\u003e2+\u003c/sub\u003e selectivity and strong HER suppression, as high local pH can be achieved at the thee-phase interface of OBC-OT based on our investigation above (Figure S23a).\u003c/p\u003e\n\u003cp\u003eBased on the villous hydrophobic structure of porous foam, the OBC-OT was directly applied in the flow cells as the cathode without an additional gas-diffusion layer (GDL) as the brief flow-cell configuration showed in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ea. The acid electrolyte of 0.5 M K\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e (pH\u0026thinsp;=\u0026thinsp;4) was employed according to the previous report.\u003csup\u003e4\u003c/sup\u003e The gas diffusion scheme of the CO\u003csub\u003e2\u003c/sub\u003eRR process on OBC-OT with the local pH variation was demonstrated in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003eb. The CO\u003csub\u003e2\u003c/sub\u003e diffused through the porous foam frame and then further diffused across the villous nanowires on OBC-OT, participated in the reaction and led to local pH variation at the triple-phase interface.\u003c/p\u003e\n\u003cp\u003eThe OBC-OT exhibited a high C\u003csub\u003e2+\u003c/sub\u003e FE of 74.4% and low H\u003csub\u003e2\u003c/sub\u003e FE of 6.6% with the current density of 300 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003ed and Figure S22), which further verified the proposed mechanism that the local pH can be elevated for improved C\u003csub\u003e2+\u003c/sub\u003e selectivity and suppress HER even in the acid electrolyte. For comparison, the Cu foam adsorbed with 1-octadecanethiol (Cu-OT) was also investigated in the flow cell (Figure S23b-c). The strong and obvious cathode flooding suggested the necessity of the villous hydrophobic structure on OBC-OT. In addition, the H\u003csub\u003e2\u003c/sub\u003e FE and C\u003csub\u003e2+\u003c/sub\u003e FE on OBC-OT with the current density of 300 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e applied were relatively stable and can be held at 13.5% and 59.5% after the 10 h operation, respectively, which further demonstrated the application prospect of OBC-OT.\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eIn summary, a hydrophobic oxide-derived copper foam with villous nanowires on the surface has been constructed, representing significant improvement on HER suppression and C\u003csub\u003e2+\u003c/sub\u003e selectivity for the CO\u003csub\u003e2\u003c/sub\u003eRR performance in H-type cell. The \u003cem\u003ein-situ\u003c/em\u003e 3D Raman mapping was adopted to probe the catalyst-electrolyte-gas triple-phase interface and indicated the significant increase of reactants and local current density at the triple-phase interface. Besides, the \u003cem\u003ein-situ\u003c/em\u003e Raman spectra further verified the variations from C\u003csub\u003e1\u003c/sub\u003e preferred to C\u003csub\u003e2+\u003c/sub\u003e preferred with the applied potential negative shifted or current density increased, which was consistent with the CO\u003csub\u003e2\u003c/sub\u003eRR performance and TPD results. Combining the measurements and simulations of micro-environmental species, high local pH and CO\u003csub\u003e2\u003c/sub\u003e mass transfer can be simultaneously allowed in the microenvironment of the triple-phase interface based on the special hydrophobic structure, being the internal mechanism of the high C\u003csub\u003e2+\u003c/sub\u003e selectivity and HER suppression. Therefore, on this mechanism, both the low HER of 6.6% and high C\u003csub\u003e2+\u003c/sub\u003e selectivity of 74.4% were achieved in the flow cell under acidic conditions at the current density of 300 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e without an additional gas-diffusion layer (GDL). This work provides valuable theoretical insights for the design of catalysts and catalytic devices and opens up promising opportunities for the application of metal foam-based GDEs without fragility.\u003c/p\u003e"},{"header":"Methods","content":"\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\n \u003cp\u003e\u003cstrong\u003eChemicals\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eCopper foam (0.3 mm, \u0026gt;\u0026thinsp;99.99%), copper foil (0.3 mm, \u0026gt;\u0026thinsp;99.99%), sodium hydroxide (NaOH, Aladdin, \u0026ge;\u0026thinsp;99%), ammonium persulfate ((NH\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e, Aladdin, \u0026ge;\u0026thinsp;99%), 1-octadecanethiol (C\u003csub\u003e18\u003c/sub\u003eH\u003csub\u003e38\u003c/sub\u003eS, Macklin, \u0026ge;\u0026thinsp;99%), potassium bicarbonate (KHCO\u003csub\u003e3\u003c/sub\u003e, Macklin, \u0026ge;\u0026thinsp;99.5%), ethanol (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eOH, Sinoreagent, AR), carbon dioxide (CO\u003csub\u003e2\u003c/sub\u003e, 99.99%), argon (Ar, 99.999%), nitrogen (N\u003csub\u003e2\u003c/sub\u003e, 99.999%), 4-mercaptobenzoic acid (4-MBA, Aladdin, \u0026ge;\u0026thinsp;99%), silver nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e, Aladdin, \u0026ge;\u0026thinsp;99.9%). chloroauric acid (HAuCl\u003csub\u003e4\u003c/sub\u003e, Aladdin, \u0026ge;\u0026thinsp;99.9%), sodium citrate (Aladdin, \u0026ge;\u0026thinsp;99.9%), ascorbic acid (Aladdin, \u0026ge;\u0026thinsp;99.9%).\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\n \u003cp\u003e\u003cstrong\u003eCatalyst Preparation\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eSynthesis of OBC materials\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe CuO nanowires were synthesized by annealing method from Cu(OH)\u003csub\u003e2\u003c/sub\u003e nanowires according to a previously reported procedure.\u003csup\u003e56\u003c/sup\u003e In a typical synthesis, the Cu foam (1 mm\u0026times;0.5 mm) was cleaned by hydrochloric acid solution (1 M), acetone, ethanol and distilled water in sequence, then the cleaned Cu foam was immediately soaked into the mixture solution with 4.8g NaOH, 2.28g (NH\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e and distilled water (100 mL) at 3℃ for 30 min. After that, the Cu foam turned to blue and a layer of Cu(OH)\u003csub\u003e2\u003c/sub\u003e nanowires was obtained on the surface after it was thoroughly rinsed with distilled water and dried in 60℃. The black CuO MPNWs were prepared after the Cu foam with a layer of Cu(OH)\u003csub\u003e2\u003c/sub\u003e nanowires was annealed in air at a preset temperature of 180\u0026deg;C for 1 h. The CuO MPNWs were used as the pre-catalysts and they were reduced to dark-red OBC materials in the 0.1M KHCO\u003csub\u003e3\u003c/sub\u003e aqueous solution with the potential of -1.0 V (vs. RHE) for 10 min before the CO\u003csub\u003e2\u003c/sub\u003e reduction test.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eSynthesis of OBC-OT/OBC-sOT materials\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe OBC-OT materials were synthesized by the functionalization of OBC materials with 1-octadecanethiol. The OBC materials were soaked in the Ar-saturated ethyl acetate solution with 10 wt% (0.01wt%) 1-octadecanethiol at room temperature for 30 min (2 min). The processed OBC materials were removed to ethyl acetate to clean the residual 1-octadecanethiol molecules which were not strongly absorbed on the OBC materials, and dried with nitrogen to obtain the OBC-OT (OBC-sOT) materials.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\n \u003ch2\u003eMaterials Characterization\u003c/h2\u003e\n \u003cp\u003eSEM and EDS measurements were performed on a scanning electron microscope (G500). The HRTEM data were obtained on a Field Emission Transmission Electron Microscope (Tecnai F30). The Raman spectroscopy was tested by a Laser confocal Raman Spectrometer (Renishaw). The X-ray photoelectron spectroscopy (XPS) was measured by the instrument ESCALAB and the X-ray diffraction (XRD) measurement was conducted by an X-ray diffractometer (SmartLab). A Kelvin probe force microscopy (KPFM, Bruker) was used to study the morphology and surface potential properties variation of the catalyst. The quantification of solution-phase and gas-phase products was carried out by nuclear magnetic resonance (NMR) spectroscopy (Figure S14) and gas chromatography (GC) (Figure S15), respectively.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e\u003cem\u003eIn-situ\u003c/em\u003e Raman spectra tests\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe \u003cem\u003ein-situ\u003c/em\u003e Raman spectra were measured via a homemade electrolytic cell with CO\u003csub\u003e2\u003c/sub\u003e-saturated 0.1 M KHCO3 aqueous solution flowing inside. This electrolytic cell was connected to the electrochemical station with a triple-electrode system, and the prepared electrode with catalysts, Ag/AgCl electrode, and Pt wire were used as work electrode, reference electrode, and counter electrode, respectively. The reduction process of the CuO MPNWs to OBC materials was monitored at the excitation laser source of 532 nm. The reaction intermediates of the CO\u003csub\u003e2\u003c/sub\u003eRR process were monitored at the excitation laser source of 785 nm.\u003csup\u003e57\u003c/sup\u003e The measured potentials were converted to V versus RHE (E\u003csub\u003eRHE\u003c/sub\u003e = E\u003csub\u003eAg/AgCl\u003c/sub\u003e + 0.197 V\u0026thinsp;+\u0026thinsp;0.0591 V \u0026times; pH) without the iR\u003csub\u003es\u003c/sub\u003e compensation.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\n \u003ch2\u003eElectrochemical measurements\u003c/h2\u003e\n \u003cp\u003eElectrochemical properties and CO\u003csub\u003e2\u003c/sub\u003eRR performance in H-type electrochemical cell were measured with three electrode system. The prepared electrode, Ag/AgCl electrode, and platinum nets electrode were used as the working, reference, and counter electrodes, respectively. The CO\u003csub\u003e2\u003c/sub\u003e-saturated 0.1 M KHCO\u003csub\u003e3\u003c/sub\u003e aqueous solution (pH\u0026sim;6.8) was used as the electrolyte and the cathode and anode chamber of the H-type electrochemical cell were separated by an anion exchange membrane (FAA-3-50). The measured potentials were converted to V versus RHE (E\u003csub\u003eRHE\u003c/sub\u003e = E\u003csub\u003eAg/AgCl\u003c/sub\u003e + 0.197 V\u0026thinsp;+\u0026thinsp;0.0591 V \u0026times; pH ‒ iR\u003csub\u003es\u003c/sub\u003e).\u003csup\u003e58\u003c/sup\u003e The R\u003csub\u003es\u003c/sub\u003e was the resistance of the electrolyte solution between the working and reference electrode, which was measured by the impedance method.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e\n \u003ch2\u003eFlow cell application test\u003c/h2\u003e\n \u003cp\u003eThe application of materials in the flow cell (Figure S23) was conducted with the acid electrolyte of 0.5 M K\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e (pH\u0026thinsp;=\u0026thinsp;4) solution. Three pieces of OBC-OT were stacked to avoid the cathode flooding and used as the working electrode without any other gas diffusion attachment because of its hydrophobic and porous properties. The Ag/AgCl electrode and platinum nets electrode were used as the reference and counter electrodes, respectively. The cathode and anode chambers were separated with the Nafion membrane (N211) in between. The liquid flow rate in the cathode and anode chamber was 3 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 40 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. The CO\u003csub\u003e2\u003c/sub\u003e flow rate was set as 30 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eECSA measurements\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe Electrochemical Active Surface area (ECSA) was evaluated by the double-layer capacitance (C\u003csub\u003edl\u003c/sub\u003e). The CV curves were taken over a range of scan rates (20, 40, 60, 80, and 100 mV/s), and the potential range was 0.15 V to 0.25 V vs. RHE.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eGC analysis\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe gas products were quantified by a gas chromatography (GC9790plus, FULI INSTRUMENTS) connecting to the cathode chamber of the electrochemical cell, which can automatically sample at the set time. The gas chromatography used Argon as the carrier gas, and it was calibrated by the standard curves obtained from a series of concentrations of the standard gas mixture. The CO\u003csub\u003e2\u003c/sub\u003e was sparged into the cathode chamber by a mass flow controller (Sevenstar) and the electrolyte was stirred (600 rpm). With the online measurement system, the gas products were typically sampled at 15, 35 and 55 min.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e\u003csup\u003e1\u003c/sup\u003eH NMR spectroscopy\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe liquid components were analyzed by \u003csup\u003e1\u003c/sup\u003eH NMR spectroscopy undertaken with a Bruker Avance III 400 MHz spectrometer. During the NMR test, the mixture solution containing 500 \u0026micro;L electrolyte after the CO\u003csub\u003e2\u003c/sub\u003eRR test, 100 \u0026micro;L D\u003csub\u003e2\u003c/sub\u003eO, and 100 \u0026micro;L DMSO aqueous solution (10 ppm, volume/volume) was added to the NMR tube for quantification. A Pre-SAT180 water suppression method was used to diminish the effect of the excessively strong water peak of each spectrum. The standard curve of each liquid product was fitted to quantify the concentration of liquid production before the CO\u003csub\u003e2\u003c/sub\u003eRR tests.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eFaradaic Efficiency calculation\u003c/strong\u003e: The Faradaic Efficiency of different gas components was calculated by the following method: FE\u003csub\u003ej\u003c/sub\u003e = (nFV\u003csub\u003eg\u003c/sub\u003e\u0026nu;p\u003csub\u003e0\u003c/sub\u003e)/(RT\u003csub\u003e0\u003c/sub\u003eI\u003csub\u003etotal\u003c/sub\u003e), where n is the electron transfer number from the CO\u003csub\u003e2\u003c/sub\u003e to its reduced gas product; F means the Faraday Constant (96485 C/mol); V\u003csub\u003eg\u003c/sub\u003e is the flow rate of CO\u003csub\u003e2\u003c/sub\u003e; \u003cem\u003e\u0026nu;\u003c/em\u003e is the gas component concentration quantified by the gas chromatography; R is the universal gas constant (8.314 J/mol\u0026middot;K); the p\u003csub\u003e0\u003c/sub\u003e and T\u003csub\u003e0\u003c/sub\u003e mean the pressure and temperature during the electrochemical catalytic reduction process; I\u003csub\u003etotal\u003c/sub\u003e is the averaged current over the whole test period. The Faradaic Efficiency of different liquid products was calculated by the following method: FE\u003csub\u003ej\u003c/sub\u003e=nFVC/Q, where n means electron transfer number from the CO\u003csub\u003e2\u003c/sub\u003e to its reduced liquid product; F is the Faraday constant (96485 C/mol); V means the volume of the electrolyte for cathode; C is the liquid component concentration calculated from the standard curve; Q means the total passed charge (C) during the whole electrochemical catalytic test period.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eIn-situ\u003c/strong\u003e \u003cstrong\u003elocal pH measurement\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe \u003cem\u003ein-situ\u003c/em\u003e local pH was tested via Raman signal of the pH-sensitive molecules (4-MBA) on the prepared SERS substrates (Figure S21a). The electrode was separated with the SERS substrate through a very thin insulating layer. As the potential was applied to the electrode, the local pH was varied and the peaks of 1372 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (\u0026nu;COO\u003csup\u003e\u0026minus;\u003c/sup\u003e) and 1633 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (\u0026nu;C\u0026thinsp;=\u0026thinsp;O) were sensed (Figure S21b). Before the pH detection, we made the standard curve based on the peak area ratio of 1372 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1633 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Figure S21c). The laser was 532 nm and the line image mode was used for local pH detection.\u003c/p\u003e\n \u003cp\u003eThe pH-sensitive SERS substrates were prepared according to previous reports.\u003csup\u003e59, 60\u003c/sup\u003e The 1.28 mL sodium citrate solution (1 wt%) was rapidly added to the boiling mixture of 31.6 mL distilled water and 390.4 \u0026micro;L HAuCl\u003csub\u003e4\u003c/sub\u003e (1 wt%), and then the Au seeds were obtained after the 30 min heating reflux. The Au@Ag soliquid was synthesized via the dropwise addition of the 2.5 mL AgNO\u003csub\u003e3\u003c/sub\u003e solution to the mixture of 32 mL distilled water, 2 mL sodium citrate (1 wt%), 630 \u0026micro;L ascorbic acid (0.1 M), and 930 \u0026micro;L Au seeds solution for 30 min. A piece of gold-plated silicon wafer was immerged in the 4-MBA solution (ethanol, 10 mM) for 24 h and then washed with massive ethanol to get the 4-MBA adsorbed gold-plated silicon wafer. Then the Au@Ag soliquid (concentrated 20 times) was dropped on the 4-MBA adsorbed gold-plated silicon wafer and dried for 12 h naturally. The obtained sample was immerged in the 4-MBA solution (ethanol, 10 mM) for 24 h, and then cleaned the dissociative 4-MBA with ethanol to gain the pH-sensitive SERS substrate.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\n \u003ch2\u003eCOMSOL simulation\u003c/h2\u003e\n \u003cp\u003eThe local pH and CO\u003csub\u003e2\u003c/sub\u003e concentration profiles were simulated with COMSOL (COMSOL Multiphysics v5.6, Stockholm, Se) based on previous publications\u003csup\u003e4, 24\u003c/sup\u003e. Two-dimensional (2D) domain (20 \u0026micro;m*100 \u0026micro;m) including the electrode surface in the left boundary (x\u0026thinsp;=\u0026thinsp;0 \u0026micro;m) and the bulk solution in the right boundary (100 \u0026micro;m) was used for simulation. The zero flux of aqueous species was set in the top and bottom boundaries. The model considered the acid-base equilibria (equations 1\u0026ndash;5) of CO\u003csub\u003e2\u003c/sub\u003e hydrolysis reactions:\u003c/p\u003e\n \u003cp\u003e\u003cimg 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\"\u003e\u003cbr\u003ewhere j meant the current density applied; F was the Faraday\u0026rsquo;s constant; \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({F}_{{CO}_{2}RR}\\)\u003c/span\u003e\u003c/span\u003e and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({F}_{HER}\\)\u003c/span\u003e\u003c/span\u003e meant the Faradaic efficiencies of the CO\u003csub\u003e2\u003c/sub\u003eRR and HER, respectively, which were set as 70% and 30%, respectively; \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({n}_{{CO}_{2}RR}\\)\u003c/span\u003e\u003c/span\u003e and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({n}_{HER}\\)\u003c/span\u003e\u003c/span\u003e was the number of electrons required for the reduction reaction. The \u0026ldquo;eps\u0026rdquo; was added to the code to avoid zero or negative concentration. The model parameters are listed in Table \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e.\u003c/p\u003e\u003c/div\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData Availability Statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe data that support the findings of this study are available from the corresponding author upon reasonable request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was financially supported by the National Natural Science Foundation of China (22172196, 21902188), the Guangxi Science and Technology Program (AD21220067), Natural Science Foundation of Guangxi Province (2022GXNSFAA035467).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u0026nbsp;Author contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eY. T. and K.W. supervised this this project. Z. X., J. Y and H. Yperformed most of the experiments and analyzed the experimental data. Q. W. and J. C helped with the physical characterization and data analysis. S. S., C. M., and K.W. \u0026nbsp;helped with visualization. Z. X., J. Y and K.W. wrote and revised the manuscript. All authors discussed the results and assisted during manuscript preparation.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interest\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing financial interest.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eObama, B., The irreversible momentum of clean energy. \u003cem\u003eScience \u003c/em\u003e\u003cstrong\u003e2017,\u003c/strong\u003e \u003cem\u003e355\u003c/em\u003e (6321), 126-129.\u003c/li\u003e\n\u003cli\u003eBirdja, Y. Y.; P\u0026eacute;rez-Gallent, E.; Figueiredo, M. C.; G\u0026ouml;ttle, A. J.; Calle-Vallejo, F.; Koper, M. T. M., Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels. \u003cem\u003eNature Energy \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e4\u003c/em\u003e (9), 732-745.\u003c/li\u003e\n\u003cli\u003eWang, G.; Chen, J.; Ding, Y.; Cai, P.; Yi, L.; Li, Y.; Tu, C.; Hou, Y.; Wen, Z.; Dai, L., Electrocatalysis for CO\u003csub\u003e2\u003c/sub\u003e conversion: from fundamentals to value-added products. \u003cem\u003eChemical Society Reviews \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e50\u003c/em\u003e (8), 4993-5061.\u003c/li\u003e\n\u003cli\u003eXie, Y.; Ou, P.; Wang, X.; Xu, Z.; Li, Y. C.; Wang, Z.; Huang, J. E.; Wicks, J.; McCallum, C.; Wang, N.; Wang, Y.; Chen, T.; Lo, B. T. W.; Sinton, D.; Yu, J. C.; Wang, Y.; Sargent, E. H., High carbon utilization in CO\u003csub\u003e2\u003c/sub\u003e reduction to multi-carbon products in acidic media. \u003cem\u003eNature Catalysis \u003c/em\u003e\u003cstrong\u003e2022,\u003c/strong\u003e \u003cem\u003e5\u003c/em\u003e (6), 564-570.\u003c/li\u003e\n\u003cli\u003eLi, F.; Li, Y. C.; Wang, Z.; Li, J.; Nam, D.-H.; Lum, Y.; Luo, M.; Wang, X.; Ozden, A.; Hung, S.-F.; Chen, B.; Wang, Y.; Wicks, J.; Xu, Y.; Li, Y.; Gabardo, C. M.; Dinh, C.-T.; Wang, Y.; Zhuang, T.-T.; Sinton, D.; Sargent, E. H., Cooperative CO\u003csub\u003e2\u003c/sub\u003e-to-ethanol conversion via enriched intermediates at molecule\u0026ndash;metal catalyst interfaces. \u003cem\u003eNature Catalysis \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e3\u003c/em\u003e (1), 75-82.\u003c/li\u003e\n\u003cli\u003ePang, Y.; Li, J.; Wang, Z.; Tan, C.-S.; Hsieh, P.-L.; Zhuang, T.-T.; Liang, Z.-Q.; Zou, C.; Wang, X.; De Luna, P.; Edwards, J. P.; Xu, Y.; Li, F.; Dinh, C.-T.; Zhong, M.; Lou, Y.; Wu, D.; Chen, L.-J.; Sargent, E. H.; Sinton, D., Efficient electrocatalytic conversion of carbon monoxide to propanol using fragmented copper. \u003cem\u003eNature Catalysis \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e2\u003c/em\u003e (3), 251-258.\u003c/li\u003e\n\u003cli\u003eWang, X.; Wang, Z.; Zhuang, T.-T.; Dinh, C.-T.; Li, J.; Nam, D.-H.; Li, F.; Huang, C.-W.; Tan, C.-S.; Chen, Z.; Chi, M.; Gabardo, C. M.; Seifitokaldani, A.; Todorović, P.; Proppe, A.; Pang, Y.; Kirmani, A. R.; Wang, Y.; Ip, A. H.; Richter, L. J.; Scheffel, B.; Xu, A.; Lo, S.-C.; Kelley, S. O.; Sinton, D.; Sargent, E. H., Efficient upgrading of CO to C\u003csub\u003e3\u003c/sub\u003e fuel using asymmetric C-C coupling active sites. \u003cem\u003eNature Communications \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e10\u003c/em\u003e (1), 5186.\u003c/li\u003e\n\u003cli\u003eWu, Z. Z.; Zhang, X. L.; Niu, Z. Z.; Gao, F. Y.; Yang, P. P.; Chi, L. P.; Shi, L.; Wei, W. S.; Liu, R.; Chen, Z.; Hu, S.; Zheng, X.; Gao, M. R., Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO\u003csub\u003e2\u003c/sub\u003e Electroreduction. \u003cem\u003eJournal of the American Chemical Society \u003c/em\u003e\u003cstrong\u003e2022,\u003c/strong\u003e \u003cem\u003e144\u003c/em\u003e (1), 259-269.\u003c/li\u003e\n\u003cli\u003eGarza, A. J.; Bell, A. T.; Head-Gordon, M., Mechanism of CO\u003csub\u003e2\u003c/sub\u003e Reduction at Copper Surfaces: Pathways to C\u003csub\u003e2\u003c/sub\u003e Products. \u003cem\u003eACS Catalysis \u003c/em\u003e\u003cstrong\u003e2018,\u003c/strong\u003e \u003cem\u003e8\u003c/em\u003e (2), 1490-1499.\u003c/li\u003e\n\u003cli\u003eKim, C.; Cho, K. M.; Park, K.; Kim, J. Y.; Yun, G. T.; Toma, F. M.; Gereige, I.; Jung, H. T., Cu/Cu\u003csub\u003e2\u003c/sub\u003eO interconnected porous aerogel catalyst for highly productive electrosynthesis of ethanol from CO\u003csub\u003e2\u003c/sub\u003e. \u003cem\u003eAdvanced Functional Materials \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e31\u003c/em\u003e (32), 2102142.\u003c/li\u003e\n\u003cli\u003eXing, Z.; Hu, L.; Ripatti, D. S.; Hu, X.; Feng, X., Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment. \u003cem\u003eNature Communications \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e12\u003c/em\u003e (1), 136.\u003c/li\u003e\n\u003cli\u003eGarg, S.; Li, M.; Weber, A. Z.; Ge, L.; Li, L.; Rudolph, V.; Wang, G.; Rufford, T. E., Advances and challenges in electrochemical CO\u003csub\u003e2\u003c/sub\u003e reduction processes: an engineering and design perspective looking beyond new catalyst materials. \u003cem\u003eJournal of Materials Chemistry A \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e8\u003c/em\u003e (4), 1511-1544.\u003c/li\u003e\n\u003cli\u003eTan, Y. C.; Lee, K. B.; Song, H.; Oh, J., Modulating Local CO\u003csub\u003e2\u003c/sub\u003e Concentration as a General Strategy for Enhancing C\u0026minus;C Coupling in CO\u003csub\u003e2\u003c/sub\u003e Electroreduction. \u003cem\u003eJoule \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e4\u003c/em\u003e (5), 1104-1120.\u003c/li\u003e\n\u003cli\u003eHiggins, D.; Hahn, C.; Xiang, C.; Jaramillo, T. F.; Weber, A. Z., Gas-Diffusion Electrodes for Carbon Dioxide Reduction: A New Paradigm. \u003cem\u003eACS Energy Letters \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e4\u003c/em\u003e (1), 317-324.\u003c/li\u003e\n\u003cli\u003eNam, D.-H.; De Luna, P.; Rosas-Hern\u0026aacute;ndez, A.; Thevenon, A.; Li, F.; Agapie, T.; Peters, J. C.; Shekhah, O.; Eddaoudi, M.; Sargent, E. H., Molecular enhancement of heterogeneous CO\u003csub\u003e2\u003c/sub\u003e reduction. \u003cem\u003eNature Materials \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e19\u003c/em\u003e (3), 266-276.\u003c/li\u003e\n\u003cli\u003eLi, R.; Xiang, K.; Peng, Z.; Zou, Y.; Wang, S., Recent Advances on Electrolysis for Simultaneous Generation of Valuable Chemicals at both Anode and Cathode. \u003cem\u003eAdvanced Energy Materials \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e11\u003c/em\u003e (46), 2102292.\u003c/li\u003e\n\u003cli\u003eK\u0026ouml;nig, M.; Vaes, J.; Klemm, E.; Pant, D., Solvents and Supporting Electrolytes in the Electrocatalytic Reduction of CO\u003csub\u003e2\u003c/sub\u003e. \u003cem\u003eiScience \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e19\u003c/em\u003e, 135-160.\u003c/li\u003e\n\u003cli\u003eTao, Z.; Rooney, C. L.; Liang, Y.; Wang, H., Accessing Organonitrogen Compounds via C\u0026ndash;N Coupling in Electrocatalytic CO\u003csub\u003e2\u003c/sub\u003e Reduction. \u003cem\u003eJournal of the American Chemical Society \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e143\u003c/em\u003e (47), 19630-19642.\u003c/li\u003e\n\u003cli\u003eXing, Z.; Hu, X.; Feng, X., Tuning the Microenvironment in Gas-Diffusion Electrodes Enables High-Rate CO\u003csub\u003e2\u003c/sub\u003e Electrolysis to Formate. \u003cem\u003eACS Energy Letters \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e6\u003c/em\u003e (5), 1694-1702.\u003c/li\u003e\n\u003cli\u003eZhang, F.; Co, A. C., Direct Evidence of Local pH Change and the Role of Alkali Cation during CO2 Electroreduction in Aqueous Media. \u003cem\u003eAngewandte Chemie International Edition \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e59\u003c/em\u003e (4), 1674-1681.\u003c/li\u003e\n\u003cli\u003eSa, Y. J.; Lee, C. W.; Lee, S. Y.; Na, J.; Lee, U.; Hwang, Y. J., Catalyst\u0026ndash;electrolyte interface chemistry for electrochemical CO\u003csub\u003e2\u003c/sub\u003e reduction. \u003cem\u003eChemical Society Reviews \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e49\u003c/em\u003e (18), 6632-6665.\u003c/li\u003e\n\u003cli\u003eWakerley, D.; Lamaison, S.; Ozanam, F.; Menguy, N.; Mercier, D.; Marcus, P.; Fontecave, M.; Mougel, V., Bio-inspired hydrophobicity promotes CO\u003csub\u003e2\u003c/sub\u003e reduction on a Cu surface. \u003cem\u003eNature Materials \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e18\u003c/em\u003e (11), 1222-1227.\u003c/li\u003e\n\u003cli\u003eGarc\u0026iacute;a de Arquer, F. P.; Dinh, C.-T.; Ozden, A.; Wicks, J.; McCallum, C.; Kirmani, A. R.; Nam, D.-H.; Gabardo, C.; Seifitokaldani, A.; Wang, X.; Li, Y. C.; Li, F.; Edwards, J.; Richter, L. J.; Thorpe, S. J.; Sinton, D.; Sargent, E. H., CO\u003csub\u003e2\u003c/sub\u003e electrolysis to multicarbon products at activities greater than 1 A cm\u003csup\u003e\u0026minus;2\u003c/sup\u003e. \u003cem\u003eScience \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e367\u003c/em\u003e (6478), 661-666.\u003c/li\u003e\n\u003cli\u003eDinh, C.-T.; Burdyny, T.; Kibria, M. G.; Seifitokaldani, A.; Gabardo, C. M.; Garc\u0026iacute;a de Arquer, F. P.; Kiani, A.; Edwards, J. P.; De Luna, P.; Bushuyev, O. S.; Zou, C.; Quintero-Bermudez, R.; Pang, Y.; Sinton, D.; Sargent, E. H., CO\u003csub\u003e2\u003c/sub\u003e electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. \u003cem\u003eScience \u003c/em\u003e\u003cstrong\u003e2018,\u003c/strong\u003e \u003cem\u003e360\u003c/em\u003e (6390), 783-787.\u003c/li\u003e\n\u003cli\u003eWang, Y.; Zou, Y.; Tao, L.; Wang, Y.; Huang, G.; Du, S.; Wang, S., Rational design of three-phase interfaces for electrocatalysis. \u003cem\u003eNano Research \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e12\u003c/em\u003e (9), 2055-2066.\u003c/li\u003e\n\u003cli\u003eZhang, W.; Huang, C.; Xiao, Q.; Yu, L.; Shuai, L.; An, P.; Zhang, J.; Qiu, M.; Ren, Z.; Yu, Y., Atypical Oxygen-Bearing Copper Boosts Ethylene Selectivity toward Electrocatalytic CO\u003csub\u003e2\u003c/sub\u003e Reduction. \u003cem\u003eJournal of the American Chemical Society \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e142\u003c/em\u003e (26), 11417-11427.\u003c/li\u003e\n\u003cli\u003eYu, L.; Zhou, H.; Sun, J.; Qin, F.; Yu, F.; Bao, J.; Yu, Y.; Chen, S.; Ren, Z., Cu nanowires shelled with NiFe layered double hydroxide nanosheets as bifunctional electrocatalysts for overall water splitting. \u003cem\u003eEnergy \u0026amp; Environmental Science \u003c/em\u003e\u003cstrong\u003e2017,\u003c/strong\u003e \u003cem\u003e10\u003c/em\u003e (8), 1820-1827.\u003c/li\u003e\n\u003cli\u003eZhong, D.; Zhao, Z.-J.; Zhao, Q.; Cheng, D.; Liu, B.; Zhang, G.; Deng, W.; Dong, H.; Zhang, L.; Li, J.; Li, J.; Gong, J., Coupling of Cu(100) and (110) Facets Promotes Carbon Dioxide Conversion to Hydrocarbons and Alcohols. \u003cem\u003eAngewandte Chemie International Edition \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e133\u003c/em\u003e (9), 4929-4935.\u003c/li\u003e\n\u003cli\u003eDilimon, V. S.; Denayer, J.; Delhalle, J.; Mekhalif, Z., Electrochemical and Spectroscopic Study of the Self-Assembling Mechanism of Normal and Chelating Alkanethiols on Copper. \u003cem\u003eLangmuir \u003c/em\u003e\u003cstrong\u003e2012,\u003c/strong\u003e \u003cem\u003e28\u003c/em\u003e (17), 6857-6865.\u003c/li\u003e\n\u003cli\u003eWang, Y.; Im, J.; Soares, J. W.; Steeves, D. M.; Whitten, J. E., Thiol Adsorption on and Reduction of Copper Oxide Particles and Surfaces. \u003cem\u003eLangmuir \u003c/em\u003e\u003cstrong\u003e2016,\u003c/strong\u003e \u003cem\u003e32\u003c/em\u003e (16), 3848-3857.\u003c/li\u003e\n\u003cli\u003eLi, H.; Liu, T.; Wei, P.; Lin, L.; Gao, D.; Wang, G.; Bao, X., High-Rate CO\u003csub\u003e2\u003c/sub\u003e Electroreduction to C\u003csub\u003e2+\u003c/sub\u003e Products over a Copper-Copper Iodide Catalyst. \u003cem\u003eAngewandte Chemie International Edition \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e60\u003c/em\u003e (26), 14329-14333.\u003c/li\u003e\n\u003cli\u003eYang, Y.; Zhang, X.; Kanchanakungwankul, S.; Lu, Z.; Noh, H.; Syed, Z. H.; Farha, O. K.; Truhlar, D. G.; Hupp, J. T., Unexpected \u0026ldquo;Spontaneous\u0026rdquo; Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles. \u003cem\u003eJournal of the American Chemical Society \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e142\u003c/em\u003e (50), 21169-21177.\u003c/li\u003e\n\u003cli\u003eScholten, F.; Nguyen, K.-L. C.; Bruce, J. P.; Heyde, M.; Roldan Cuenya, B., Identifying Structure\u0026ndash;Selectivity Correlations in the Electrochemical Reduction of CO\u003csub\u003e2\u003c/sub\u003e: A Comparison of Well-Ordered Atomically Clean and Chemically Etched Copper Single-Crystal Surfaces. \u003cem\u003eAngewandte Chemie International Edition \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e60\u003c/em\u003e (35), 19169-19175.\u003c/li\u003e\n\u003cli\u003eJia, Y.; Zhang, L.; Zhuang, L.; Liu, H.; Yan, X.; Wang, X.; Liu, J.; Wang, J.; Zheng, Y.; Xiao, Z.; Taran, E.; Chen, J.; Yang, D.; Zhu, Z.; Wang, S.; Dai, L.; Yao, X., Identification of active sites for acidic oxygen reduction on carbon catalysts with and without nitrogen doping. \u003cem\u003eNature Catalysis \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e2\u003c/em\u003e (8), 688-695.\u003c/li\u003e\n\u003cli\u003eKim, J.-H.; Hwang, J. H.; Suh, J.; Tongay, S.; Kwon, S.; Hwang, C. C.; Wu, J.; Young Park, J., Work function engineering of single layer graphene by irradiation-induced defects. \u003cem\u003eApplied Physics Letters \u003c/em\u003e\u003cstrong\u003e2013,\u003c/strong\u003e \u003cem\u003e103\u003c/em\u003e (17), 171604.\u003c/li\u003e\n\u003cli\u003eLin, L.; Li, H.; Wang, Y.; Li, H.; Wei, P.; Nan, B.; Si, R.; Wang, G.; Bao, X., Temperature-Dependent CO\u003csub\u003e2\u003c/sub\u003e Electroreduction over Fe-N-C and Ni-N-C Single-Atom Catalysts. \u003cem\u003eAngewandte Chemie International Edition \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e60\u003c/em\u003e (51), 26582-26586.\u003c/li\u003e\n\u003cli\u003eWang, Q.; Liu, K.; Fu, J.; Cai, C.; Li, H.; Long, Y.; Chen, S.; Liu, B.; Li, H.; Li, W.; Qiu, X.; Zhang, N.; Hu, J.; Pan, H.; Liu, M., Atomically Dispersed s-Block Magnesium Sites for Electroreduction of CO\u003csub\u003e2\u003c/sub\u003e to CO. \u003cem\u003eAngewandte Chemie International Edition \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e60\u003c/em\u003e (48), 25241-25245.\u003c/li\u003e\n\u003cli\u003eBagger, A.; Ju, W.; Varela, A. S.; Strasser, P.; Rossmeisl, J., Electrochemical CO\u003csub\u003e2\u003c/sub\u003e Reduction: Classifying Cu Facets. \u003cem\u003eACS Catalysis \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e9\u003c/em\u003e (9), 7894-7899.\u003c/li\u003e\n\u003cli\u003eFeng, J.; Zhang, L.; Liu, S.; Xu, L.; Ma, X.; Tan, X.; Wu, L.; Qian, Q.; Wu, T.; Zhang, J.; Sun, X.; Han, B., Modulating adsorbed hydrogen drives electrochemical CO\u003csub\u003e2\u003c/sub\u003e-to-C\u003csub\u003e2\u003c/sub\u003e products. \u003cem\u003eNature Communications \u003c/em\u003e\u003cstrong\u003e2023,\u003c/strong\u003e \u003cem\u003e14\u003c/em\u003e (1), 4615.\u003c/li\u003e\n\u003cli\u003eZhou, Y.; Che, F.; Liu, M.; Zou, C.; Liang, Z.; De Luna, P.; Yuan, H.; Li, J.; Wang, Z.; Xie, H.; Li, H.; Chen, P.; Bladt, E.; Quintero-Bermudez, R.; Sham, T.-K.; Bals, S.; Hofkens, J.; Sinton, D.; Chen, G.; Sargent, E. H., Dopant-induced electron localization drives CO\u003csub\u003e2\u003c/sub\u003e reduction to C\u003csub\u003e2\u003c/sub\u003e hydrocarbons. \u003cem\u003eNature Chemistry \u003c/em\u003e\u003cstrong\u003e2018,\u003c/strong\u003e \u003cem\u003e10\u003c/em\u003e (9), 974-980.\u003c/li\u003e\n\u003cli\u003eZhao, Y.; Zhang, X.-G.; Bodappa, N.; Yang, W.-M.; Liang, Q.; Radjenovica, P. M.; Wang, Y.-H.; Zhang, Y.-J.; Dong, J.-C.; Tian, Z.-Q.; Li, J.-F., Elucidating electrochemical CO\u003csub\u003e2\u003c/sub\u003e reduction reaction processes on Cu(hkl) single-crystal surfaces by in situ Raman spectroscopy. \u003cem\u003eEnergy \u0026amp; Environmental Science \u003c/em\u003e\u003cstrong\u003e2022,\u003c/strong\u003e \u003cem\u003e15\u003c/em\u003e (9), 3968-3977.\u003c/li\u003e\n\u003cli\u003eGong, S.; Niu, Y.; Liu, X.; Xu, C.; Chen, C.; Meyer, T. J.; Chen, Z., Selective CO\u003csub\u003e2\u003c/sub\u003e Photoreduction to Acetate at Asymmetric Ternary Bridging Sites. \u003cem\u003eACS Nano \u003c/em\u003e\u003cstrong\u003e2023,\u003c/strong\u003e \u003cem\u003e17\u003c/em\u003e (5), 4922-4932.\u003c/li\u003e\n\u003cli\u003eGao, D.; Ar\u0026aacute;n-Ais, R. M.; Jeon, H. S.; Roldan Cuenya, B., Rational catalyst and electrolyte design for CO\u003csub\u003e2\u003c/sub\u003e electroreduction towards multicarbon products. \u003cem\u003eNature Catalysis \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e2\u003c/em\u003e (3), 198-210.\u003c/li\u003e\n\u003cli\u003eZhang, X.-G.; Zhao, Y.; Chen, S.; Xing, S.-M.; Dong, J.-C.; Li, J.-F., Electrolyte effect for carbon dioxide reduction reaction on copper electrode interface: A DFT prediction. \u003cem\u003eThe Journal of Chemical Physics \u003c/em\u003e\u003cstrong\u003e2023,\u003c/strong\u003e \u003cem\u003e158\u003c/em\u003e (9), 094704.\u003c/li\u003e\n\u003cli\u003eLi, J.; Li, C.; Hou, J.; Gao, W.; Chang, X.; Lu, Q.; Xu, B., Intercepting Elusive Intermediates in Cu-Mediated CO Electrochemical Reduction with Alkyl Species. \u003cem\u003eJournal of the American Chemical Society \u003c/em\u003e\u003cstrong\u003e2022,\u003c/strong\u003e \u003cem\u003e144\u003c/em\u003e (44), 20495-20506.\u003c/li\u003e\n\u003cli\u003eWang, C.; Chen, Y.; Su, D.; Man, W.-L.; Lau, K.-C.; Han, L.; Zhao, L.; Zhan, D.; Zhu, X., In situ Electropolymerized 3D Microporous Cobalt-Porphyrin Nanofilm for Highly Effective Molecular Electrocatalytic Reduction of Carbon Dioxide. \u003cem\u003eAdvanced Materials \u003c/em\u003e\u003cstrong\u003e2023\u003c/strong\u003e, 2303179.\u003c/li\u003e\n\u003cli\u003eVasileff, A.; Zhu, Y.; Zhi, X.; Zhao, Y.; Ge, L.; Chen, H. M.; Zheng, Y.; Qiao, S.-Z., Electrochemical Reduction of CO\u003csub\u003e2\u003c/sub\u003e to Ethane through Stabilization of an Ethoxy Intermediate. \u003cem\u003eAngewandte Chemie International Edition \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e59\u003c/em\u003e (44), 19649-19653.\u003c/li\u003e\n\u003cli\u003eHokmabad, B. V.; Ghaemi, S., Effect of Flow and Particle-Plastron Collision on the Longevity of Superhydrophobicity. \u003cem\u003eScientific Reports \u003c/em\u003e\u003cstrong\u003e2017,\u003c/strong\u003e \u003cem\u003e7\u003c/em\u003e (1), 41448.\u003c/li\u003e\n\u003cli\u003eDinh, C.-T.; Li, Y. C.; Sargent, E. H., Boosting the Single-Pass Conversion for Renewable Chemical Electrosynthesis. \u003cem\u003eJoule \u003c/em\u003e\u003cstrong\u003e2019,\u003c/strong\u003e \u003cem\u003e3\u003c/em\u003e (1), 13-15.\u003c/li\u003e\n\u003cli\u003eKibria Nabil, S.; McCoy, S.; Kibria, M. G., Comparative life cycle assessment of electrochemical upgrading of CO\u003csub\u003e2\u003c/sub\u003e to fuels and feedstocks. \u003cem\u003eGreen Chemistry \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e23\u003c/em\u003e (2), 867-880.\u003c/li\u003e\n\u003cli\u003eMa, M.; Clark, E. L.; Therkildsen, K. T.; Dalsgaard, S.; Chorkendorff, I.; Seger, B., Insights into the carbon balance for CO\u003csub\u003e2\u003c/sub\u003e electroreduction on Cu using gas diffusion electrode reactor designs. \u003cem\u003eEnergy \u0026amp; Environmental Science \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e13\u003c/em\u003e (3), 977-985.\u003c/li\u003e\n\u003cli\u003eZhang, J.; Luo, W.; Z\u0026uuml;ttel, A., Crossover of liquid products from electrochemical CO\u003csub\u003e2\u003c/sub\u003e reduction through gas diffusion electrode and anion exchange membrane. \u003cem\u003eJournal of Catalysis \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e385\u003c/em\u003e, 140-145.\u003c/li\u003e\n\u003cli\u003eSalvatore, D. A.; Gabardo, C. M.; Reyes, A.; O\u0026rsquo;Brien, C. P.; Holdcroft, S.; Pintauro, P.; Bahar, B.; Hickner, M.; Bae, C.; Sinton, D.; Sargent, E. H.; Berlinguette, C. P., Designing anion exchange membranes for CO\u003csub\u003e2\u003c/sub\u003e electrolysers. \u003cem\u003eNature Energy \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e6\u003c/em\u003e (4), 339-348.\u003c/li\u003e\n\u003cli\u003eGoyal, A.; Marcandalli, G.; Mints, V. A.; Koper, M. T. M., Competition between CO\u003csub\u003e2\u003c/sub\u003e Reduction and Hydrogen Evolution on a Gold Electrode under Well-Defined Mass Transport Conditions. \u003cem\u003eJournal of the American Chemical Society \u003c/em\u003e\u003cstrong\u003e2020,\u003c/strong\u003e \u003cem\u003e142\u003c/em\u003e (9), 4154-4161.\u003c/li\u003e\n\u003cli\u003eZhang, Y.-J.; Sethuraman, V.; Michalsky, R.; Peterson, A. A., Competition between CO\u003csub\u003e2\u003c/sub\u003e Reduction and H\u003csub\u003e2\u003c/sub\u003e Evolution on Transition-Metal Electrocatalysts. \u003cem\u003eACS Catalysis \u003c/em\u003e\u003cstrong\u003e2014,\u003c/strong\u003e \u003cem\u003e4\u003c/em\u003e (10), 3742-3748.\u003c/li\u003e\n\u003cli\u003eMikkelsen, M.; J\u0026oslash;rgensen, M.; Krebs, F., Energy Environ. Sci. 2010, 3, 43.(b) Riduan, SN; Zhang, Y. \u003cem\u003eDalton Trans \u003c/em\u003e\u003cstrong\u003e2010,\u003c/strong\u003e \u003cem\u003e39\u003c/em\u003e, 3347.\u003c/li\u003e\n\u003cli\u003eZhong, D.; Zhao, Z.; Zhao, Q.; Cheng, D.; Liu, B.; Zhang, G.; Deng, W.; Dong, H.; Zhang, L.; Li, J.; Li, J.; Gong, J., Coupling of Cu(100) and (110) Facets Promotes Carbon Dioxide Conversion to Hydrocarbons and Alcohols. \u003cem\u003eAngewandte Chemie international edtion \u003c/em\u003e\u003cstrong\u003e2021,\u003c/strong\u003e \u003cem\u003e133\u003c/em\u003e (9), 4929-4935.\u003c/li\u003e\n\u003cli\u003eLiu, G.; Zheng, F.; Li, J.; Zeng, G.; Ye, Y.; Larson, D. M.; Yano, J.; Crumlin, E. J.; Ager, J. W.; Wang, L.; Toma, F. M., Investigation and mitigation of degradation mechanisms in Cu\u003csub\u003e2\u003c/sub\u003eO photoelectrodes for CO\u003csub\u003e2\u003c/sub\u003e reduction to ethylene. \u003cem\u003eNature Energy \u003c/em\u003e\u003cstrong\u003e2021\u003c/strong\u003e.\u003c/li\u003e\n\u003cli\u003eHu, S.; Liu, B.-J.; Feng, J.-M.; Zong, C.; Lin, K.-Q.; Wang, X.; Wu, D.-Y.; Ren, B., Quantifying Surface Temperature of Thermoplasmonic Nanostructures. \u003cem\u003eJournal of the American Chemical Society \u003c/em\u003e\u003cstrong\u003e2018,\u003c/strong\u003e \u003cem\u003e140\u003c/em\u003e (42), 13680-13686.\u003c/li\u003e\n\u003cli\u003eXu, M.; Ma, X.; Wei, T.; Lu, Z.-X.; Ren, B., In Situ Imaging of Live-Cell Extracellular pH during Cell Apoptosis with Surface-Enhanced Raman Spectroscopy. \u003cem\u003eAnalytical Chemistry \u003c/em\u003e\u003cstrong\u003e2018,\u003c/strong\u003e \u003cem\u003e90\u003c/em\u003e (23), 13922-13928.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"CO2RR, Copper, hydrophobicity, triple-phase interface, microenvironment ","lastPublishedDoi":"10.21203/rs.3.rs-3812973/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3812973/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe local microenvironment of electricity-powered CO\u003csub\u003e2\u003c/sub\u003e electroreduction reaction (CO\u003csub\u003e2\u003c/sub\u003eRR) surrounding the catalyst-electrolyte-gas triple-phase interface plays a crucial role in catalytic activity and selectivity as it affects reaction pathways and species transport. However, it still needs to be explored and understood regarding the impact of microenvironment evolution on the CO\u003csub\u003e2\u003c/sub\u003eRR performance. We report here a hydrophobic oxide-derived copper foam with villous nanowires on the surface that demonstrates significant suppressed HER and enhanced C\u003csub\u003e2+\u003c/sub\u003e selectivity in H-type cell. \u003cem\u003eIn-situ\u003c/em\u003e 3D Raman mapping and \u003cem\u003ein-situ\u003c/em\u003e Raman spectra investigation on micro-environmental species reveal that high local pH and fast CO\u003csub\u003e2\u003c/sub\u003e mass transfer were simultaneously allowed in the microenvironment of the triple-phase interface because of the special hydrophobic structure. On this mechanism, the material reaches a minimum H\u003csub\u003e2\u003c/sub\u003e Faradaic efficiency (FE) of 6.6% and maximum C\u003csub\u003e2+\u003c/sub\u003e FE of 74.4% at the current density of 300 mA cm\u003csup\u003e-2 \u003c/sup\u003ein a flow cell under acidic conditions (pH=4) without an additional gas-diffusion layer (GDL). This study not only highlighted the importance of the microenvironment but also provided an effective method for tuning the triple-phase interface of CO\u003csub\u003e2\u003c/sub\u003eRR and demonstrated a promising application of the pure metal foam-based GDEs.\u003c/p\u003e","manuscriptTitle":"Microenvironment Evolution at Triple-phase Interface on the CO2RR Process of Hydrophobic Oxide-derived Copper","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-01-12 03:09:35","doi":"10.21203/rs.3.rs-3812973/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"51d0a55d-41b7-4550-ab1b-56c2f69f1ee1","owner":[],"postedDate":"January 12th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":28081016,"name":"Physical sciences/Engineering/Chemical engineering"},{"id":28081017,"name":"Physical sciences/Chemistry/Catalysis/Electrocatalysis"}],"tags":[],"updatedAt":"2024-02-12T11:25:12+00:00","versionOfRecord":[],"versionCreatedAt":"2024-01-12 03:09:35","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3812973","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3812973","identity":"rs-3812973","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}