Selective electrosynthesis of 1,3-butadiene by tailoring the coverage of acetylene and water

Selective electrosynthesis of 1,3-butadiene by tailoring the coverage of acetylene and water | 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 Selective electrosynthesis of 1,3-butadiene by tailoring the coverage of acetylene and water Bin Zhang, Chuanqi Cheng, Jiajun Wang, Fanpeng Chen, Yanran Han, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5240353/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Jul, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract 1,3-Butadiene (C 4 H 6 ), the main raw material for producing important chemicals (nylon, synthetic resin, rubber), relies on petroleum cracking with intensive carbon emissions. The electrocatalytic dimeric hydrogenation of natural gas/coal-derived C 2 H 2 to C 4 H 6 provides a nonpetroleum pathway. However, C 4 H 6 , as a byproduct of C 2 H 2 hydrogenation, is usually neglected because of its very low Faradaic efficiency. Here, we theoretically and experimentally report a mechanism comprising acetylene dimerization and subsequent hydrogenation. The first dimerization process can be accelerated under appropriate coverage of acetylene and water. A ligand-modifying strategy is subsequently proposed to regulate the wettability of Cu nanoarrays to enable suitable coverages. The optimized 1-dodecanethiol-modified Cu nanoarrays deliver a 65.3% C 4 H 6 Faradaic efficiency at 100 mA cm −2 . The C 4 H 6 formation kinetics become sluggish at the two ends of the surface C 2 H 2 /H 2 O ratios, and moderate C 2 H 2 /H 2 O coverage accelerates the C‒C coupling process to promote C 4 H 6 production. Moreover, life cycle assessment demonstrates its sustainability. Physical sciences/Chemistry/Electrochemistry/Electrocatalysis Physical sciences/Chemistry/Green chemistry/Sustainability Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction The reliance on limited petroleum reserves, the tilt of ethylene (C 2 H 4 ) in the petrochemical industry, and the frequent fluctuations in crude oil prices threaten the supply of 1,3-butadiene (C 4 H 6 ). 1−4 In addition, the high energy requirement of the traditional oil-dependent pathway is environmentally unfriendly (Scheme 1a ), 5−8 making it highly desirable to seek an alternative green and petroleum-independent synthesis strategy. 9−10 Acetylene (C 2 H 2 ), obtained from natural gas/coal and acting as one of the primary feedstocks for commodity chemicals in the first half of the last century, 1 has gradually become recognized as a nonpetroleum raw material with the development of arc-plasma technology 11−12 since it is highly active and can be hydrogenated and/or dimerized to C 2 H 4 and/or C 4 H 6 under specific conditions (Scheme 1b ). 13 A Ru-based homogeneous catalyst can drive controlled dimerization of C 2 H 2 under high pressure (10 − 50 bar) to obtain C 4 H 6 , 14 but the reliance on noble metals and their subsequent separation makes this process costly. For the reported heterogeneous catalysts, high pressures and temperatures are also needed, accompanied by safety risks and technical difficulties. 15−17 Therefore, further development of a petroleum-independent, sustainable, and mild strategy for the hydrodimerization of C 2 H 2 to C 4 H 6 is urgently needed. With advancements in electrocatalytic C 2 H 2 hydrogenation (EAH), the electrorefining of rough ethylene (C 2 H 4 ) 18−20 and the electrosynthesis of C 2 H 4 21−22 are currently achieved over copper-based materials. Although trace amounts of the C 4 H 6 product have been observed in EAH, it is always neglected as a byproduct because of its extremely low yield and selectivity (C 4 H 6 Sele. < 10%). 13, 20 , 23−24 Very recently, a well-designed iodide-induced Cu δ+ -Cu 0 sites was reported for promoting C 4 H 6 electrosynthesis. 25 However, the interface properties of acetylene and water on the C − C coupling synthetic mechanism is still not clear. Inspired by studies on CO 2 electroreduction coupling to C 2 H 4 , 26−27 it is reasonable to infer that multiple C − C coupling pathways exist in the EAH process and that appropriate regulation of the coupling behavior will benefit C 4 H 6 electrosynthesis. In addition, the surface coverage of acetylene is speculated to influence the C − C coupling process. But, understanding and regulating the coverage of acetylene and water how regulate the coupling process in EAH to increase the activity and selectivity of C 4 H 6 will be highly desirable for synthesizing C 4 H 6 under mild conditions. In this work, our preliminary experiments and theoretical calculations of the EAH process over commercial Cu nanoparticles (Cu NPs) model catalysts demonstrate that C 4 H 6 generation via the precoupling and rehydrogenation pathways benefits from moderate coverage of C 2 H 2 and H 2 O. Next, we construct ligand-modified Cu nanoarrays with continuously tunable wettability, which are suitable models for researching the effects of surface coverage. We find that 1-dodecanethiol-modified Cu nanoarrays (denoted as Cu-12SH-NAs) deliver a C 4 H 6 Faradaic efficiency (FE) of 65.3% at a current density of 100 mA cm − 2 with a C 4 H 6 production rate of 0.49 mmol mg − 1 h − 1 , substantially outperforming other counterparts. Cu-12SH-NAs with moderate wettability are revealed to enrich surface C 2 H 2 and accelerate the coupling kinetics, thus enabling high C 4 H 6 FE over a wide potential range. As a proof-of-concept application, a 50 cm 2 reactor with a Cu-12SH-NAs catalyst is implemented and maintains stable operation for 13 hours at a current of 1.0 A, with a C 4 H 6 production of 325 mmol. Furthermore, a cradle-to-gate life cycle assessment confirms the sustainability of the proposed C 4 H 6 electrosynthesis strategy. Results and Discussion Calculation-assisted reaction analysis Since C 2 H 4 and C 4 H 6 are the main C 2 H 2 -based products produced during the EAH process over commercial Cu NPs model catalysts (Fig. 1a and Supplementary Figs. 1, 2), reaction analysis is necessary to selectively increase the yield of C 4 H 6 for the rational design of catalysts. First, the stoichiometric ratios of C 2 H 2 and *H aimed at the production of one molecule of C 2 H 4 and C 4 H 6 are 0.5 and 1, respectively (Formulas 1,2), which account for the relatively high C 4 H 6 selectivity in the low current density region with slow hydrogenation kinetics (Fig. 1a). That is, maintaining the required high *C 2 H 2 /*H ratio under negatively shifted potentials is a promising way to simultaneously increase the activity and selectivity of the target C 4 H 6 . In addition, exploration of the mechanism of C−C coupling is also important for the production of C 4 H 6 . Then, the reaction pathway involving the coupling process was further analysed. Specifically, for the electrocatalytic dimeric hydrogenation of C 2 H 2 to C 4 H 6 , there are two kinds of reaction modes: (i) the precoupling and rehydrogenation (C-H) pathways (Formula 3) and (ii) prehydrogenation and recoupling, the latter of which can be further divided into two pathways (H-C-1 & H-C-2) (Formulas 4,5). In these regards, primary density functional theory (DFT) calculations are conducted to evaluate the three proposed reaction pathways over periodic Cu slabs. The energy barriers of the coupling steps are higher than those of hydrogenation for all three paths (Figs. 1b, c, Supplementary Figs. 3−6, and Supplementary Note 1), indicating that the C−C coupling process can be regarded as the rate-determining step (RDS). In this case, the C‒H pathway is proposed as the theoretical optimum path because it results in the lowest coupling and hydrogenation barrier (Fig. 1c). To further distinguish these pathways, the Bulter‒Volmer function is applied to deduce the three theoretical rate expressions, 28 -29 taking the coupling process as the RDS (details in Supplementary Note 2). As shown in Fig. 1d, the reaction order of H + /H 2 O in the three pathways is 0, 1, and 2, respectively. Thus, the reaction pathway can be ascertained through experimental analysis of the reaction order towards H + /H 2 O. Accordingly, pH-dependent and kinetic isotope effect (KIE) experiments efficiently reflect the relevance of H + /H 2 O in electrocatalytic hydrogenation reactions and the corresponding experimental reaction order. 28, 30 -31 Thus, to determine the influence of the H + concentration and H 2 O dissociation on the activity of C 4 H 6 electrosynthesis, potential-dependent C 4 H 6 partial current densities ( j C 4 H 6 ) with different pH values and KIEs were explored over a Cu NPs model catalyst. As shown in Fig. 1e, the apparent activity of C 4 H 6 electrosynthesis is almost the same for electrolytes with different pH values (Supplementary Figs. 7, 8). Similarly, j C 4H 6 remains unchanged within the error range when D 2 O is used as a replacement for H 2 O; that is, the KIE value is approximately close to 1 (Fig. 1f and Supplementary Figs. 9, 10). These results demonstrate that the reaction order of C 4 H 6 electrosynthesis through the EAH process to H + /H 2 O is 0, 28, 32 which is consistent with the theoretical value of the C‒H pathway, revealing that C 4 H 6 electrosynthesis follows the C‒H pathway. Considering the aforementioned *C 2 H 2 /*H stoichiometric ratio discussion, the selected C‒H pathway was further optimized through DFT calculations, and the results suggest that moderate coverage of C 2 H 2 and *H is promising for reducing the barrier difference between coupling and hydrogenation and even achieving a lower coupling barrier than hydrogenation (Figs. 1g, h and Supplementary Figs. 11‒16). Owing to the *H sources from H 2 O during the EAH process, modulating the microenvironment of the Cu-based catalyst, increasing the mass transfer of the C 2 H 2 feedstock, and adjusting its wettability to enable an optimal C 2 H 2 /H 2 O ratio can efficiently boost the activity and selectivity of the target C 4 H 6 . Wettability tuning electrocatalyst synthesis and optimization To increase the mass transfer of gaseous C 2 H 2 feedstocks, Cu-based hydroxide nanoarrays (denoted as Cu NAs) were designed and synthesized through reported liquid deposition on a Cu mesh. The successful formation and nanoarray-like morphology were characterized by X−ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images (Supplementary Fig. 17). Then, continuous wettability regulation was achieved by a well-developed ligand-modified strategy using alkanethiols with different lengths of an alkyl chain (denoted as Cu-xSH-NAs, where x represents the number of carbon atoms in the alkyl chain) (Supplementary Figs. 18, 19). The increasing trend of the contact angle along with the growth of the carbon chain suggests reduced wettability (Fig. 2a). 33 In addition, confocal laser scanning microscopy (CLSM) was performed to explore the gas‒liquid distribution principle over the interface between the electrolyte and electrode. 34 Specifically, the height of the electrolyte over the pores of the Cu mesh tends to decrease with increasing length of the carbon chain (Fig. 2b and Supplementary Fig. 20), indicating that the permeability decreases. In addition, since the light absorption and blocking effects of the gas and solid phases are extremely different (solid > gas), 34 the tail effect of the fluorescent agent in the electrolyte over the electrolyte‒electrode interface is used to describe the C 2 H 2 /H 2 O distribution behavior. The decay distances of the fluorescence intensity through the z -axis direction monotonically increase with increasing growth of the carbon chain (Fig. 2c and Supplementary Figs. 21, 22), indicating enhanced hydrophobicity. This means that the liquid‒solid interface is gradually transformed into a gas‒solid interface after wettability modulation, which is promising for controlling the C 2 H 2 /H 2 O ratio. For gas-involved electrocatalytic reactions, the gaseous reactants are always impeded by aqueous H 2 O with a dense cluster structure in the electrical double layer (EDL); thus, breaking the hydrogen bond (HB) in the H 2 O cluster creates channels for gases; that is, the statistical ratios of H 2 O with saturated (4−HB H 2 O) and unsaturated (1, 2, 3−HB H 2 O) coordination in the EDL could be used as a descriptor of gas accessibility. 35 -36 Therefore, molecular dynamics simulations were conducted to obtain corresponding H 2 O-type information after ligand modification. As shown in Fig. 2d, the relative presence of 4−HB H 2 O decreases from 27% to 23% and 12% as the number of carbon chains increases from 2 to 6 and 12, whereas that of 1, 2, 3−HB H 2 O increases from 72% to 77% and 87%, respectively, indicating that the network structure of H 2 O clusters has been broken. Moreover, both the oxygen and hydrogen density distributions along the z direction, which are regarded as measurements of gas diffusion tunnels tend to decrease with increasing carbon chain length (Fig. 2e), suggesting broadened channels for gas diffusion. 37 In addition, the decreased statistical number of HBs over the whole model with increasing carbon number of the ligands further verifies that the continuity of the HBs has been reduced (Supplementary Fig. 23). Taken together, these results demonstrate that the accessibility of C 2 H 2 could be increased via alkanethiol modification, thus enabling a moderate C 2 H 2 /H 2 O ratio. Therefore, Cu-xSH-NAs catalysts are suitable for C 4 H 6 synthesis through the EAH process. The optimization of the aforementioned catalysts is executed in a flow cell with a gas diffusion electrode under potentiostatic conditions using pure C 2 H 2 as the feed gas. First, the performance of the Cu-xSH-NAs was evaluated to explore the appropriate length of carbon chains (Supplementary Fig. 23). As shown in Figs. 2f,g, the Cu-12SH-NAs deliver the highest FE and j C 4H 6 . In addition, although both j C 2H 4 and j C 4H 6 exhibit a volcano-like profile along with the length of the carbon chains, the peak of j C 2H 4 is located at a carbon number of 10 (Fig. 2g), which is more hydrophilic than that of j C 4H 6 , responding to the aforementioned difference in the required *C 2 H 2 /*H ratio towards C 2 H 4 and C 4 H 6 in the reaction analysis. Next, to further link moderate wettability to optimum C 4 H 6 production, an electrokinetic evaluation was conducted through Tafel analysis (Supplementary Figs. 27, 28). 33 As shown in Fig. 2g, the Tafel slopes for both C 2 H 4 and C 4 H 6 first decrease but then increase with increasing hydrophobicity. The decreasing region indicates faster C 2 H 2 hydrogenation kinetics because of a more sufficient C 2 H 2 supply. Similarly, in the increasing section, the greater the Tafel slope is, the slower the kinetics of the EAH are, which is caused by an insufficient *H supply. 33 Note that the fastest kinetics for C 2 H 4 and C 4 H 6 are located at the same position as the peak point of j C 2H 4 and j C 4H 6 in Fig. 2f, further confirming that a gap exists in the required *C 2 H 2 /*H ratio toward the electrosynthesis of C 2 H 4 and C 4 H 6 . Thus, the moderate wettability generated by the Cu-12SH-NAs could lead to a predominance of C 4 H 6 production. Electrocatalytic acetylene dimeric hydrogenation towards C 4 H 6 Since a suitable C 2 H 2 /H 2 O ratio is highly important for C 4 H 6 production, acetylene at different concentrations (60%−100%) was introduced to optimize the performance of C 4 H 6 electrosynthesis over the selected Cu-12SH-NAs (Supplementary Figs. 29−32). First, with 80% C 2 H 2 as the optimized feed gas, the highest C 4 H 6 FE of 65.3% was achieved at −0.4 V vs. RHE, and the corresponding C 4 H 6 yield rate reached 0.49 mmol mg −1 h −1 with a current density of 100 mA cm −2 , which is superior to those of most reported electrocatalytic processes regarding C 4 H 6 as a byproduct and comparable to the most recently reported case for C 4 H 6 production 25 (Supplementary Figs. 33, 34). Notably, the quantification of the EAH process revealed that C 4 H 6 was the main C 4 product and that the total selectivity of the generated butene and butane was approximately 1% (Supplementary Table 3). In addition, the FE of C 4 H 6 reached above 40% in the potential range from −0.3 to −0.7 V vs. RHE over the Cu-12SH-NAs but was generally below 40% across the full test range of the Cu NAs (Supplementary Fig. 35), again supporting the conclusion that tailoring the C 2 H 2 /H 2 O ratio is quite important in the proposed C 4 H 6 electrosynthesis strategy. Online differential electrochemical mass spectrometry (DEMS) was conducted in linear sweep voltammetry (LSV) mode to further analyse the EAH process. First, the LSV curves of the Cu-12SH-NAs and Cu NAs exhibited lower overpotentials than those of the commercial Cu NPs (Figs. 1a, 3d), suggesting that the nanoarray morphology significantly improves the mass transfer of the gaseous C 2 H 2 . The signal monitored by mass spectrometry (MS) provides more information about the origin of the electric current. 23, 38 As shown by the MS signals at m / z = 39 and m / z = 28, the signals of C 4 H 6 begin to increase (−0.23 V vs. RHE) after the C 2 H 4 onset potential (−0.22 V vs. RHE) over the Cu NAs. However, the Cu-12SH-NAs deliver a more positive onset potential for C 4 H 6 (−0.18 V vs. RHE) than for C 2 H 4 (−0.19 V vs. RHE), indicating that the coupling kinetics increase after ligand modification. In addition, the slope of the ion current for C 4 H 6 (1.51 × 10 −12 V −1 ) over the Cu-12SH-NAs is greater than that over the Cu NAs (1.29 × 10 −12 V −1 ), and the corresponding slope of C 2 H 4 for the Cu-12SH-NAs (2.12 × 10 −12 V −1 ) is lower than that for the Cu NAs (2.42 × 10 −12 V −1 ), demonstrating the better ability for C 4 H 6 generation over the Cu-12SH-NAs (Figs. 3e,f). Moreover, the MS signal intensity of C 4 H 6 over the Cu NAs displays a volcanic shape, which is similar to that of commercial Cu NPs, and begins to decrease at −0.55 V vs. RHE (Figs 1a, 3e), indicating that the coupling becomes kinetically unoptimized in the rapid hydrogenation region. Conversely, the C 4 H 6 signal of the Cu-12SH-NAs presented a nearly monotonically increasing trend with negatively shifted potentials (Fig. 3f), demonstrating that tailoring the wettability of the catalyst surface could efficiently expand the kinetically favourable region of C 4 H 6 generation. In addition, the results of the DEMS test under square wave potentials show that the C 4 H 6 signal over the Cu-12SH-NAs remained almost unchanged with negatively shifted potentials, which is quite different from the decreased C 4 H 6 signal observed for the Cu NAs, indicating better C 4 H 6 selectivity and stability of the Cu-12SH-NAs (Fig. 3g and Supplementary Fig. 36). Furthermore, both the FE of C 4 H 6 and the current density over the Cu-12SH-NAs remained unchanged within the error range during the 13 h continuous test at a potential of −0.4 V vs. RHE, suggesting robust durability (Fig. 3h and Supplementary Fig. 37). Mechanism of the high selectivity for 1,3-butadiene To determine the reason for the increased C 4 H 6 FE and selectivity after ligand modification, a series of characterizations were performed. Specifically, in situ Raman and in situ attenuated total reflectance−Fourier transform infrared (ATR−FTIR) spectroscopy with high surface species sensitivity was conducted to evaluate the status and coverage of C 2 H 2 and the corresponding intermediates on the catalytic surface. As shown in Figs. 4a,b, the signals of both ν (C≡C) (~1700 cm −1 ) 10, 39 and ν (π bond of C≡C) (~1950 cm −1 ) 23, 40 over the Cu-12SH-NAs remained more notable than their Cu NAs counterparts at each potential, indicating improved C 2 H 2 mass transfer and enrichment effects over the Cu-12SH- NAs due to the designed hydrophobic−aerophilic interface. In addition, a characteristic peak located at ~2100 cm −1 , attributed to a CH 2 =CH‒C≡CH species (Supplementary Fig. 38), 41 an isomer of the directly coupled CH=CH−CH=CH intermediate, could be observed only over the Cu-12SH-NAs, experimentally confirming the C‒H pathway and suggesting that the coupling kinetics are enhanced after ligand modification (Figs. 4a,b). In addition, the signals of reactants (C 2 H 2 , H 2 O) and product-relevant intermediates (*C 4 H 6 , and *C 2 H 3 ) were also detected via in situ ATR−FTIR spectroscopy (Figs. 4c, d and Supplementary Figs. 39, 40). Accordingly, the integrals of the IR bands are directly proportional to the coverage of the respective surface adsorbate, and the area ratio between ν(C≡C) and δ(H-O-H) has been used as a descriptor of the relative coverage ratio of C 2 H 2 and H 2 O over the catalyst surface. 23, 42 The plot of ν (C≡C)/ δ (H-O-H) over the Cu-12SH-NAs was larger than that over the Cu NAs, demonstrating that the coverage ratio between C 2 H 2 and H 2 O after ligand modification is greater and more suitable for C 4 H 6 generation over the whole applied potential range (Fig. 4e). 23 Similarly, the higher value of ν (*C 4 H 6 )/ ν (C≡C), accompanied by the lower value of ν (*C 2 H 3 )/ ν (C≡C) over the Cu-12SH-NAs than over their Cu NAs counterparts, indicates that more C 2 H 2 feedstocks are converted to the target C 4 H 6 after modification, further accounting for the enhanced C 4 H 6 FE and selectivity (Supplementary Fig. 41). Finally, the in-depth origins of the enhanced C 4 H 6 selectivity obtained over the Cu-12SH-NAs are summarized in Fig. 4f. The C 2 H 2 feedstocks can be enriched over the hydrophobic−aerophilic interface caused by ligand modification, consequently resulting in moderate C 2 H 2 /H 2 O coverage. The lower C‒H pathway energy barrier due to the suitable C 2 H 2 /H 2 O ratio accelerated the C‒C coupling process, thus leading to satisfactory C 4 H 6 selectivity and FE over Cu-12SH-NAs. A sustainable proof-of-concept application in a 50 cm 2 two-electrode system Encouraged by this, we implemented the Cu-12SH-NAs catalyst in a reactor with a 50 cm 2 geometric electrode (Fig. 5a). Notably, moist C 2 H 2 , which benefits C 2 H 2 /H 2 O coverage regulation, is directly injected into the cathode chamber. As a result, the C 4 H 6 FE approached and remained above 50% in the voltage range from 1.9 to 2.4 V (Fig. 5b). This performance (∼2.0 V at 1.0 A) is retained for at least 13 h of continuous operation and 325 mmol C 4 H 6 was obtained (Fig. 5c and Supplementary Figs. 42, 43). Note that the observed C 4 H 6 FE fluctuations arise as a result of the permeation of the anode electrolyte following a simple drying regeneration process (Supplementary Fig. 44). Given the promising performance of the Cu-12SH-NAs catalyst, a life cycle assessment (LCA) of CO 2 emissions from cradle to gate was then performed to evaluate the environmental feasibility of this new oil-independent C 4 H 6 synthesis technology (Supplementary Note 3 and Supplementary Table 4). The amount of CO 2 emissions per kilogram of C 4 H 6 as a function of electricity carbon intensity is shown in Fig. 5d. Fortunately, our strategy is greener than traditional petroleum-cracking strategies when the carbon intensity of the electricity is lower than 110 g of CO 2 equivalent per kWh, which can be reached via the use of renewable electricity (such as solar and wind electricity). 21 The abovementioned results indicate that the proposed C 4 H 6 electrosynthesis strategy has environmentally friendly potential and deserves to be developed. Conclusion In summary, a primary reaction analysis based on a commercial Cu model catalyst is first proposed both theoretically and experimentally for C 4 H 6 electrosynthesis through the EAH process. The combined results of the DFT calculations and controlled experiments show that C 4 H 6 is generated by acetylene dimerization and the subsequent dimer hydrogenation process. In addition, further theoretical prediction demonstrates that the kinetics of the rate-limiting dimerization process is likely accelerated under the appropriate coverage of C 2 H 2 and *H, leading to increased C 4 H 6 production. A ligand-modifying strategy is then designed to enable an optimum *C 2 H 2 /*H ratio by adjusting the coverage of C 2 H 2 and H 2 O. As a result, the selected Cu-12SH-NAs catalyst delivers up to 65.3% C 4 H 6 Faraday efficiency at a current density of 100 mA cm − 2 , with a C 4 H 6 production rate of 0.49 mmol mg − 1 h − 1 . In addition, the mechanism exploration indicates that the C 2 H 2 feedstocks are enriched, consequently resulting in moderate C 2 H 2 /H 2 O coverage suitable for C 4 H 6 generation. As a proof-of-concept application, 325 mmol C 4 H 6 is obtained through the proposed electrosynthesis strategy under 1.0 A for 13 h over Cu-12SH-NAs in a 50 cm − 2 reactor. Furthermore, the proposed strategy is a potential alternative or complementary method to the petroleum route, as shown by cradle-to-gate LCA. Our work not only provides a case study of a mechanism analysis-inspired method for selectively modulating chemical reactions but also demonstrates a facile petroleum-independent C 4 H 6 electrosynthesis pathway. Methods Electrochemical measurements in the flow cell Before the electrochemical measurements in the flow cell, the commercial GDL-CP and the Cu-xSH-NAs (or Cu NAs) were cut into square shapes with a size of 2.5 × 2.5 cm 2 and then pressed together via a heating press. Electrochemical measurements were carried out via a CS150H electrochemical workstation in a typical flow cell consisting of a working electrode (Cu NPs, Cu-xSH-NAs, or Cu NAs), Pt foil as the counter electrode, and Hg/HgO as the reference electrode. The cathode cell and anode cell were separated by a Nafion 117 proton exchange membrane. The cathode and anode electrolytes were both composed of a 1 M KOH solution, and a peristaltic pump was used to circulate the liquid phase. The gas flow rate was controlled by a mass flowmeter. Before the performance tests, the working electrode was fixed at the interface between the gas flow block and the cathodic electrolyte block by conductive copper tape. First, the electrochemical semihydrogenation of acetylene was conducted at different applied potentials for 10 − 20 min to achieve relatively stable and reliable performance parameters before quantitative analysis. The gas at the flow cell outlet was directly introduced into the gas chromatography system for analysis of the products. All the LSV curves were not iR compensated. The current density of the Tafel slopes was iR corrected with a compensation level of 80%, using the logarithms of the current density as the x-axis and the potential as the y-axis. The slopes obtained for the linear part of the figure are the Tafel slopes. The electrode potentials were rescaled to the RHE via the following equation (Formula 6): E RHE = E Hg/HgO + 0.098 + 0.0591 × pH (Formula 6) Electrochemical operando online DEMS analysis Operando online DEMS analysis was conducted with a QAS 100 instrument provided by Linglu Instruments (Shanghai) Co., Ltd. Because the products in the proposed EAH process were all in the gas phase, operando experiments were conducted to monitor the distribution of the products during the on-stream reaction, clarifying the selectivity issues more directly and clearly. The flow cell used in the performance evaluation and the DEMS were coupled to ensure that the gas at the flow cell outlet was directly injected into the negatively pressured gas circuit system of the DEMS through a quartz capillary that was inserted into the outlet of the flow cell. Note that all the ion currents plotted in this work are provided without any correction or subtraction. The LSV test and rectangular wave potentials were applied from − 0.1 to − 0.9 V vs. RHE with a constant interval of 95 s using a CS150H electrochemical workstation. During the experiment, the flow rates of C 2 H 2 gas and the electrolyte were set the same as those used for the performance evaluation. Electrochemical in situ ATR − FTIR measurements In situ ATR − FTIR was performed on a Nicolet 6700 FTIR spectrometer equipped with an MCTA detector with silicon as the prismatic window and an ECIR-II cell by Linglu Instruments. The Cu NAs or Cu-12SH-NAs served as the working electrode. Pt foil and Hg/HgO with an internal reference electrolyte were used as the counter and reference electrodes, respectively. A 1 M KOH solution was used as the electrolyte. The electrolyte was presaturated with pure C 2 H 2 gas, and the gas was continuously bubbled through during the entire measurement. The spectrum was recorded every 30 s under an applied potential ranging from − 0.3 to − 0.8 V vs. RHE. Electrochemical in situ Raman measurements In situ electrochemical Raman spectra were recorded via an electrochemical workstation on a Renishaw inVia reflex Raman microscope under 633 nm laser excitation under controlled potentials. We used a homemade Teflon electrolytic cell equipped with a piece of round quartz glass for the incidence of lasers and protection of the tested samples. Before the experiments, the electrolyte was pretreated with pure C 2 H 2 gas to obtain C 2 H 2 -saturated KOH. The working electrode was parallel to the quartz glass to maintain the plane of the sample perpendicular to the incident laser. The Pt wire was rolled to a circle around the working electrode to serve as the counter electrode. The reference electrode was Hg/HgO with an internal reference electrolyte of 1 M KOH. The spectrum was recorded under applied potentials ranging from − 0.3 to − 0.8 V vs. RHE. Confocal laser scanning microscopy (CLSM) The variation in available water at the interface can be estimated via confocal laser scanning microscopy (Nikon A1R+, Japan) with a confocal microscope. One hundred microliters of fluorescein-labelled 1 M KOH was added to the confocal dishes, and then 5 × 5 mm 2 Cu NAs, Cu-12SH-NAs, and Cu-16SH-NAs were placed on the liquid droplet with the catalyst side in contact with the electrolyte. The interfacial contact state of catalysts with different wettabilities can be directly reconstructed by analysing a series of CLSM images at different depths within the catalyst layer. A 561 nm laser was used as the excitation source, the microscope was equipped with a ×20 objective lens, and the step size was 0.5 µm. Declarations Data availability The data that support the plots within this paper are available from the corresponding author upon request. Acknowledgments The authors are grateful to the National Key Research and Development Program of China (2024YFA151010 to B.Z. and B.H.Z.) and the National Natural Science Foundation of China (22209120 to B.H.Z.). This work is also supported by the Fundamental Research Funds for the Central Universities of China. Author contributions B.Z. conceived the idea and directed the research. B.H.Z., F.C. and B.Z. designed the experiments. B.H.Z., F.C., and J.W. synthesized the materials and carried out most of the experiments. J.W., Y.H., and Y.H. assisted with the experiments. C.C. contributed to the theoretical calculations. B.H.Z., F.C. and B.Z. analysed the data. B.H.Z. and F.C. wrote the paper. B.Z. revised the paper with comments from all the authors. Competing f inancial i nterests The authors declare that they have no competing interests. References Trotuş, I.-T., Zimmermann, T. & Schüth, F. Catalytic reactions of acetylene: A feedstock for the chemical industry revisited. Chem. 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Kilowatt-scale tandem CO 2 electrolysis for enhanced acetate and ethylene production. Nat. Chem. Eng. 1 , 421–429 (2024). Deng, W., Zhang, P., Seger, B. & Gong, J. Unraveling the rate-limiting step of two-electron transfer electrochemical reduction of carbon dioxide. Nat. Commun. 13 , 803 (2022). Su, L. , et al. Electric-double-layer origin of the kinetic pH effect of hydrogen electrocatalysis revealed by a universal hydroxide adsorption-dependent inflection-point behavior. J. Am. Chem. Soc. 145 , 12051–12058 (2023). Goyal, A. & Koper, M.T.M. The interrelated effect of cations and electrolyte pH on the hydrogen evolution reaction on gold electrodes in alkaline media. Angew. Chem., Int. Ed. 60 , 13452–13462 (2021). Strmcnik, D. , et al. Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. Nat. Chem. 5 , 300–306 (2013). Varela, A.S. , et al. 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Scheme Scheme 1 is available in the Supplementary Files section. Additional Declarations There is NO Competing Interest. Supplementary Files Supportinginformation241224.pdf Supplementary Information Scheme1.docx Cite Share Download PDF Status: Published Journal Publication published 01 Jul, 2025 Read the published version in Nature Communications → 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-5240353","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":409087490,"identity":"7e60f7ed-29ed-48a6-ac07-e6805db28e08","order_by":0,"name":"Bin 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1","display":"","copyAsset":false,"role":"figure","size":170312,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePreliminary experiment and theoretical calculation-assisted reaction analysis. a\u003c/strong\u003e Linear-sweep voltammetry of commercial Cu NPs at 5 mV s\u003csup\u003e−1\u003c/sup\u003e in a 1 M KOH electrolyte (no \u003cem\u003eiR\u003c/em\u003e compensation) and the corresponding Operando DEMS signals. \u003cstrong\u003eb\u003c/strong\u003e, \u003cstrong\u003ec\u003c/strong\u003e Free energy diagram of the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e dimeric hydrogenation process over Cu NPs (b) and the corresponding activation energy \u003cem\u003eE\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e of each elementary reaction (c). \u003cstrong\u003ed\u003c/strong\u003e Expression of the reaction control steps and reaction order for the C‒H, H‒C‒1, and H‒C‒2 pathways. \u003cstrong\u003ee\u003c/strong\u003e, \u003cstrong\u003ef\u003c/strong\u003e Potential-dependent partial current density of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e over commercial Cu NPs under different pH values (e) and isotope-substituted conditions (f). \u003cstrong\u003eg, h\u003c/strong\u003e Free energy diagram of the first step of the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e dimeric hydrogenation process under different coverage conditions (g) and the corresponding activation energy difference values under different coverage conditions (h).\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5240353/v1/548f2caf8a3deae4c6318f5c.png"},{"id":75152942,"identity":"d406dbb9-ad65-42a2-abcc-698c2058802a","added_by":"auto","created_at":"2025-01-31 09:38:03","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":359848,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eEffect of ligand modification on the behavior of interfacial H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO via controllable wettability.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e The average electrolyte (1 M KOH) droplet contact angle of the ligand-modified Cu NAs. The insets show photographs of the water droplets. \u003cstrong\u003eb\u003c/strong\u003e 3D reconstructed microstructure derived from fluorescence spectroscopy of Cu-based catalysts with different modified ligands. The fluorescence intensity represents the height of the penetrated electrolytes. Scale bars, 100 μm. \u003cstrong\u003ec\u003c/strong\u003e Corresponding \u003cem\u003ez\u003c/em\u003e-axis fluorescence intensity line scans of labelled regions. \u003cstrong\u003ed\u003c/strong\u003e Percentages of different types of interfacial water structures over different catalysts determined from the MD models. \u003cstrong\u003ee\u003c/strong\u003e Schematic of the interfacial model of the Cu-xSH-NA (x=2, 6, 12) surface and the corresponding O and H densities along the \u003cem\u003ez\u003c/em\u003e-axis direction. \u003cstrong\u003ef\u003c/strong\u003e Contour plots of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e FE over a Cu-based catalyst with different modified ligands. \u003cstrong\u003eg, h\u003c/strong\u003e Partial current density (g) and Tafel analysis (h) for C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production over Cu-based catalysts with different modified ligands. The a.u. stands for arbitrary units. The error bars represent the standard deviation from at least three independent measurements.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5240353/v1/fcd6614a7e25a6f60f59447c.png"},{"id":75153523,"identity":"7640a28f-9612-4675-8c25-d9e84f6feb96","added_by":"auto","created_at":"2025-01-31 09:46:03","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":175316,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePerformance of 1,3-butadiene synthesis through EAH. a\u003c/strong\u003e FE ratios of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e to C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e at different concentrations. \u003cstrong\u003eb, c\u003c/strong\u003e Potential-dependent current densities and FEs of the obtained products over the Cu-NAs and Cu-12SH-NAs under 80% C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e. \u003cstrong\u003ed\u003c/strong\u003e LSV curves of different catalysts. \u003cstrong\u003ee, f\u003c/strong\u003e DEMS signals for C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e of the Cu NAs (e) and Cu-12SH-NAs (f) in LSV mode. \u003cstrong\u003eg\u003c/strong\u003e DEMS signals for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e of the Cu NAs and Cu-12SH-NAs under square wave potentials. \u003cstrong\u003eh\u003c/strong\u003e Continuous tests of the Cu-12SH-NAs catalyst for the EAH process for 13 h.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5240353/v1/b3b7c7162c4b67d64f075634.png"},{"id":75152950,"identity":"cbfdd9e7-122c-45e9-9a05-9afa4f133467","added_by":"auto","created_at":"2025-01-31 09:38:03","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":418032,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eExploration of the origin of the performance enhancement.\u003c/strong\u003e \u003cstrong\u003ea, b\u003c/strong\u003e In situ Raman spectra of the Cu-12SH-NAs (a) and Cu NAs (b) in a C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e-saturated electrolyte (633 nm laser, from −0.3 V to −0.8 V versus RHE in 1 M KOH). \u003cstrong\u003ec, d\u003c/strong\u003e In situ ATR−FTIR spectra over the Cu-12SH-NAs (c) and Cu NAs (d) when C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e was used as the feed gas (from −0.3 V to −0.8 V versus RHE in 1 M KOH). \u003cstrong\u003ee\u003c/strong\u003e Area ratios of absorbed C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e to H\u003csub\u003e2\u003c/sub\u003eO, C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e to C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e, and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e to C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e. \u003cstrong\u003ef\u003c/strong\u003e Schematic illustration of the mechanism of enhanced C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production over Cu-12SH-NAs.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5240353/v1/73b9951b48f592c47dbdc5e5.png"},{"id":75152946,"identity":"10cec7e2-b451-4830-83fb-c1d6e9d9aaa1","added_by":"auto","created_at":"2025-01-31 09:38:03","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":125567,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eFull-cell performance and sustainability evaluation of the process\u003c/strong\u003e. \u003cstrong\u003ea\u003c/strong\u003e Illustration of the enlarged two-electrode system. \u003cstrong\u003eb\u003c/strong\u003e Performance of the Cu-12SH-NAs (without \u003cem\u003eiR\u003c/em\u003e correction) over the two-electrode reactor. Commercial Ti felt coated with iridium oxide was used as the cathodic material. \u003cstrong\u003ec\u003c/strong\u003e Chronopotentiometric stability test of the Cu-12SH-NAs at a current of 1.0 A in the enlarged two-electrode reactor at room temperature for 13 h. \u003cstrong\u003ed\u003c/strong\u003e CO\u003csub\u003e2\u003c/sub\u003e emission of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production through the EAH process for coal-derived acetylene (red line) with electricity from different sources and different carbon intensities and the reference CO\u003csub\u003e2\u003c/sub\u003e emission of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production via the traditional oil route. CO\u003csub\u003e2\u003c/sub\u003ee, CO\u003csub\u003e2\u003c/sub\u003e equivalent.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-5240353/v1/9e7d33f28fd05f7d7c6ca80d.png"},{"id":85830983,"identity":"d9d36bee-caed-4886-82d1-35fdbd8cf7e3","added_by":"auto","created_at":"2025-07-02 07:44:07","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2121184,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5240353/v1/b7bca3f1-984d-4225-9f2e-f70ec5f50a2f.pdf"},{"id":75152948,"identity":"327ee1eb-2f2a-4eba-a2db-1e69d8151b23","added_by":"auto","created_at":"2025-01-31 09:38:03","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":3005096,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"Supportinginformation241224.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5240353/v1/18a75d6d46094e39844e4cc0.pdf"},{"id":75152944,"identity":"0d373cd3-3d0f-4eba-92e5-169c00a013da","added_by":"auto","created_at":"2025-01-31 09:38:03","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":34011,"visible":true,"origin":"","legend":"","description":"","filename":"Scheme1.docx","url":"https://assets-eu.researchsquare.com/files/rs-5240353/v1/e12ba33da94b4020a20ab9fe.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Selective electrosynthesis of 1,3-butadiene by tailoring the coverage of acetylene and water","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe reliance on limited petroleum reserves, the tilt of ethylene (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e) in the petrochemical industry, and the frequent fluctuations in crude oil prices threaten the supply of 1,3-butadiene (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e).\u003csup\u003e1\u0026minus;4\u003c/sup\u003e In addition, the high energy requirement of the traditional oil-dependent pathway is environmentally unfriendly (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1a\u003c/span\u003e),\u003csup\u003e5\u0026minus;8\u003c/sup\u003e making it highly desirable to seek an alternative green and petroleum-independent synthesis strategy.\u003csup\u003e9\u0026minus;10\u003c/sup\u003e Acetylene (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e), obtained from natural gas/coal and acting as one of the primary feedstocks for commodity chemicals in the first half of the last century,\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e has gradually become recognized as a nonpetroleum raw material with the development of arc-plasma technology\u003csup\u003e11\u0026minus;12\u003c/sup\u003e since it is highly active and can be hydrogenated and/or dimerized to C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and/or C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e under specific conditions (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1b\u003c/span\u003e).\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e A Ru-based homogeneous catalyst can drive controlled dimerization of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e under high pressure (10\u0026thinsp;\u0026minus;\u0026thinsp;50 bar) to obtain C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e,\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e but the reliance on noble metals and their subsequent separation makes this process costly. For the reported heterogeneous catalysts, high pressures and temperatures are also needed, accompanied by safety risks and technical difficulties.\u003csup\u003e15\u0026minus;17\u003c/sup\u003e Therefore, further development of a petroleum-independent, sustainable, and mild strategy for the hydrodimerization of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e to C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e is urgently needed.\u003c/p\u003e \u003cp\u003eWith advancements in electrocatalytic C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e hydrogenation (EAH), the electrorefining of rough ethylene (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e)\u003csup\u003e18\u0026minus;20\u003c/sup\u003e and the electrosynthesis of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e21\u0026minus;22\u003c/sup\u003e are currently achieved over copper-based materials. Although trace amounts of the C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e product have been observed in EAH, it is always neglected as a byproduct because of its extremely low yield and selectivity (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e Sele. \u0026lt; 10%).\u003csup\u003e13, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, 23\u0026minus;24\u003c/sup\u003e Very recently, a well-designed iodide-induced Cu\u003csup\u003eδ+\u003c/sup\u003e-Cu\u003csup\u003e0\u003c/sup\u003e sites was reported for promoting C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis.\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e However, the interface properties of acetylene and water on the C\u0026thinsp;\u0026minus;\u0026thinsp;C coupling synthetic mechanism is still not clear. Inspired by studies on CO\u003csub\u003e2\u003c/sub\u003e electroreduction coupling to C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e,\u003csup\u003e26\u0026minus;27\u003c/sup\u003e it is reasonable to infer that multiple C\u0026thinsp;\u0026minus;\u0026thinsp;C coupling pathways exist in the EAH process and that appropriate regulation of the coupling behavior will benefit C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis. In addition, the surface coverage of acetylene is speculated to influence the C\u0026thinsp;\u0026minus;\u0026thinsp;C coupling process. But, understanding and regulating the coverage of acetylene and water how regulate the coupling process in EAH to increase the activity and selectivity of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e will be highly desirable for synthesizing C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e under mild conditions.\u003c/p\u003e \u003cp\u003eIn this work, our preliminary experiments and theoretical calculations of the EAH process over commercial Cu nanoparticles (Cu NPs) model catalysts demonstrate that C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e generation via the precoupling and rehydrogenation pathways benefits from moderate coverage of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003eO. Next, we construct ligand-modified Cu nanoarrays with continuously tunable wettability, which are suitable models for researching the effects of surface coverage. We find that 1-dodecanethiol-modified Cu nanoarrays (denoted as Cu-12SH-NAs) deliver a C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e Faradaic efficiency (FE) of 65.3% at a current density of 100 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e with a C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production rate of 0.49 mmol mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, substantially outperforming other counterparts. Cu-12SH-NAs with moderate wettability are revealed to enrich surface C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and accelerate the coupling kinetics, thus enabling high C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e FE over a wide potential range. As a proof-of-concept application, a 50 cm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e reactor with a Cu-12SH-NAs catalyst is implemented and maintains stable operation for 13 hours at a current of 1.0 A, with a C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production of 325 mmol. Furthermore, a cradle-to-gate life cycle assessment confirms the sustainability of the proposed C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis strategy.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003e\u003cstrong\u003eCalculation-assisted reaction analysis\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSince C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e are the main C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e-based products produced during the EAH process over commercial Cu NPs model catalysts (Fig. 1a and Supplementary Figs. 1, 2), reaction analysis is necessary to selectively increase the yield of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e for the rational design of catalysts. First, the stoichiometric ratios of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and *H aimed at the production of one molecule of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e are 0.5 and 1, respectively (Formulas 1,2), which account for the relatively high C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e selectivity in the low current density region with slow hydrogenation kinetics (Fig. 1a). That is, maintaining the required high *C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/*H ratio under negatively shifted potentials is a promising way to simultaneously increase the activity and selectivity of the target C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e. In addition, exploration of the mechanism of C\u0026minus;C coupling is also important for the production of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e. Then, the reaction pathway involving the coupling process was further analysed.\u0026nbsp;Specifically, for the electrocatalytic dimeric hydrogenation of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e to C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, there are two kinds of reaction modes: (i) the precoupling and rehydrogenation (C-H) pathways (Formula 3) and (ii) prehydrogenation and recoupling, the latter of which can be further divided into two pathways (H-C-1 \u0026amp; H-C-2) (Formulas 4,5). In these regards, primary density functional theory (DFT) calculations are conducted to evaluate the three proposed reaction pathways over periodic Cu slabs. The energy barriers of the coupling steps are higher than those of hydrogenation for all three paths (Figs. 1b, c, Supplementary Figs. 3\u0026minus;6, and Supplementary Note 1), indicating that the C\u0026minus;C coupling process can be regarded as the rate-determining step (RDS). In this case, the C‒H pathway is proposed as the theoretical optimum path because it results in the lowest coupling and hydrogenation barrier (Fig.\u0026nbsp;1c). To further distinguish these pathways, the Bulter‒Volmer function is applied to deduce the three theoretical rate expressions,\u003csup\u003e28\u003c/sup\u003e\u003csup\u003e-29\u003c/sup\u003e taking the coupling process as the RDS (details in Supplementary Note 2). As shown in Fig. 1d, the reaction order of H\u003csup\u003e+\u003c/sup\u003e/H\u003csub\u003e2\u003c/sub\u003eO in the three pathways is 0, 1, and 2, respectively. Thus, the reaction pathway can be ascertained through experimental analysis of the reaction order towards H\u003csup\u003e+\u003c/sup\u003e/H\u003csub\u003e2\u003c/sub\u003eO.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\"\u003e\u003c/p\u003e\n\u003cp\u003eAccordingly, pH-dependent and kinetic isotope effect (KIE) experiments efficiently reflect the relevance of H\u003csup\u003e+\u003c/sup\u003e/H\u003csub\u003e2\u003c/sub\u003eO in electrocatalytic hydrogenation reactions and the corresponding experimental reaction order.\u003csup\u003e28, 30\u003c/sup\u003e\u003csup\u003e-31\u003c/sup\u003e Thus, to determine the influence of the H\u003csup\u003e+\u003c/sup\u003e concentration and H\u003csub\u003e2\u003c/sub\u003eO dissociation on the activity of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis, potential-dependent C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e partial current densities (\u003cem\u003ej\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e4\u003c/sub\u003e\u003csub\u003eH\u003c/sub\u003e\u003csub\u003e6\u003c/sub\u003e) with different pH values and KIEs were explored over a Cu NPs model catalyst. As shown in Fig. 1e, the apparent activity of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis is almost the same for electrolytes with different pH values (Supplementary Figs. 7, 8). Similarly, \u003cem\u003ej\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e4H\u003c/sub\u003e\u003csub\u003e6\u003c/sub\u003e remains unchanged within the error range when D\u003csub\u003e2\u003c/sub\u003eO is used as a replacement for H\u003csub\u003e2\u003c/sub\u003eO;\u0026nbsp;that is, the KIE value is approximately close to 1\u0026nbsp;(Fig. 1f and Supplementary Figs. 9, 10). These results demonstrate that the reaction order of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis through the EAH process to H\u003csup\u003e+\u003c/sup\u003e/H\u003csub\u003e2\u003c/sub\u003eO is 0,\u003csup\u003e28, 32\u003c/sup\u003e which is consistent with the theoretical value of the C‒H pathway, revealing that C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis follows the C‒H pathway. Considering the aforementioned *C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/*H stoichiometric ratio discussion, the selected C‒H pathway was further optimized through DFT calculations, and the results suggest that moderate coverage of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and *H is promising for reducing the barrier difference between coupling and hydrogenation and even achieving a lower coupling barrier than hydrogenation (Figs. 1g, h and Supplementary Figs. 11‒16). Owing to the *H sources from H\u003csub\u003e2\u003c/sub\u003eO during the EAH process, modulating the microenvironment of the Cu-based catalyst, increasing the mass transfer of the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e feedstock, and adjusting its wettability to enable an optimal C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO ratio can\u0026nbsp;efficiently\u0026nbsp;boost the\u0026nbsp;activity and\u0026nbsp;selectivity of the target C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eWettability tuning electrocatalyst synthesis and optimization\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo increase the mass transfer of gaseous C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e feedstocks, Cu-based hydroxide nanoarrays (denoted as Cu NAs) were designed and synthesized through reported liquid deposition on a Cu mesh. The successful formation and nanoarray-like morphology were characterized by X\u0026minus;ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images (Supplementary Fig. 17). Then, continuous wettability regulation was achieved by a well-developed ligand-modified strategy using alkanethiols with different lengths of an alkyl chain (denoted as Cu-xSH-NAs, where x represents the number of carbon atoms in the alkyl chain) (Supplementary Figs. 18, 19). The increasing trend of the contact angle along with the growth of the carbon chain suggests reduced wettability (Fig. 2a).\u003csup\u003e33\u003c/sup\u003e In addition, confocal laser scanning microscopy (CLSM) was performed to explore the gas‒liquid distribution principle over the interface between the electrolyte and electrode.\u003csup\u003e34\u003c/sup\u003e Specifically, the height of the electrolyte over the pores of the Cu mesh tends to decrease with increasing length of the carbon chain (Fig. 2b and Supplementary Fig. 20), indicating that the permeability decreases. In addition, since the light absorption and blocking effects of the gas and solid phases are extremely different (solid \u0026gt; gas),\u003csup\u003e34\u003c/sup\u003e the tail effect of the fluorescent agent in the electrolyte over the electrolyte‒electrode interface is used to describe the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO distribution behavior. The decay distances of the fluorescence intensity through the \u003cem\u003ez\u003c/em\u003e-axis direction monotonically increase with increasing growth of the carbon chain\u0026nbsp;(Fig. 2c and Supplementary Figs. 21, 22), indicating enhanced hydrophobicity. This means that the liquid‒solid interface is gradually transformed into a gas‒solid interface after wettability modulation, which is promising for controlling the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO ratio.\u0026nbsp;For gas-involved electrocatalytic reactions, the gaseous reactants are always impeded by aqueous H\u003csub\u003e2\u003c/sub\u003eO with a dense cluster structure in the electrical double layer (EDL); thus, breaking the hydrogen bond (HB) in the H\u003csub\u003e2\u003c/sub\u003eO cluster creates channels for gases; that is, the statistical ratios of H\u003csub\u003e2\u003c/sub\u003eO with saturated (4\u0026minus;HB H\u003csub\u003e2\u003c/sub\u003eO) and unsaturated (1, 2, 3\u0026minus;HB H\u003csub\u003e2\u003c/sub\u003eO) coordination in the EDL could be used as a descriptor of gas accessibility.\u003csup\u003e35\u003c/sup\u003e\u003csup\u003e-36\u003c/sup\u003e Therefore, molecular dynamics simulations were conducted to obtain corresponding H\u003csub\u003e2\u003c/sub\u003eO-type information after ligand modification. As shown in Fig.\u0026nbsp;2d, the relative presence of 4\u0026minus;HB H\u003csub\u003e2\u003c/sub\u003eO decreases from 27% to 23% and 12% as the number of carbon chains increases from 2 to 6 and 12, whereas that of\u0026nbsp;1,\u0026nbsp;2, 3\u0026minus;HB H\u003csub\u003e2\u003c/sub\u003eO increases from 72% to 77% and 87%, respectively, indicating that the network structure of H\u003csub\u003e2\u003c/sub\u003eO clusters has been broken. Moreover, both the oxygen and hydrogen density distributions along the \u003cem\u003ez\u003c/em\u003e direction, which are regarded as measurements of gas diffusion tunnels tend to decrease with increasing carbon chain length (Fig. 2e), suggesting broadened channels for gas diffusion.\u003csup\u003e37\u003c/sup\u003e In addition, the decreased statistical number of HBs over the whole model with increasing carbon number of the ligands further verifies that the continuity of the HBs has been reduced (Supplementary Fig. 23). Taken together, these results demonstrate that the accessibility of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e could be increased via alkanethiol modification, thus enabling a moderate C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO ratio. Therefore, Cu-xSH-NAs catalysts are suitable for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e synthesis through the EAH process.\u003c/p\u003e\n\u003cp\u003eThe optimization of the aforementioned catalysts is executed in a flow cell\u0026nbsp;with a gas diffusion electrode under potentiostatic conditions using pure C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e as the feed gas. First, the performance of the Cu-xSH-NAs was evaluated to explore the appropriate length of carbon chains (Supplementary Fig. 23). As shown in Figs.\u0026nbsp;2f,g, the Cu-12SH-NAs deliver the highest FE and \u003cem\u003ej\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e4H\u003c/sub\u003e\u003csub\u003e6\u003c/sub\u003e. In addition, although both \u003cem\u003ej\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e2H\u003c/sub\u003e\u003csub\u003e4\u003c/sub\u003e\u003cem\u003e\u0026nbsp;\u003c/em\u003eand\u003cem\u003e\u0026nbsp;j\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e4H\u003c/sub\u003e\u003csub\u003e6\u003c/sub\u003e exhibit a volcano-like profile along with the length of the carbon chains, the peak of \u003cem\u003ej\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e2H\u003c/sub\u003e\u003csub\u003e4\u003c/sub\u003e\u003cem\u003e\u0026nbsp;\u003c/em\u003eis located at a carbon\u0026nbsp;number\u0026nbsp;of 10 (Fig.\u0026nbsp;2g), which is more hydrophilic than that of \u003cem\u003ej\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e4H\u003c/sub\u003e\u003csub\u003e6\u003c/sub\u003e, responding to the aforementioned difference in the required *C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/*H ratio towards C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e in the reaction analysis. Next, to further link moderate wettability to optimum C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production, an electrokinetic evaluation was conducted through Tafel analysis (Supplementary Figs. 27, 28).\u003csup\u003e33\u003c/sup\u003e As shown in Fig.\u0026nbsp;2g, the Tafel slopes for both C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e first decrease but then increase with increasing hydrophobicity. The decreasing region indicates faster C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e hydrogenation kinetics because of a more sufficient C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e supply. Similarly, in the increasing section, the greater the Tafel slope is, the slower the kinetics of the EAH are, which is caused by an insufficient\u0026nbsp;*H supply.\u003csup\u003e33\u003c/sup\u003e Note that the fastest kinetics for C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e are located at the same position as the peak point of \u003cem\u003ej\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e2H\u003c/sub\u003e\u003csub\u003e4\u003c/sub\u003e and \u003cem\u003ej\u003c/em\u003e\u003csub\u003eC\u003c/sub\u003e\u003csub\u003e4H\u003c/sub\u003e\u003csub\u003e6\u003c/sub\u003e in Fig.\u0026nbsp;2f, further confirming that a gap exists in the required *C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/*H ratio toward the electrosynthesis of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e. Thus, the moderate wettability generated by the Cu-12SH-NAs could lead to a predominance of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eElectrocatalytic acetylene dimeric hydrogenation towards C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSince a suitable C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO ratio is highly important for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production, acetylene at different concentrations (60%\u0026minus;100%) was introduced to optimize the performance of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis over the selected Cu-12SH-NAs (Supplementary Figs. 29\u0026minus;32). First, with 80% C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e as the optimized feed gas, the highest C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e FE of 65.3% was achieved at \u0026minus;0.4 V vs. RHE, and the corresponding C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e yield rate reached 0.49\u0026thinsp;mmol mg\u003csup\u003e\u0026minus;1\u003c/sup\u003e \u0026thinsp;h\u003csup\u003e\u0026minus;1\u003c/sup\u003e with a current density of 100 mA cm\u003csup\u003e\u0026minus;2\u003c/sup\u003e, which is superior to those of most reported electrocatalytic processes regarding C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e as a byproduct and comparable to the most recently reported case for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production\u003csup\u003e25\u003c/sup\u003e (Supplementary Figs. 33, 34). Notably, the quantification of the EAH process revealed that C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e was the main C\u003csub\u003e4\u003c/sub\u003e product and that the total selectivity of the generated butene and butane was approximately 1% (Supplementary Table 3). In addition, the FE of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e reached above 40% in the potential range from \u0026minus;0.3 to \u0026minus;0.7 V vs. RHE over the Cu-12SH-NAs but was generally below 40% across the full test range of the Cu NAs (Supplementary Fig. 35), again supporting the conclusion that tailoring the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO ratio is quite important\u0026nbsp;in the proposed C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis strategy. Online differential electrochemical mass spectrometry (DEMS) was conducted in linear sweep voltammetry (LSV) mode to further analyse the EAH process. First, the LSV curves of the Cu-12SH-NAs and Cu NAs exhibited lower overpotentials than those of the commercial Cu NPs (Figs. 1a, 3d), suggesting that the nanoarray morphology significantly improves the mass transfer of the gaseous C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e. The signal monitored by mass spectrometry (MS) provides more information about the origin of the electric current.\u003csup\u003e23, 38\u003c/sup\u003e As shown by the MS signals at \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u0026nbsp;\u003c/em\u003e= 39 and \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u0026nbsp;\u003c/em\u003e= 28, the signals of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e begin to increase (\u0026minus;0.23 V vs. RHE) after the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e onset potential (\u0026minus;0.22 V vs. RHE) over the Cu NAs. However, the Cu-12SH-NAs deliver a more positive onset potential for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e (\u0026minus;0.18 V vs. RHE) than for C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e (\u0026minus;0.19 V vs. RHE), indicating that the coupling kinetics increase after ligand modification. In addition, the slope of the ion current for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e (1.51 \u0026times; 10\u003csup\u003e\u0026minus;12\u003c/sup\u003e V\u003csup\u003e\u0026minus;1\u003c/sup\u003e) over the Cu-12SH-NAs is greater than that over the Cu NAs (1.29 \u0026times; 10\u003csup\u003e\u0026minus;12\u003c/sup\u003e V\u003csup\u003e\u0026minus;1\u003c/sup\u003e), and the corresponding slope of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e for the Cu-12SH-NAs (2.12 \u0026times; 10\u003csup\u003e\u0026minus;12\u003c/sup\u003e V\u003csup\u003e\u0026minus;1\u003c/sup\u003e) is lower than that for the Cu NAs (2.42 \u0026times; 10\u003csup\u003e\u0026minus;12\u003c/sup\u003e V\u003csup\u003e\u0026minus;1\u003c/sup\u003e), demonstrating the better ability for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e generation over the Cu-12SH-NAs (Figs. 3e,f). Moreover, the MS signal intensity of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e over the Cu NAs displays a volcanic shape, which is similar to that of commercial Cu NPs, and\u003c/p\u003e\n\u003cp\u003ebegins to decrease at \u0026minus;0.55 V vs. RHE (Figs 1a,\u0026nbsp;3e), indicating that the coupling becomes kinetically unoptimized in the rapid hydrogenation region. Conversely, the C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e signal of the Cu-12SH-NAs presented a nearly monotonically increasing trend with negatively shifted potentials (Fig.\u0026nbsp;3f), demonstrating that tailoring the wettability of the catalyst surface could efficiently expand the kinetically favourable region of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e generation. In addition, the results of the DEMS test under square wave potentials show that the C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e signal over the Cu-12SH-NAs remained almost unchanged with negatively shifted potentials, which is quite different from the decreased C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e signal observed for the Cu NAs, indicating better C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e selectivity and stability of the Cu-12SH-NAs (Fig. 3g and Supplementary Fig. 36). Furthermore, both the FE of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e and the current density over the Cu-12SH-NAs remained unchanged within the error range during the 13\u0026thinsp;h continuous test at a potential of \u0026minus;0.4 V vs. RHE, suggesting robust durability (Fig. 3h\u0026nbsp;and Supplementary Fig. 37).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMechanism of the high selectivity for 1,3-butadiene\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo determine the reason for the increased C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e FE and selectivity after ligand modification, a series of characterizations were performed. Specifically, in situ Raman and in situ attenuated total reflectance\u0026minus;Fourier transform infrared (ATR\u0026minus;FTIR) spectroscopy with high surface species sensitivity was conducted to evaluate the status and coverage of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and the corresponding intermediates on the catalytic surface. As shown in Figs. 4a,b, the signals of both \u003cem\u003e\u0026nu;\u003c/em\u003e(C\u0026equiv;C) (~1700 cm\u003csup\u003e\u0026minus;1\u003c/sup\u003e)\u003csup\u003e10, 39\u003c/sup\u003e and \u003cem\u003e\u0026nu;\u003c/em\u003e(\u0026pi; bond of C\u0026equiv;C) (~1950 cm\u003csup\u003e\u0026minus;1\u003c/sup\u003e)\u003csup\u003e23, 40\u003c/sup\u003e over the Cu-12SH-NAs remained more notable than their Cu NAs counterparts at each potential, indicating improved C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e mass transfer and enrichment effects over the Cu-12SH- NAs due to the designed hydrophobic\u0026minus;aerophilic interface. In addition, a characteristic peak located at ~2100 cm\u003csup\u003e\u0026minus;1\u003c/sup\u003e, attributed to a CH\u003csub\u003e2\u003c/sub\u003e=CH‒C\u0026equiv;CH species (Supplementary Fig. 38),\u003csup\u003e41\u003c/sup\u003e an isomer of the directly coupled CH=CH\u0026minus;CH=CH intermediate, could be observed only over the Cu-12SH-NAs, experimentally confirming the C‒H pathway and suggesting that the coupling kinetics are enhanced after ligand modification (Figs. 4a,b). In addition, the signals of reactants (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e, H\u003csub\u003e2\u003c/sub\u003eO) and product-relevant intermediates (*C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, and *C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e3\u003c/sub\u003e) were also detected via in situ ATR\u0026minus;FTIR spectroscopy (Figs. 4c, d and Supplementary Figs. 39, 40). Accordingly,\u0026nbsp;the integrals of the IR bands are directly proportional to the coverage of the respective surface adsorbate, and the area ratio between \u0026nu;(C\u0026equiv;C) and \u0026delta;(H-O-H) has been used as a descriptor of the relative coverage ratio of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003eO over the catalyst surface.\u003csup\u003e23, 42\u003c/sup\u003e The plot of \u003cem\u003e\u0026nu;\u003c/em\u003e(C\u0026equiv;C)/\u003cem\u003e\u0026delta;\u003c/em\u003e(H-O-H) over the Cu-12SH-NAs was larger than that over the Cu NAs, demonstrating that the coverage ratio between C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003eO after ligand modification is greater and more suitable for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e generation over the whole applied potential range (Fig. 4e).\u003csup\u003e23\u003c/sup\u003e Similarly, the higher value of \u003cem\u003e\u0026nu;\u003c/em\u003e(*C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e)/\u003cem\u003e\u0026nu;\u003c/em\u003e(C\u0026equiv;C), accompanied by the lower value of \u003cem\u003e\u0026nu;\u003c/em\u003e(*C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e3\u003c/sub\u003e)/\u003cem\u003e\u0026nu;\u003c/em\u003e(C\u0026equiv;C) over the Cu-12SH-NAs than over their Cu NAs counterparts, indicates that more C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e feedstocks are converted to the target C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e after modification, further accounting for the enhanced C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u0026nbsp;\u003c/sub\u003eFE\u0026nbsp;and selectivity\u0026nbsp;(Supplementary Fig. 41). Finally, the in-depth origins of the enhanced C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e selectivity obtained over the Cu-12SH-NAs are summarized in Fig. 4f. The C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e feedstocks can be enriched over the hydrophobic\u0026minus;aerophilic interface caused by ligand modification, consequently resulting in moderate C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO coverage. The lower C‒H pathway energy barrier due to the suitable C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO ratio accelerated the C‒C coupling process, thus leading to satisfactory C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e selectivity and FE over Cu-12SH-NAs.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eA sustainable proof-of-concept application in a 50 cm\u003csup\u003e2\u003c/sup\u003e two-electrode system\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eEncouraged by this, we implemented the Cu-12SH-NAs catalyst in a reactor with a 50 cm\u003csup\u003e2\u003c/sup\u003e geometric electrode (Fig. 5a). Notably, moist C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e, which benefits C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO coverage regulation, is directly injected into the cathode chamber.\u0026nbsp;As a result, the C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e FE approached and remained above 50% in the voltage range from 1.9 to 2.4 V (Fig. 5b). This performance (\u0026sim;2.0 V at 1.0 A) is retained for at least 13 h of continuous operation and 325 mmol C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e was obtained (Fig. 5c and Supplementary Figs. 42, 43). Note that the observed C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e FE fluctuations arise as a result of the permeation of the anode electrolyte following a simple drying regeneration process (Supplementary Fig. 44). Given the promising performance of the Cu-12SH-NAs catalyst, a life cycle assessment (LCA) of CO\u003csub\u003e2\u003c/sub\u003e emissions from cradle to gate was then performed to evaluate the environmental feasibility of this new oil-independent C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e synthesis technology (Supplementary Note 3 and Supplementary Table 4). The amount of CO\u003csub\u003e2\u003c/sub\u003e emissions per kilogram of C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e as a function of electricity carbon intensity is shown in Fig. 5d. Fortunately, our strategy is greener than traditional petroleum-cracking strategies when the carbon intensity of the electricity is lower than 110 g of CO\u003csub\u003e2\u003c/sub\u003e equivalent per kWh, which can be reached via the use of renewable electricity (such as solar and wind electricity).\u003csup\u003e21\u003c/sup\u003e The abovementioned results indicate that the proposed C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis strategy has environmentally friendly potential and deserves to be developed.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, a primary reaction analysis based on a commercial Cu model catalyst is first proposed both theoretically and experimentally for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis through the EAH process. The combined results of the DFT calculations and controlled experiments show that C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e is generated by acetylene dimerization and the subsequent dimer hydrogenation process. In addition, further theoretical prediction demonstrates that the kinetics of the rate-limiting dimerization process is likely accelerated under the appropriate coverage of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and *H, leading to increased C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production. A ligand-modifying strategy is then designed to enable an optimum *C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/*H ratio by adjusting the coverage of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003eO. As a result, the selected Cu-12SH-NAs catalyst delivers up to 65.3% C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e Faraday efficiency at a current density of 100 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, with a C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production rate of 0.49 mmol mg\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. In addition, the mechanism exploration indicates that the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e feedstocks are enriched, consequently resulting in moderate C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO coverage suitable for C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e generation. As a proof-of-concept application, 325 mmol C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e is obtained through the proposed electrosynthesis strategy under 1.0 A for 13 h over Cu-12SH-NAs in a 50 cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e reactor. Furthermore, the proposed strategy is a potential alternative or complementary method to the petroleum route, as shown by cradle-to-gate LCA. Our work not only provides a case study of a mechanism analysis-inspired method for selectively modulating chemical reactions but also demonstrates a facile petroleum-independent C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e electrosynthesis pathway.\u003c/p\u003e"},{"header":"Methods","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\n \u003ch2\u003eElectrochemical measurements in the flow cell\u003c/h2\u003e\n \u003cp\u003eBefore the electrochemical measurements in the flow cell, the commercial GDL-CP and the Cu-xSH-NAs (or Cu NAs) were cut into square shapes with a size of 2.5 \u0026times; 2.5 cm\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e and then pressed together via a heating press. Electrochemical measurements were carried out via a CS150H electrochemical workstation in a typical flow cell consisting of a working electrode (Cu NPs, Cu-xSH-NAs, or Cu NAs), Pt foil as the counter electrode, and Hg/HgO as the reference electrode. The cathode cell and anode cell were separated by a Nafion 117 proton exchange membrane. The cathode and anode electrolytes were both composed of a 1 M KOH solution, and a peristaltic pump was used to circulate the liquid phase. The gas flow rate was controlled by a mass flowmeter. Before the performance tests, the working electrode was fixed at the interface between the gas flow block and the cathodic electrolyte block by conductive copper tape. First, the electrochemical semihydrogenation of acetylene was conducted at different applied potentials for 10\u0026thinsp;\u0026minus;\u0026thinsp;20 min to achieve relatively stable and reliable performance parameters before quantitative analysis. The gas at the flow cell outlet was directly introduced into the gas chromatography system for analysis of the products. All the LSV curves were not \u003cem\u003eiR\u003c/em\u003e compensated. The current density of the Tafel slopes was \u003cem\u003eiR\u003c/em\u003e corrected with a compensation level of 80%, using the logarithms of the current density as the x-axis and the potential as the y-axis. The slopes obtained for the linear part of the figure are the Tafel slopes. The electrode potentials were rescaled to the RHE via the following equation (Formula 6):\u003c/p\u003e\n \u003cp\u003e\u003cem\u003eE\u003c/em\u003e \u003csub\u003eRHE\u003c/sub\u003e = \u003cem\u003eE\u003c/em\u003e\u003csub\u003eHg/HgO\u003c/sub\u003e + 0.098\u0026thinsp;+\u0026thinsp;0.0591 \u0026times; pH (Formula 6)\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e\n \u003ch2\u003eElectrochemical operando online DEMS analysis\u003c/h2\u003e\n \u003cp\u003eOperando online DEMS analysis was conducted with a QAS 100 instrument provided by Linglu Instruments (Shanghai) Co., Ltd. Because the products in the proposed EAH process were all in the gas phase, operando experiments were conducted to monitor the distribution of the products during the on-stream reaction, clarifying the selectivity issues more directly and clearly. The flow cell used in the performance evaluation and the DEMS were coupled to ensure that the gas at the flow cell outlet was directly injected into the negatively pressured gas circuit system of the DEMS through a quartz capillary that was inserted into the outlet of the flow cell. Note that all the ion currents plotted in this work are provided without any correction or subtraction. The LSV test and rectangular wave potentials were applied from \u0026minus;\u0026thinsp;0.1 to \u0026minus;\u0026thinsp;0.9 V vs. RHE with a constant interval of 95 s using a CS150H electrochemical workstation. During the experiment, the flow rates of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e gas and the electrolyte were set the same as those used for the performance evaluation.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e\n \u003ch2\u003eElectrochemical in situ ATR\u0026thinsp;\u0026minus;\u0026thinsp;FTIR measurements\u003c/h2\u003e\n \u003cp\u003eIn situ ATR\u0026thinsp;\u0026minus;\u0026thinsp;FTIR was performed on a Nicolet 6700 FTIR spectrometer equipped with an MCTA detector with silicon as the prismatic window and an ECIR-II cell by Linglu Instruments. The Cu NAs or Cu-12SH-NAs served as the working electrode. Pt foil and Hg/HgO with an internal reference electrolyte were used as the counter and reference electrodes, respectively. A 1 M KOH solution was used as the electrolyte. The electrolyte was presaturated with pure C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e gas, and the gas was continuously bubbled through during the entire measurement. The spectrum was recorded every 30 s under an applied potential ranging from \u0026minus;\u0026thinsp;0.3 to \u0026minus;\u0026thinsp;0.8 V vs. RHE.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\n \u003ch2\u003eElectrochemical in situ Raman measurements\u003c/h2\u003e\n \u003cp\u003eIn situ electrochemical Raman spectra were recorded via an electrochemical workstation on a Renishaw inVia reflex Raman microscope under 633 nm laser excitation under controlled potentials. We used a homemade Teflon electrolytic cell equipped with a piece of round quartz glass for the incidence of lasers and protection of the tested samples. Before the experiments, the electrolyte was pretreated with pure C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e gas to obtain C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e-saturated KOH. The working electrode was parallel to the quartz glass to maintain the plane of the sample perpendicular to the incident laser. The Pt wire was rolled to a circle around the working electrode to serve as the counter electrode. The reference electrode was Hg/HgO with an internal reference electrolyte of 1 M KOH. The spectrum was recorded under applied potentials ranging from \u0026minus;\u0026thinsp;0.3 to \u0026minus;\u0026thinsp;0.8 V vs. RHE.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec14\" class=\"Section2\"\u003e\n \u003ch2\u003eConfocal laser scanning microscopy (CLSM)\u003c/h2\u003e\n \u003cp\u003eThe variation in available water at the interface can be estimated via confocal laser scanning microscopy (Nikon A1R+, Japan) with a confocal microscope. One hundred microliters of fluorescein-labelled 1 M KOH was added to the confocal dishes, and then 5 \u0026times; 5 mm\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e Cu NAs, Cu-12SH-NAs, and Cu-16SH-NAs were placed on the liquid droplet with the catalyst side in contact with the electrolyte. The interfacial contact state of catalysts with different wettabilities can be directly reconstructed by analysing a series of CLSM images at different depths within the catalyst layer. A 561 nm laser was used as the excitation source, the microscope was equipped with a \u0026times;20 objective lens, and the step size was 0.5 \u0026micro;m.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe data that support the plots within this paper are available from the corresponding author upon request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors are grateful to the National Key Research and Development Program of China\u0026nbsp;(2024YFA151010 to B.Z. and B.H.Z.) and the National Natural Science Foundation of China (22209120 to B.H.Z.). This work is also supported by the Fundamental Research Funds for the Central Universities of China.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eB.Z. conceived the idea and directed the research. B.H.Z., F.C. and B.Z. designed the experiments. B.H.Z., F.C., and J.W. synthesized the materials and carried out most of the experiments. J.W., Y.H., and Y.H. assisted with the experiments. C.C. contributed to the theoretical calculations. B.H.Z., F.C. and B.Z. analysed the data. B.H.Z. and F.C. wrote the paper. B.Z. revised the paper with comments from all the authors.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003ef\u003c/strong\u003e\u003cstrong\u003einancial\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003ei\u003c/strong\u003e\u003cstrong\u003enterests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eTrotuş, I.-T., Zimmermann, T. \u0026amp; Sch\u0026uuml;th, F. Catalytic reactions of acetylene: A feedstock for the chemical industry revisited. \u003cem\u003eChem. Rev.\u003c/em\u003e \u003cstrong\u003e114\u003c/strong\u003e, 1761\u0026ndash;1782 (2014).\u003c/li\u003e\n\u003cli\u003eQi, L.\u003cem\u003e, et al.\u003c/em\u003e Ethanol conversion to butadiene over isolated zinc and yttrium Sites grafted onto dealuminated beta zeolite. \u003cem\u003eJ. Am. Chem. 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Phys.\u003c/em\u003e \u003cstrong\u003e17\u003c/strong\u003e, 74\u0026ndash;78 (1949).\u003c/li\u003e\n\u003cli\u003eMoon, J.\u003cem\u003e, et al.\u003c/em\u003e Discriminating the role of surface hydride and hydroxyl for acetylene semihydrogenation over ceria through in situ neutron and infrared spectroscopy. \u003cem\u003eACS Catal.\u003c/em\u003e \u003cstrong\u003e10\u003c/strong\u003e, 5278\u0026ndash;5287 (2020).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Scheme","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-5240353/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5240353/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003e1,3-Butadiene (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e), the main raw material for producing important chemicals (nylon, synthetic resin, rubber), relies on petroleum cracking with intensive carbon emissions. The electrocatalytic dimeric hydrogenation of natural gas/coal-derived C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e to C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e provides a nonpetroleum pathway. However, C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, as a byproduct of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e hydrogenation, is usually neglected because of its very low Faradaic efficiency. Here, we theoretically and experimentally report a mechanism comprising acetylene dimerization and subsequent hydrogenation. The first dimerization process can be accelerated under appropriate coverage of acetylene and water. A ligand-modifying strategy is subsequently proposed to regulate the wettability of Cu nanoarrays to enable suitable coverages. The optimized 1-dodecanethiol-modified Cu nanoarrays deliver a 65.3% C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e Faradaic efficiency at 100 mA cm\u003csup\u003e−2\u003c/sup\u003e. The C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e formation kinetics become sluggish at the two ends of the surface C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO ratios, and moderate C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003eO coverage accelerates the C‒C coupling process to promote C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e production. Moreover, life cycle assessment demonstrates its sustainability.\u003c/p\u003e","manuscriptTitle":"Selective electrosynthesis of 1,3-butadiene by tailoring the coverage of acetylene and water","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-31 09:37:58","doi":"10.21203/rs.3.rs-5240353/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"61108e61-e4a0-4b43-b680-e662781e90ff","owner":[],"postedDate":"January 31st, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":43622173,"name":"Physical sciences/Chemistry/Electrochemistry/Electrocatalysis"},{"id":43622174,"name":"Physical sciences/Chemistry/Green chemistry/Sustainability"}],"tags":[],"updatedAt":"2025-07-02T07:44:01+00:00","versionOfRecord":{"articleIdentity":"rs-5240353","link":"https://doi.org/10.1038/s41467-025-60881-4","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2025-07-01 04:00:00","publishedOnDateReadable":"July 1st, 2025"},"versionCreatedAt":"2025-01-31 09:37:58","video":"","vorDoi":"10.1038/s41467-025-60881-4","vorDoiUrl":"https://doi.org/10.1038/s41467-025-60881-4","workflowStages":[]},"version":"v1","identity":"rs-5240353","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5240353","identity":"rs-5240353","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}