Efficient charge separation in Z-scheme heterojunctions induced by chemical bonding-enhanced internal electric field for promoting photocatalytic conversion of corn stover to C1/C2 gases

Efficient charge separation in Z-scheme heterojunctions induced by chemical bonding-enhanced internal electric field for promoting photocatalytic conversion of corn stover to C1/C2 gases | 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 Research Article Efficient charge separation in Z-scheme heterojunctions induced by chemical bonding-enhanced internal electric field for promoting photocatalytic conversion of corn stover to C1/C2 gases Guoyang Gao, Yuxin Dai, Ying Lin, Houjuan Qi, Zhanhua Huang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5122454/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 19 Nov, 2024 Read the published version in Advanced Composites and Hybrid Materials → Version 1 posted 9 You are reading this latest preprint version Abstract The direct conversion of corn stover into high value-added C 1 /C 2 gases using photocatalysis is a challenging and prospective endeavor. In this work, a sulfur/oxygen dual-vacancies CdS/Co 3 O 4 (CdS-S v /Co 3 O 4 -O v ) Z-scheme heterojunction was designed for direct raw corn stover powder (RCSP) conversion in a photoreactive system. The internal electric field (IEF) formed in CdS-S v /Co 3 O 4 -O v can effectively promote the photogenerated charge separation and transfer, and the chemical bond formed at the heterogeneous interface can be used as a channel for the directional migration of photogenerated charges to accelerate the inter-interface charge transfer. Experimental results combined with DFT calculations confirmed the formation of Z-scheme heterojunction and IEF. The results of the photocatalytic RCSP reaction showed that the CO, CH 4 , C 2 H 6 , and C 2 H 4 production rates of the proposed catalytic system were as high as 691.99, 2057.69, 202.93 and 187.29 µmol/g, with the corresponding CH 4 selectivity and total hydrocarbon selectivity of 65.53% and 77.96%, respectively. What’s more, we propose a photocatalytic reaction mechanism in which raw biomass undergoes depolymerization and cascading oxidation to high value-added products. This study provides a new idea for high-performance photocatalytic direct conversion of RCSP into high-value-added C 1 /C 2 gases through the rational design of photocatalysts and reaction systems. corn stover photo-conversion Z-scheme heterojunction internal electric field sulfur/oxygen dual-vacancies Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1 Introduction Growing global energy demand and environmental concerns have greatly contributed to the utilization and development of sustainable and clean energy sources. Therefore, there is an urgent need to seek sustainable alternatives to traditional fossil energy sources. Lignocellulose is a good renewable resource that is carbon-neutral, economical and readily available. Therefore, efficient utilization of lignocellulose will help reduce dependence on fossil fuels [ 1 – 3 ]. Corn stover is the most stable part of the non-food lignocellulosic biomass resource and is the most conveniently available biomass resource. High-value utilization of corn stover not only solves the environmental problems caused by massive burning, but also promises the conversion of agricultural and forestry wastes into important platform compounds and gases [ 4 – 6 ]. With the development of photocatalytic technology, the use of solar energy to drive the conversion of biomass into high-value chemicals offers a highly promising approach [ 7 – 9 ]. In recent years, the conversion of lignocellulose into platform compounds and hydrogen using photocatalytic technology has been of interest to researchers [ 10 – 12 ]. However, due to the complex composition of corn stover, the products of photocatalytic conversion of macromolecular compounds often suffer from complex composition, low conversion efficiency, and poor selectivity. Although photocatalytic stover can achieve hydrogen production, the source of hydrogen protons mostly originates from water, which will not be able to effectively realize the utilization and conversion of corn stover resources. Compared with hydrogen, gaseous compounds containing one or two carbons (C 1 /C 2 gases) are important chemical raw materials and intermediates [ 13 , 14 ]. As a carbon-rich carrier, the conversion of corn stover into CH 4 , CO, C 2 H 4 , and C 2 H 6 through photocatalytic technology will be more promising to realize the high value-added utilization of corn stover. In recent years, many types of photocatalysts such as metal oxides, metal sulfides, metal-organic frameworks (MOFs), organic polymers, and covalent organic frameworks have been developed [ 15 – 17 ]. Heterojunction photocatalysts offer significant advantages over individual catalysts in inhibiting photogenerated electron-hole separation complexes and addressing the low redox capacity of the catalysts [ 18 , 19 ]. The Z-scheme heterojunction retains a strong redox capacity and its charge transfer mechanism greatly facilitates the spatial separation of carriers compared to conventional type-I and type-II [ 20 , 21 ]. The photocatalytic efficiency does not only depend on the type of catalyst, but often the catalyst's properties such as morphology dimension and surface structure will also affect the catalytic efficiency. Hollow nanostructured materials have attracted much attention because they can capture more incident photons through multiple scattering and can promote space charge separation and extend radiation lifetime through suitable catalyst modification [ 22 – 24 ]. Zeolitic Imidazolate Frameworks (ZIFs) is an important class of MOFs, and its derivatives with hollow structures can be prepared by high-temperature pyrolysis and can well maintain the original morphological features [ 25 , 26 ]. Therefore, the construction of Z-scheme heterojunction hollow-structured photocatalysts based on ZIF derivatives is a promising pathway expected to realize efficient photocatalytic conversion of corn stover. Here, we designed and prepared a sulfur/oxygen dual-vacancies CdS/Co 3 O 4 (CdS-S v /Co 3 O 4 -O v ) Z-scheme heterojunction for photocatalytic conversion of raw corn stover powder (RCSP). The hollow Co 3 O 4 -O v prepared by pyrolysis of ZIF-67 not only maintains the original three-dimensional morphology well, but also expands the light absorption range. The growth of CdS-S v nanoparticles on the hollow Co 3 O 4 -O v surface was further realized by a simple oil bath method. A series of characterization results indicate that the electron transfer between Co 3 O 4 -O v and CdS-S v follows a Z-scheme heterojunction under light irradiation. The regionally enhanced internal electric field (IEF) and interfacial chemical bonding effectively facilitate the photogenerated charge separation and transfer. Moreover, density functional theory (DFT) calculations confirm the interaction between heterogeneous interfaces and the formation of internal electric fields. The photocatalytic reaction results indicate that the raw corn stover powder (RCSP) can be efficiently converted to CH 4 , CO, C 2 H 4 and C 2 H 6 with high yields of 691.99, 2057.69, 202.93 and 187.29 µmol/g, respectively. The selectivities of CH 4 and C x H y were 65.53% and 77.96%, respectively. The radical trapping experiments showed ·OH and ·O 2 − as the main radical active species. On this basis, we further propose possible mechanisms for product transformation. This work provides a feasible strategy for the photocatalytic conversion of RCSP, an agroforestry waste, into high value-added hydrocarbon gases. 2 Experimental Synthesis of CdS nanoparticles. In a typical procedure, 300 mg TAA and 790 mg CdCl 2 were dissolved in 40 ml of deionized water. The mixed solution was placed in a three-necked flask and stirred continuously for 20 min. The reaction was then carried out in an oil bath at 80°C and kept for 2 h. In addition, we also prepared CdS nanoparticles with different CdCl 2 and TAA molar ratios. After cooling naturally to room temperature, the orange-yellow precipitate was collected by centrifugation. The product was further washed several times with water and ethanol and then dried under vacuum at 60°C for 12 hours. The final product CdS-S v was obtained as an orange-yellow powder. In addition, the CdS nanoparticles prepared only by varying the CdCl 2 and TAA molar ratios (1:1, 1:2, and 1:3), and the other conditions were consistent with the preparation process described above. Synthesis of ZIF-67 and Co 3 O 4 nanocages. ZIF-67 dodecahedron was first prepared as a template, which was further subjected to pyrolysis to prepare Co 3 O 4 -O v . In a typical procedure, 0.5 g of Co(NO 3 ) 2 and 0.6 g of dimethylimidazole were dissolved in 20 mL of methanol, respectively. Further the dimethylimidazole solution was injected into the Co(NO 3 ) 2 solution under vigorous stirring and stirring was continued for 1 h. The mixed solution was then aged at room temperature for 12 h. Finally, the purple precipitate was washed three times with methanol and dried under vacuum for 12 h. ZIF-67 purple powder was obtained. The prepared ZIF-67 powder was further pyrolyzed in tube furnace under flowing air at 400°C for 1h (3°C/min). The Co 3 O 4− O v nanocages powder was collected after cooling to room temperature. Synthesis of CdS/Co 3 O 4 composites. CdS nanoparticles were grown on Co 3 O 4 nanocages surface by oil bath method. Generally, 300 mg of TAA, 790 mg of CdCl 2 and a certain mass of Co 3 O 4 powder were dissolved in 40 mL of deionized water. The mixed solution was then placed in a three-necked flask and stirred vigorously for 20 min. The reaction was then carried out in an oil bath at 80°C and kept for 2 h. After cooling naturally to room temperature, the precipitate was collected by centrifugation and washed three times with ethanol and water, respectively. The precipitates were vacuum dried at 60°C for 12 h to obtain CdS-S v /Co 3 O 4− O v composites. The weight of Co 3 O 4 in a series of CdS-S v /Co 3 O 4− O v composites was 20 mg, 40 mg, and 60mg, which were labeled as CS/CO-20, CS/CO-40, and CS/CO-60. 3 Results and discussion 3.1 Preparation and characterization CdS-S v /Co 3 O 4 -O v with different Co 3 O 4 -O v mass loadings were prepared by high-temperature pyrolysis and in situ growth strategies, as shown in Fig. 1 a. ZIF-67 was used as a template to obtain Co 3 O 4 -O v nanocages by high-temperature pyrolysis under air atmosphere. Further, CdS-S v nanoparticles were grown in-situ on the surface of Co 3 O 4 -O v nanocages by a simple oil bath method. The scanning electron microscopy (SEM) image show that the prepared ZIF-67 is a typical orthododecahedral structure (Fig. 1 b). The Co 3 O 4 -O v nanocages obtained further by high-temperature pyrolysis retained the dodecahedral structure of ZIF-67 (Fig. 1 c). In addition, we have also prepared CdS with different CdCl 2 to TAA molar ratios, and all of them have nanoparticles in their morphological structures (Fig. S1 ). SEM images of CS/CO-x (x = 20, 40, and 60) composites show that CdS-S v nanoparticles grow uniformly on the CO 3 O 4 -O v nanocages surface (Fig. 1 d and Fig. S2-S4). Figure 1 e demonstrates the transmission electron microscopy (TEM) image of the CS/CO-40, which further confirms the uniform growth of CdS-S v nanoparticles on the Co 3 O 4 -O v nanocages surface. More importantly, the interface formed by CdS-S v nanoparticles and Co 3 O 4 -O v nanocages two-phase material was directly observed by high-resolution TEM image. The two phases of material at the interface can be aligned for the (101) lattice plane of CdS-S v nanoparticles and the (311) lattice plane of Co 3 O 4 -O v nanocages, respectively. Furthermore, the TEM energy dispersive spectrometer (EDS) elemental mapping results of individual CS/CO-40 (Fig. 2 e) further confirmed the uniform distribution of Co, O, Cd and S elements in the CS/CO-40 composite. And the corresponding EDS spectrum are shown in Fig. S5. All these results indicate that CdS-S v /Co 3 O 4 -O v composites have been successfully prepared. We further analyzed the phase composition of the photocatalysts by X-ray diffraction (XRD). As shown in Fig. 2 a, pure hexagonal CdS (JCPDS 41-1049) and pure cubic Co 3 O 4 (JCPDS 42-1467) have been successfully obtained. The ZIF-67 precursor has been completely converted to Co 3 O 4 -O v by pyrolysis (Fig. S6). The diffraction peaks of the CS/CO-20, CS/CO-40 and CS/CO-60 composite photocatalysts corresponded to the CdS-S v phase and Co 3 O 4 -O v phase, respectively. This indicates that Co 3 O 4 -O v is able to maintain excellent stability in the oil bath reaction for secondary in situ growth of CdS-S v . In addition, we have also investigated the effect of different CdCl 2 and TAA molar ratios on the crystal surface structure during CdS-S v preparation. The results show that an increase in TAA content will lead to a decrease in the relative diffraction intensity of the (101) plane (Fig. S7). The molecular structure of the photocatalyst was further investigated by FTIR spectroscopy (Fig. S8). The strong absorption peaks at 659 cm − 1 and 570 cm − 1 can be observed for the Co 3 O 4 -O v , CS/CO-20, CS/CO-40, and CS/CO-60, which are considered as the characteristic peaks of spinel Co 3 O 4− Ov. And the absorption peaks at 659 cm − 1 and 570 cm − 1 are attributed to the stretching vibrational modes of Co 2+ -O and Co 3+ -O, where Co 2+ and Co 3+ are tetrahedral and octahedral coordinated, respectively [ 27 ]. Moreover, it also confirms that Co 3 O 4 -O v maintains its structural stability in the secondary reaction. No characteristic peaks of the ZIF-67 precursor were detected in the FT-IR spectroscopy of Co 3 O 4 -O v (Fig. S9), further indicating that ZIF-67 has been completely converted to Co 3 O 4 -O v by pyrolysis treatment. The results of FT-IR analysis are in agreement with those of XRD analysis. The light absorption capacity of the photocatalysts was analyzed by UV-vis diffuse reflectance spectroscopy (UV-Vis DRS). The absorption edge of CdS-S v nanoparticles is located at 550 nm (Fig. S10). Co 3 O 4 -O v and CS/CO-40 showed strong light absorption in both UV and visible regions. According to the plot of transformed Kubelka–Munk function versus the energy of exciting light, the band gap values of CdS-S v and Co 3 O 4 -O v were estimated to be 2.7 eV and 2.4 eV, respectively (Fig. S10). Furthermore, based on the Mott-Schottky plots (Fig. S11), the flat band potentials of CdS-S v and Co 3 O 4 -O v are − 0.34 V and 0.51 V versus Ag/AgCl, respectively, which are equivalent to -0.14 V and 0.71 V versus the normal hydrogen electrode (NHE), respectively. In general, the conduction band (CB) potential of n-type semiconductors and the valence band (VB) potential of p-type semiconductors are more negative and more positive, respectively, than the flat-band potential [ 28 , 29 ]. Thus, the CB of CdS-S v and the VB of Co 3 O 4 -O v are − 0.34 V and 0.91 V versus NHE, respectively. According to the band gap value, the VB of CdS-S v and CB of Co 3 O 4 -O v can be further calculated as 2.02 V and − 0.58 V respectively. In general, the larger the specific surface area and the richer the pore structure, the more adsorption sites are found in the photocatalysts. Therefore, the physical properties of specific surface area and pore structure of CdS-S v , Co 3 O 4 -O v , and CS/CO-x (x = 20, 40, and 60) photocatalysts were further investigated (Fig. S12a). For the CdS photocatalysts, no significant hysteresis loops were observed on the N 2 adsorption-desorption isotherm. In contrast, Co 3 O 4 -O v , CS/CO-20, CS/CO-40, and CS/CO-60 all exhibited typical type-IV adsorption-desorption isotherms, suggesting the possible presence of meso- and macropores (Fig. S12b). The rich pore structure of Co 3 O 4 -O v will be more favorable for the in situ confined growth of CdS-S v nanoparticles, which will lead to the formation of tightly packed heterostructures. The BET surface area of Co 3 O 4 -O v , CS/ CO-20, CS/CO-40, and CS/CO-60 had BET surface areas of 133.3464, 12.2690, 28.6469, and 44.9606 m 2 /g, respectively, which are much higher than that of the simple CdS-S v photocatalyst (2.6295 m 2 /g). We confirmed the presence of oxygen defects and sulfur defects in the prepared photocatalysts by electron paramagnetic resonance (EPR) tests. As shown in Fig. 2 b, the strong EPR signal detected at g = 2.004 is able to indicate the presence of oxygen and sulfur vacancies in Co 3 O 4 -O v and CdS-S v , respectively [ 30 , 31 ]. And stronger EPR signals for Co 3 O 4 -O v , CdS-S v and CS/CO-40 indicate the presence of a higher number of unpaired electrons, which is favourable for the generation of photogenerated carriers [ 30 – 32 ]. In addition, the EPR signal intensity of CS/CO-40 is slightly lower than that of CdS-S v and Co 3 O 4 -O v , suggesting that CS/CO has a lower proportion of unpaired electrons, which may be due to the bonding effect between the interfaces that allows the oxygen/sulfur vacancies to be compensated. X-ray photoelectron spectroscopy (XPS) full and high-resolution spectra demonstrate the surface elemental composition and chemical state of CdS-S v , Co 3 O 4 -O v and CS/CO-40, respectively, as shown in Fig. S13 and Fig. 2 (c-f). The Cd 3d 3/2 and Cd 3d 5/2 spin-orbit splitting peaks of CS/CO-40 are located at 411.60 and 404.80 eV, respectively (Fig. 2 c), and are attributed to the presence of Cd-S bond. Interestingly, CS/CO-40 shows additional Cd 3d signal peaks at low binding energies compared to CdS-S v , which may be attributed to the Cd-O bonds formed at the heterogeneous interface. The peaks located at 162.58 and 161.28 eV can correspond to S 2p 1/2 and S 2p 3/2 of CS/CO-40, respectively (Fig. 2 d). Compared to the S 2p high-resolution spectrum of CdS-S v , additional S species were also detected at the low binding energy (160.08 eV) of CS/CO-40. Combined with the EPR results, the presence of oxygen vacancies and sulfur vacancies would contribute to the formation of chemical bonds at the interface of CdS-S v and Co 3 O 4 -O v [ 33 , 34 ]. Based on this, the peaks at low binding energy of the high-resolution spectra of Cd 3d and S 2p of CS/CO-40 can be attributed to the presence of Cd-O and S-Co bonds, respectively [ 35 – 37 ]. The Co 2p high-resolution spectra of Co 3 O 4 -O v and CS/CO-40 (Fig. 2 e) show typical fitted peaks corresponding to Co 2+ 2p 1/2 , Co 3+ 2p 1/2 , Co 2+ 2p 3/2 , and Co 3+ 2p 3/2 , respectively. The O1s spectrum of Co 3 O 4 -O v was fitted to three peaks, which were attributed to lattice oxygen (~ 529.48 eV, O L ), oxygen vacancy (~ 530.88 eV, O V ) and chemisorbed oxygen (~ 532.48 eV, O abs ), respectively (Fig. 2 f). In contrast, the O1s spectrum of CS/CO-40 can identify four fitted peaks for O L (O-Cd), O L (O-Co), O V , and O abs . More importantly, the binding energies of both Cd 3d and S 2p in CS/CO-40 are negatively shifted compared with that of CdS-S v . On the contrary, the binding energies of both Co 2p and O1s in the composite photocatalyst are positively shifted compared with that of Co 3 O 4 -O v . This result indicates that when CdS-S v is in close contact with Co 3 O 4 -O v , the electrons on Co 3 O 4 -O v are transferred to CdS-S v up to the Fermi energy level (E F ) equilibrium, which induces energy band bending, and thus induces the formation of a IEF pointing from Co 3 O 4 -O v to CdS-S v at the interface. 3.2 Photocatalytic performance and charge separation The reactivity of the photocatalysts was evaluated under simulated sunlight using RCSP as a biomass reaction substrate. In contrast to some of the typical current photocatalytic research work on the use of raw biomass and biomass polymers as reaction substrates (Table S1 ), we have innovatively achieved the one-step photocatalytic conversion of RCSP to high value-added C 1 /C 2 gases. The results of the photocatalytic reaction showed that CO, CH 4 , C 2 H 6 , and C 2 H 4 were the main C 1 and C 2 gas products, and almost no CO 2 was produced (Fig. S14). Firstly, we investigated the photocatalytic properties of CdS nanoparticles prepared with different CdCl 2 and TAA ratios (1:1, 1:2, and 1:3). In the normal reaction, CO, CH 4 , C 2 H 6 and C 2 H 4 were detected in the photocatalytic reaction products of all CdS nanoparticles (Fig. S15). Further we also prepared CdS/Co 3 O 4 with different Cd 2+ /S 2− molar ratios and evaluated the photocatalytic properties. The results show that CS/CO-40 (Cd 2+ /S 2− = 1:1) has a higher C 1 /C 2 gas yield (Fig. S16). Based on these results, we further prepared CS/CO-x (x = 20, 40, and 60) photocatalysts to evaluate the photocatalytic activity. As shown in Fig. 3 a, the C 1 /C 2 gas products evolution rates of CS/CO-x (x = 20, 40, and 60) are significantly higher than those of CdS-S v and Co 3 O 4 -O v , and this result further confirms that the heterostructure building can effectively improve the photocatalytic performance. CS/CO-40 exhibited the best photocatalytic activity with CO, CH 4 , C 2 H 6 and C 2 H 4 evolution rates of 691.99, 2057.69, 202.93 and 187.29 µmol/g, respectively. And it reveals that the CO yield was increased by about 2.3 and 4.7 times, the CH 4 yield was increased by 5.4 and 7.2 times, the C 2 H 6 yield was increased by 3.1 and 4.0 times, and the C 2 H 4 yield was increased by 2.9 and 3.3 times compared with CdS-S v and Co 3 O 4 -O v , respectively. And among all the prepared photocatalysts, CS/CO-40 showed the highest CH 4 selectivity and total hydrocarbon (C x H y ) gas selectivity of 65.53% and 77.96%, respectively (Fig. 3 b). The results of time-dependent photocatalytic product yields of CdS-S v , Co 3 O 4 -O v and CS/CO-x (x = 20, 40, and 60) are displayed in Fig. 3 c and Fig. S (17–20). We further explored the effect of photocatalytic reaction conditions on the activity. As shown in Fig. 3 d, when only DMSO was not added to the reaction system, only CO and CH 4 were detected in the photocatalytic products. Experimental group-3 demonstrated that small amounts of CO, CH 4 , C 2 H 6 and C 2 H 4 could also be produced in the photoreactive system without a catalyst. Experimental group-4 further confirmed that small amounts of CO and CH 4 as well as trace amounts of C 2 H 6 and C 2 H 4 could be detected in the absence of catalyst and NaOH. However, only a small amount of CO could be detected in the photoreactive system in the presence of only NaOH without catalyst and DMSO. All experimental control group results illustrate the important auxiliary roles of DMSO and NaOH for promoting the photocatalytic conversion of structurally complex natural polymers to C 1 /C 2 gases. In order to investigate the photogenerated charge separation efficiency of the photocatalysts, transient photocurrent and electrochemical impedance spectroscopy tests were performed. By continuously recording the transient photocurrent response for several on/off cycles under light irradiation, it was confirmed that the photocurrent of the photocatalysts exhibited high reproducibility and stability over multiple cycles (Fig. 4 a). The CdS-S v /Co 3 O 4 -O v composite photocatalysts showed stronger photocurrent intensity compared with CdS-S v and Co 3 O 4 -O v , which further confirmed that the composite photocatalysts possessed higher photogenerated electron-hole separation efficiency. Similarly, electrochemical impedance spectroscopy (EIS) demonstrated that the composite photocatalysts have smaller charge transfer resistance and thus more efficient photogenerated charge separation efficiency (Fig. 4 b). In addition, the effect of heterogeneous structure building on photogenerated charge separation was further revealed by PL spectra. It is generally believed that a slower radiative recombination between photogenerated carriers will lead to a lower PL emission intensity [ 38 , 39 ]. The PL emission intensity of the composite photocatalysts are weaker than that of CdS-S v (Fig. S21), which indicates that the successful construction of the heterojunction can effectively promote the charge separation efficiency. All of the above photoelectrochemical test results show that CS/CO-40 has a superior photogenerated charge separation ability, which is consistent with the photocatalytic reaction results. Reactive radicals are essential for a deeper understanding of the photocatalytic reaction mechanism and play an important role in photocatalytic reactions. To further identify the main oxidatively active species during the photocatalytic reaction, we performed free radical trapping experiments using benzoquinone (BQ), isopropanol (IPA) and ethylenediaminetetraacetic acid (EDTA) as superoxide radicals (·O 2− ), hydroxyl radicals (·OH) and hole (h + ) trapping agents, respectively. As shown in Fig. S22, the addition of all scavengers had a significant effect on product generation. In the experimental group with the addition of BQ, the production of C 2 H 4 and C 2 H 6 was suppressed while the evolution rate of CH 4 was significantly promoted. Interestingly, scavenging of ·OH by isopropanol inhibited methane production while having less effect on the evolution rates of CO, C 2 H 4 and C 2 H 6 . When the h + were captured by EDTA, the evolution rate of all products decreased. The analysis of the above results indicates that ·O 2− and ·OH are the two major oxidatively active radicals, which play a key role in the production of C 2 products and CH 4 , respectively. The ·O 2− and ·OH enerated during the reaction were determined using ESR tests with DMPO as the trapping agent, and the results are shown in Fig. 4 (c, d). Under dark conditions, neither DMPO-·O 2− nor DMPO-·OH ESR signals were detected. Under light, the photocatalyst exhibited strong DMPO-·O 2− and DMPO-·OH ESR signal peaks. And the DMPO-·O 2− and DMPO-·OH ESR signal intensities are enhanced with the increase of irradiation time. The ability of the VB of CdS-S v and the CB of Co 3 O 4 -O v to satisfy the standard potentials of H 2 O/·OH (1.99 V vs. NHE) and O 2 /·O 2− (− 0.33 V vs. NHE), respectively, demonstrates that the charge transfer between CdS-S v and Co 3 O 4 -O v follows the Z-scheme pathway [ 40 , 41 ]. The above results also indicate that ·O 2− and ·OH are the main active radicals produced during the photocatalytic reaction. 3.3 DFT calculation and photocatalytic mechanism Interfacial interactions and built-in electric fields between CdS-S v and Co 3 O 4 -O v interfaces in CdS-S v /Co 3 O 4 -O v heterojunctions are crucial to promote efficient photogenerated charge transfer. It is well known that when two semiconductors with different E F and work functions (Φ) are in close contact, a IEF will be formed at the interface [ 42 , 43 ]. The interfacial interactions and charge transfer mechanisms in CdS-S v /Co 3 O 4 -O v heterojunctions are further revealed by DFT calculations. The structures of CdS-S v , Co 3 O 4 -O v , and CdS-S v /Co 3 O 4 -O v heterojunctions model were successfully established (Fig. S23). The crystal structure models of CdS-S v and Co 3 O 4 -O v from different views are shown in Fig. S24 and S25. The Φ and E F of CdS-S v and Co 3 O 4 -O v were simulated with first principles (Fig. 5 a and 5 b). The Φ of CdS is significantly larger than that of Co 3 O 4 -O v , which implies that the electrons of the latter are more likely to escape. When the heterogeneous interface is in contact, the difference in E F will result in the transfer of electrons from Co 3 O 4 -O v to CdS-S v . The electron density distribution at the heterojunction interface was further simulated with charge density difference to visualize the inter-interface electron transfer (Fig. 5 c and 5 d) [ 44 , 45 ]. The results confirm the coupled connection of chemical bonds between the interfaces of the two materials and the presence of strong interfacial interactions. A spontaneous interfacial charge transfer pathway from Co 3 O 4 -O v to CdS-S v is theorized to exist when the two materials are in close contact, and the interfacial chemical bonding can act as a channel to facilitate inter-interfacial charge transfer. The results of the above analysis are consistent with the XPS analysis. Based on these results, a charge transfer mechanism for heterojunction photocatalysts is proposed. The energy band structure was determined by UV-vis DRS and Mott Schottky tests. The energy band structure of the CdS-S v /Co 3 O 4 -O v system before and after contact is shown in Fig. 5 e. When CdS-S v is in contact with Co 3 O 4 -O v , the electrons in Co 3 O 4 -O v are transferred to CdS-S v until the E F are balanced, resulting in the formation of a unique IEF. Under illumination, the IEF promotes the transfer of photoexcited electrons from CdS-S v to the VB in Co 3 O 4 -O v , and the composite is realized through Z-scheme charge transfer. The photogenerated electrons in the CB of Co 3 O 4 -O v reduce O 2 to ·O 2− , while the holes generated in the VB of CdS-S v oxidize H 2 O to form ·OH. The ESR results and DFT calculations further indicate that the current system should be a Z-scheme heterojunction rather than type-II heterojunction. In addition, the chemical bonds formed at the heterointerface between CdS and Co 3 O 4 -O v can act as interfacial charge transfer channels and also play an important role in accelerating the charge transfer between CdS-S v and Co 3 O 4 -O v . Photocatalytic conversion of RCSP to high value-added C 1 /C 2 gases under the synergistic effect of photoactive radicals, DMSO and NaOH (Fig. 6 a). In a world, the CdS-S v /Co 3 O 4 -O v heterojunction has a high performance photocatalytic RCSP conversion performance due to its strong light absorption ability, follows a Z-scheme charge transfer pathway in order to retain a strong redox capacity, and is able to promote charge transfer through interfacial chemical bonding. For further in-depth analysis of the reaction mechanisms, glucose, fructose and xylose were further investigated as typical lignocellulose-derived monomers. The results of photocatalytic experiments using glucose, fructose and xylose as reaction substrates showed that gas-phase products such as CO, CH 4 , C 2 H 4 and C 2 H 6 were detected, which is in agreement with the results of the RCSP photocatalytic experiments (Fig. S26). And liquid phase product analysis showed that organic acids such as lactic acid, acetic acid, propionic acid and formic acid were the main products, with lactic acid having the highest yield (Fig. S27). Combined with previous studies [ 11 , 46 ], we propose possible reaction pathways for the conversion of glucose, fructose, and xylose to organic acids, as shown in Fig. S28 and Fig. S29. Glucose is oxidised by α- and β-oxidation to formic acid, intermediate-I, ethanedioic acid, and intermediate-II. Ethanedioic acid can produce acetic acid and formic acid by dehydration and C-C bond breaking, respectively. Formic acid can also be produced when the C-C bond of intermediate-I is broken. The isomerisation of glucose to fructose is further followed by retro-aldol condensation reaction to produce glyceraldehyde and 1,3-dihydroxyacetone. Lactic acid is then further produced by dehydration and 1,2-hydride shift. During the oxidation of xylose, xylose is first isomerised into intermediate I and intermediate II. And then Intermediate-I generates glyceraldehyde and ethanedioic acid by retro-aldol condensation reaction. Intermediate-II generates acetic acid and ethanedioic acid by α- and β-oxidation. The above products were further converted to lactic acid and formic acid, respectively. Lactic acid dehydrates to form propionic acid. We speculate that the production of products such as CO, CH 4 , C 2 H 4 and C 2 H 6 may be attributed to the further oxidation of organic acids during photocatalysis. In order to verify the conjecture, the product distribution of photocatalysis was further evaluated using organic acids such as formic acid, lactic acid, propionic acid and acetic acid as reaction substrates. The results were as expected (Fig. S26), lactic acid, acetic acid, formic acid, and propionic acid showed high selectivity for the conversion of CH 4 , CO, C 2 H 4 , and C 2 H 6 , respectively. Based on the above findings and previous studies, we propose a possible mechanism of transformation, as shown in Fig. 6 b. Typical lignocellulosic monomers such as glucose and xylose are oxidised in the presence of oxidatively active species to produce organic acids such as lactic, propionic and acetic acids as well as formic acid through cascade-by-cascade oxidation and C-C bond breaking, which are ultimately oxidised completely to form methane. 4 Conclusion In conclusion, we have successfully constructed an efficient Z-scheme reaction system for the photocatalytic conversion of corn stover meal to C 1 /C 2 gases. In terms of material design, a CdS-S v /Co 3 O 4 -O v Z-scheme heterojunction with excellent light-absorbing ability was successfully designed. The IEF in the CdS-S v /Co 3 O 4 -O v heterojunction effectively promotes photogenerated charge transfer, while the interfacial chemical bonds can act as additional electronic bridges to accelerate electron transfer. Both XPS and ESR results have demonstrated that the CdS-S v /Co 3 O 4 -O v heterojunction follows a Z-scheme charge transfer mechanism. DFT calculations simulate the work functions, Fermi energy levels, and charge density variations at the heterojunction interface, which further validates the creation of an IEF. Under simulated solar irradiation, RCSP can be efficiently and directly converted into high value-added C 1 /C 2 gases. The CO, CH 4 , C 2 H 6 and C 2 H 4 yields of this reaction system could reach up to 691.99, 2057.69, 202.93 and 187.29 µmol/g, respectively, and the selectivities of CH 4 and C x H y were as high as 65.53% and 77.96%, respectively. Combining the analysis of the series of characterisation data and the results of the photocatalysis experiments, we further discuss the possible photocatalytic mechanisms and conversion pathways. This work provides new ideas for high-value utilization of agroforestry waste through green conversion technology, which has a positive effect on accelerating the process of carbon neutrality. Declarations Competing interests The authors declare no competing interests. Funding This work was financially supported by the National Natural Science Foundation of China (No. 32071713) and the Outstanding Youth Foundation Project of Heilongjiang Province (No. JQ2019C001). Author Contribution Guoyang Gao: conceptualization, methodology, formal analysis, investigation, validation, and writing. Yuxin Dai and Ying Lin: formal analysis, investigation, and writing. Houjuan Qi: methodology, formal analysis and supervision. Zhanhua Huang: conceptualization, project administration, funding acquisition, editing, and supervision. All authors reviewed the manuscript. Data availability No datasets were generated or analysed during the current study. References Sun Z, Bottari G, Afanasenko A, Stuart M, Deuss P, Fridrich B, Barta K (2018) Complete lignocellulose conversion with integrated catalyst recycling yielding valuable aromatics and fuels. 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Supplementary Files Supporttinginformation.docx Cite Share Download PDF Status: Published Journal Publication published 19 Nov, 2024 Read the published version in Advanced Composites and Hybrid Materials → Version 1 posted Editorial decision: Revision requested 09 Oct, 2024 Reviews received at journal 06 Oct, 2024 Reviews received at journal 06 Oct, 2024 Reviewers agreed at journal 30 Sep, 2024 Reviewers agreed at journal 26 Sep, 2024 Reviewers invited by journal 26 Sep, 2024 Editor assigned by journal 26 Sep, 2024 Submission checks completed at journal 25 Sep, 2024 First submitted to journal 20 Sep, 2024 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. 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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-5122454","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":364070625,"identity":"18fd987f-7228-45f5-813e-9dc2dab3addd","order_by":0,"name":"Guoyang Gao","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Guoyang","middleName":"","lastName":"Gao","suffix":""},{"id":364070626,"identity":"24e2ffe5-56b4-47bc-8159-75ebdc1c1365","order_by":1,"name":"Yuxin Dai","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Yuxin","middleName":"","lastName":"Dai","suffix":""},{"id":364070627,"identity":"ddf35ceb-8e83-4309-bfb4-c5b6ecf8ae74","order_by":2,"name":"Ying Lin","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Ying","middleName":"","lastName":"Lin","suffix":""},{"id":364070628,"identity":"f67e4571-3224-40df-97e0-f40ed74947c7","order_by":3,"name":"Houjuan Qi","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Houjuan","middleName":"","lastName":"Qi","suffix":""},{"id":364070629,"identity":"d6ca4660-1b63-4a79-8284-96070a609c37","order_by":4,"name":"Zhanhua Huang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA40lEQVRIiWNgGAWjYBACAwh1gIdf/v3DBwkVNcRrkZFsyGE2eHDmGPFabAwO5LBJPmxhJqzFXCL52cMvf+7wGBw4e6wisYGNgb+9OwGvFssZaebGMjzPeCQP9qXdSNwhwyBx5uwG/A67kWAmLSFxmIfvMIPZjcQzbAwGErmEtKR/k5YwOMzDcIzBrCCxjZkYLTlmkh8SDvMInOExYyBOy5k3ZdIMBw7zSM5gS5ZIOHOMh7Bfjqdvk/zx57A9vwTzwY8/Kmrk+Nt78WsBAWYeJA4PTmXIgPEHUcpGwSgYBaNgxAIAbXlM+C6+B44AAAAASUVORK5CYII=","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":true,"prefix":"","firstName":"Zhanhua","middleName":"","lastName":"Huang","suffix":""}],"badges":[],"createdAt":"2024-09-20 09:29:12","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5122454/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5122454/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s42114-024-01073-4","type":"published","date":"2024-11-19T15:58:04+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":68195417,"identity":"11028167-de82-46c8-a78f-abe1094e91f0","added_by":"auto","created_at":"2024-11-04 14:36:04","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":595153,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Schematic illustration of the preparation of CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e composites. SEM images of (b) ZIF-67, (c) Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e nanocages, and (d) CS/CO-40. (e) TEM image and (f) High-resolution TEM image of CS/CO-40. (g) High-angle annular dark field-scanning TEM image and (h-k) the corresponding EDS elemental mapping results of CS/CO-40.\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5122454/v1/cfcfe58728f32a751df03a7c.jpeg"},{"id":68196453,"identity":"69e38db5-66b5-4fb4-8040-6b037549c71b","added_by":"auto","created_at":"2024-11-04 14:44:04","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":3518257,"visible":true,"origin":"","legend":"\u003cp\u003e(a) XRD patterns of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, CdS-S\u003csub\u003ev\u003c/sub\u003e, CS/CO-x (x=20, 40, and 60). (b) EPR spectra of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, CdS-S\u003csub\u003ev\u003c/sub\u003e, and CS/CO-40. XPS high-resolution spectra of CdS-S\u003csub\u003ev\u003c/sub\u003e and CS/CO-40 in the Cd 3d region (c) and the S 2p region (d). XPS high-resolution spectra of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e and CS/CO-40 in the Co 2p region (e) and the O 1s region (f).\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5122454/v1/b605d6aa1d936839b5e8ac89.jpeg"},{"id":68195418,"identity":"f6fcb0bb-2a0a-4d1a-9217-a8dae0a2819c","added_by":"auto","created_at":"2024-11-04 14:36:04","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":4282071,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Gas-phase product evolution rates of CdS-S\u003csub\u003ev\u003c/sub\u003e, Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, and CS/CO-x (x=20, 40, and 60). (b) CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e, and total hydrocarbon product selectivities of CdS, Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, and CS/CO-x (x=20, 40, and 60). (c) Time-dependent products evolution rates of CS/CO-40. (d) Gas-phase product evolution rates of experimental groups under different conditions (The normal reaction consists of RCSP, water, catalysts, DMSO and NaOH. Experimental group 1 is the normal experimental group. Experimental groups 2-5 are variable control groups.).\u0026nbsp;\u003c/p\u003e","description":"","filename":"floatimage3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5122454/v1/67924230193564d879f5338f.jpeg"},{"id":68195422,"identity":"7da13162-48fd-46e2-8077-5b122cf752a6","added_by":"auto","created_at":"2024-11-04 14:36:04","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":4897425,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Photocurrent-time responses curves and (b) electrochemical impedance spectroscopy of CdS-S\u003csub\u003ev\u003c/sub\u003e, Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, and CS/CO-x (x=20, 40, and 60). DMPO spin-trapping ESR spectra recorded for (c) ·O\u003csup\u003e2–\u003c/sup\u003e (a) and (d) ·OH of CS/CO-40.\u003c/p\u003e","description":"","filename":"floatimage4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5122454/v1/cf866964367156ffc82fd66b.jpeg"},{"id":68195421,"identity":"bd552204-cb13-4536-8364-279a880f2b59","added_by":"auto","created_at":"2024-11-04 14:36:04","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":408275,"visible":true,"origin":"","legend":"\u003cp\u003eCalculated model and electrostatic potentials of (a) CdS-S\u003csub\u003ev\u003c/sub\u003e and (b) Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e. (c) Top and side views of the optimized and (d) the charge density difference CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e heterojunction model, the electron accumulation and depletion are shown in yellow and blue, respectively. (e) Band energy positions of CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e before contact and after contact, and Z-scheme charge transfer mechanism under irradiation.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-5122454/v1/3672342a28dcdcb95af76325.png"},{"id":68196866,"identity":"de28748a-b33a-4c1a-b350-b8f363fee561","added_by":"auto","created_at":"2024-11-04 14:52:04","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":206668,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Schematic diagram of photocatalytic conversion of RCSP to high value-added C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases. Possible conversion pathways for the photocatalytic conversion of monosaccharides to CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e, and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-5122454/v1/13e5105d2b9df326cf96eef2.png"},{"id":69835789,"identity":"eceacea5-d61a-4173-8b95-0cb791ec354a","added_by":"auto","created_at":"2024-11-25 16:14:25","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":14648108,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5122454/v1/41c5596f-2ec9-4e5f-89ec-91c08b22718d.pdf"},{"id":68195424,"identity":"b8a47535-e417-4fbd-9637-62f6fbe44792","added_by":"auto","created_at":"2024-11-04 14:36:05","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":5043093,"visible":true,"origin":"","legend":"","description":"","filename":"Supporttinginformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-5122454/v1/d2076591acdbfd9f849e9323.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Efficient charge separation in Z-scheme heterojunctions induced by chemical bonding-enhanced internal electric field for promoting photocatalytic conversion of corn stover to C1/C2 gases","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eGrowing global energy demand and environmental concerns have greatly contributed to the utilization and development of sustainable and clean energy sources. Therefore, there is an urgent need to seek sustainable alternatives to traditional fossil energy sources. Lignocellulose is a good renewable resource that is carbon-neutral, economical and readily available. Therefore, efficient utilization of lignocellulose will help reduce dependence on fossil fuels [\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Corn stover is the most stable part of the non-food lignocellulosic biomass resource and is the most conveniently available biomass resource. High-value utilization of corn stover not only solves the environmental problems caused by massive burning, but also promises the conversion of agricultural and forestry wastes into important platform compounds and gases [\u003cspan additionalcitationids=\"CR5\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eWith the development of photocatalytic technology, the use of solar energy to drive the conversion of biomass into high-value chemicals offers a highly promising approach [\u003cspan additionalcitationids=\"CR8\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. In recent years, the conversion of lignocellulose into platform compounds and hydrogen using photocatalytic technology has been of interest to researchers [\u003cspan additionalcitationids=\"CR11\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. However, due to the complex composition of corn stover, the products of photocatalytic conversion of macromolecular compounds often suffer from complex composition, low conversion efficiency, and poor selectivity. Although photocatalytic stover can achieve hydrogen production, the source of hydrogen protons mostly originates from water, which will not be able to effectively realize the utilization and conversion of corn stover resources. Compared with hydrogen, gaseous compounds containing one or two carbons (C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases) are important chemical raw materials and intermediates [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. As a carbon-rich carrier, the conversion of corn stover into CH\u003csub\u003e4\u003c/sub\u003e, CO, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e, and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e through photocatalytic technology will be more promising to realize the high value-added utilization of corn stover.\u003c/p\u003e \u003cp\u003eIn recent years, many types of photocatalysts such as metal oxides, metal sulfides, metal-organic frameworks (MOFs), organic polymers, and covalent organic frameworks have been developed [\u003cspan additionalcitationids=\"CR16\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Heterojunction photocatalysts offer significant advantages over individual catalysts in inhibiting photogenerated electron-hole separation complexes and addressing the low redox capacity of the catalysts [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. The Z-scheme heterojunction retains a strong redox capacity and its charge transfer mechanism greatly facilitates the spatial separation of carriers compared to conventional type-I and type-II [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. The photocatalytic efficiency does not only depend on the type of catalyst, but often the catalyst's properties such as morphology dimension and surface structure will also affect the catalytic efficiency. Hollow nanostructured materials have attracted much attention because they can capture more incident photons through multiple scattering and can promote space charge separation and extend radiation lifetime through suitable catalyst modification [\u003cspan additionalcitationids=\"CR23\" citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. Zeolitic Imidazolate Frameworks (ZIFs) is an important class of MOFs, and its derivatives with hollow structures can be prepared by high-temperature pyrolysis and can well maintain the original morphological features [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Therefore, the construction of Z-scheme heterojunction hollow-structured photocatalysts based on ZIF derivatives is a promising pathway expected to realize efficient photocatalytic conversion of corn stover.\u003c/p\u003e \u003cp\u003eHere, we designed and prepared a sulfur/oxygen dual-vacancies CdS/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e) Z-scheme heterojunction for photocatalytic conversion of raw corn stover powder (RCSP). The hollow Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e prepared by pyrolysis of ZIF-67 not only maintains the original three-dimensional morphology well, but also expands the light absorption range. The growth of CdS-S\u003csub\u003ev\u003c/sub\u003e nanoparticles on the hollow Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e surface was further realized by a simple oil bath method. A series of characterization results indicate that the electron transfer between Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e and CdS-S\u003csub\u003ev\u003c/sub\u003e follows a Z-scheme heterojunction under light irradiation. The regionally enhanced internal electric field (IEF) and interfacial chemical bonding effectively facilitate the photogenerated charge separation and transfer. Moreover, density functional theory (DFT) calculations confirm the interaction between heterogeneous interfaces and the formation of internal electric fields. The photocatalytic reaction results indicate that the raw corn stover powder (RCSP) can be efficiently converted to CH\u003csub\u003e4\u003c/sub\u003e, CO, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e with high yields of 691.99, 2057.69, 202.93 and 187.29 \u0026micro;mol/g, respectively. The selectivities of CH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003ex\u003c/sub\u003eH\u003csub\u003ey\u003c/sub\u003e were 65.53% and 77.96%, respectively. The radical trapping experiments showed \u0026middot;OH and \u0026middot;O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e as the main radical active species. On this basis, we further propose possible mechanisms for product transformation. This work provides a feasible strategy for the photocatalytic conversion of RCSP, an agroforestry waste, into high value-added hydrocarbon gases.\u003c/p\u003e"},{"header":"2 Experimental","content":"\u003cp\u003e \u003cb\u003eSynthesis of CdS nanoparticles.\u003c/b\u003e In a typical procedure, 300 mg TAA and 790 mg CdCl\u003csub\u003e2\u003c/sub\u003e were dissolved in 40 ml of deionized water. The mixed solution was placed in a three-necked flask and stirred continuously for 20 min. The reaction was then carried out in an oil bath at 80\u0026deg;C and kept for 2 h. In addition, we also prepared CdS nanoparticles with different CdCl\u003csub\u003e2\u003c/sub\u003e and TAA molar ratios. After cooling naturally to room temperature, the orange-yellow precipitate was collected by centrifugation. The product was further washed several times with water and ethanol and then dried under vacuum at 60\u0026deg;C for 12 hours. The final product CdS-S\u003csub\u003ev\u003c/sub\u003e was obtained as an orange-yellow powder. In addition, the CdS nanoparticles prepared only by varying the CdCl\u003csub\u003e2\u003c/sub\u003e and TAA molar ratios (1:1, 1:2, and 1:3), and the other conditions were consistent with the preparation process described above.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of ZIF-67 and Co\u003c/b\u003e \u003csub\u003e \u003cb\u003e3\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003csub\u003e \u003cb\u003e4\u003c/b\u003e \u003c/sub\u003e \u003cb\u003enanocages.\u003c/b\u003e ZIF-67 dodecahedron was first prepared as a template, which was further subjected to pyrolysis to prepare Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e. In a typical procedure, 0.5 g of Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e and 0.6 g of dimethylimidazole were dissolved in 20 mL of methanol, respectively. Further the dimethylimidazole solution was injected into the Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e solution under vigorous stirring and stirring was continued for 1 h. The mixed solution was then aged at room temperature for 12 h. Finally, the purple precipitate was washed three times with methanol and dried under vacuum for 12 h. ZIF-67 purple powder was obtained. The prepared ZIF-67 powder was further pyrolyzed in tube furnace under flowing air at 400\u0026deg;C for 1h (3\u0026deg;C/min). The Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026minus;\u003c/sub\u003eO\u003csub\u003ev\u003c/sub\u003e nanocages powder was collected after cooling to room temperature.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of CdS/Co\u003c/b\u003e \u003csub\u003e \u003cb\u003e3\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO\u003c/b\u003e \u003csub\u003e \u003cb\u003e4\u003c/b\u003e \u003c/sub\u003e \u003cb\u003ecomposites.\u003c/b\u003e CdS nanoparticles were grown on Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanocages surface by oil bath method. Generally, 300 mg of TAA, 790 mg of CdCl\u003csub\u003e2\u003c/sub\u003e and a certain mass of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e powder were dissolved in 40 mL of deionized water. The mixed solution was then placed in a three-necked flask and stirred vigorously for 20 min. The reaction was then carried out in an oil bath at 80\u0026deg;C and kept for 2 h. After cooling naturally to room temperature, the precipitate was collected by centrifugation and washed three times with ethanol and water, respectively. The precipitates were vacuum dried at 60\u0026deg;C for 12 h to obtain CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026minus;\u003c/sub\u003eO\u003csub\u003ev\u003c/sub\u003e composites. The weight of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e in a series of CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026minus;\u003c/sub\u003eO\u003csub\u003ev\u003c/sub\u003e composites was 20 mg, 40 mg, and 60mg, which were labeled as CS/CO-20, CS/CO-40, and CS/CO-60.\u003c/p\u003e"},{"header":"3 Results and discussion","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Preparation and characterization\u003c/h2\u003e \u003cp\u003eCdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e with different Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e mass loadings were prepared by high-temperature pyrolysis and in situ growth strategies, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea. ZIF-67 was used as a template to obtain Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e nanocages by high-temperature pyrolysis under air atmosphere. Further, CdS-S\u003csub\u003ev\u003c/sub\u003e nanoparticles were grown in-situ on the surface of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e nanocages by a simple oil bath method. The scanning electron microscopy (SEM) image show that the prepared ZIF-67 is a typical orthododecahedral structure (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb). The Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e nanocages obtained further by high-temperature pyrolysis retained the dodecahedral structure of ZIF-67 (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec). In addition, we have also prepared CdS with different CdCl\u003csub\u003e2\u003c/sub\u003e to TAA molar ratios, and all of them have nanoparticles in their morphological structures (Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). SEM images of CS/CO-x (x\u0026thinsp;=\u0026thinsp;20, 40, and 60) composites show that CdS-S\u003csub\u003ev\u003c/sub\u003e nanoparticles grow uniformly on the CO\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003enanocages surface (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed and Fig. S2-S4). Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ee demonstrates the transmission electron microscopy (TEM) image of the CS/CO-40, which further confirms the uniform growth of CdS-S\u003csub\u003ev\u003c/sub\u003e nanoparticles on the Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e nanocages surface. More importantly, the interface formed by CdS-S\u003csub\u003ev\u003c/sub\u003e nanoparticles and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003enanocages two-phase material was directly observed by high-resolution TEM image. The two phases of material at the interface can be aligned for the (101) lattice plane of CdS-S\u003csub\u003ev\u003c/sub\u003e nanoparticles and the (311) lattice plane of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e nanocages, respectively. Furthermore, the TEM energy dispersive spectrometer (EDS) elemental mapping results of individual CS/CO-40 (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ee) further confirmed the uniform distribution of Co, O, Cd and S elements in the CS/CO-40 composite. And the corresponding EDS spectrum are shown in Fig. S5. All these results indicate that CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003ecomposites have been successfully prepared.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eWe further analyzed the phase composition of the photocatalysts by X-ray diffraction (XRD). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, pure hexagonal CdS (JCPDS 41-1049) and pure cubic Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (JCPDS 42-1467) have been successfully obtained. The ZIF-67 precursor has been completely converted to Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e by pyrolysis (Fig. S6). The diffraction peaks of the CS/CO-20, CS/CO-40 and CS/CO-60 composite photocatalysts corresponded to the CdS-S\u003csub\u003ev\u003c/sub\u003e phase and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e phase, respectively. This indicates that Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e is able to maintain excellent stability in the oil bath reaction for secondary in situ growth of CdS-S\u003csub\u003ev\u003c/sub\u003e. In addition, we have also investigated the effect of different CdCl\u003csub\u003e2\u003c/sub\u003e and TAA molar ratios on the crystal surface structure during CdS-S\u003csub\u003ev\u003c/sub\u003e preparation. The results show that an increase in TAA content will lead to a decrease in the relative diffraction intensity of the (101) plane (Fig. S7). The molecular structure of the photocatalyst was further investigated by FTIR spectroscopy (Fig. S8). The strong absorption peaks at 659 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 570 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e can be observed for the Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, CS/CO-20, CS/CO-40, and CS/CO-60, which are considered as the characteristic peaks of spinel Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u0026minus;\u003c/sub\u003eOv. And the absorption peaks at 659 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 570 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are attributed to the stretching vibrational modes of Co\u003csup\u003e2+\u003c/sup\u003e-O and Co\u003csup\u003e3+\u003c/sup\u003e-O, where Co\u003csup\u003e2+\u003c/sup\u003e and Co\u003csup\u003e3+\u003c/sup\u003e are tetrahedral and octahedral coordinated, respectively [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. Moreover, it also confirms that Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e maintains its structural stability in the secondary reaction. No characteristic peaks of the ZIF-67 precursor were detected in the FT-IR spectroscopy of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e (Fig. S9), further indicating that ZIF-67 has been completely converted to Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e by pyrolysis treatment. The results of FT-IR analysis are in agreement with those of XRD analysis.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe light absorption capacity of the photocatalysts was analyzed by UV-vis diffuse reflectance spectroscopy (UV-Vis DRS). The absorption edge of CdS-S\u003csub\u003ev\u003c/sub\u003e nanoparticles is located at 550 nm (Fig. S10). Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e and CS/CO-40 showed strong light absorption in both UV and visible regions. According to the plot of transformed Kubelka\u0026ndash;Munk function versus the energy of exciting light, the band gap values of CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e were estimated to be 2.7 eV and 2.4 eV, respectively (Fig. S10). Furthermore, based on the Mott-Schottky plots (Fig. S11), the flat band potentials of CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e are \u0026minus;\u0026thinsp;0.34 V and 0.51 V versus Ag/AgCl, respectively, which are equivalent to -0.14 V and 0.71 V versus the normal hydrogen electrode (NHE), respectively. In general, the conduction band (CB) potential of n-type semiconductors and the valence band (VB) potential of p-type semiconductors are more negative and more positive, respectively, than the flat-band potential [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. Thus, the CB of CdS-S\u003csub\u003ev\u003c/sub\u003e and the VB of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e are \u0026minus;\u0026thinsp;0.34 V and 0.91 V versus NHE, respectively. According to the band gap value, the VB of CdS-S\u003csub\u003ev\u003c/sub\u003e and CB of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e can be further calculated as 2.02 V and \u0026minus;\u0026thinsp;0.58 V respectively.\u003c/p\u003e \u003cp\u003eIn general, the larger the specific surface area and the richer the pore structure, the more adsorption sites are found in the photocatalysts. Therefore, the physical properties of specific surface area and pore structure of CdS-S\u003csub\u003ev\u003c/sub\u003e, Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, and CS/CO-x (x\u0026thinsp;=\u0026thinsp;20, 40, and 60) photocatalysts were further investigated (Fig. S12a). For the CdS photocatalysts, no significant hysteresis loops were observed on the N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption isotherm. In contrast, Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, CS/CO-20, CS/CO-40, and CS/CO-60 all exhibited typical type-IV adsorption-desorption isotherms, suggesting the possible presence of meso- and macropores (Fig. S12b). The rich pore structure of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e will be more favorable for the in situ confined growth of CdS-S\u003csub\u003ev\u003c/sub\u003e nanoparticles, which will lead to the formation of tightly packed heterostructures. The BET surface area of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, CS/ CO-20, CS/CO-40, and CS/CO-60 had BET surface areas of 133.3464, 12.2690, 28.6469, and 44.9606 m\u003csup\u003e2\u003c/sup\u003e/g, respectively, which are much higher than that of the simple CdS-S\u003csub\u003ev\u003c/sub\u003e photocatalyst (2.6295 m\u003csup\u003e2\u003c/sup\u003e/g).\u003c/p\u003e \u003cp\u003eWe confirmed the presence of oxygen defects and sulfur defects in the prepared photocatalysts by electron paramagnetic resonance (EPR) tests. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb, the strong EPR signal detected at g\u0026thinsp;=\u0026thinsp;2.004 is able to indicate the presence of oxygen and sulfur vacancies in Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e and CdS-S\u003csub\u003ev\u003c/sub\u003e, respectively [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. And stronger EPR signals for Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, CdS-S\u003csub\u003ev\u003c/sub\u003e and CS/CO-40 indicate the presence of a higher number of unpaired electrons, which is favourable for the generation of photogenerated carriers [\u003cspan additionalcitationids=\"CR31\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. In addition, the EPR signal intensity of CS/CO-40 is slightly lower than that of CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, suggesting that CS/CO has a lower proportion of unpaired electrons, which may be due to the bonding effect between the interfaces that allows the oxygen/sulfur vacancies to be compensated.\u003c/p\u003e \u003cp\u003eX-ray photoelectron spectroscopy (XPS) full and high-resolution spectra demonstrate the surface elemental composition and chemical state of CdS-S\u003csub\u003ev\u003c/sub\u003e, Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e and CS/CO-40, respectively, as shown in Fig. S13 and Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(c-f). The Cd 3d\u003csub\u003e3/2\u003c/sub\u003e and Cd 3d\u003csub\u003e5/2\u003c/sub\u003e spin-orbit splitting peaks of CS/CO-40 are located at 411.60 and 404.80 eV, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec), and are attributed to the presence of Cd-S bond. Interestingly, CS/CO-40 shows additional Cd 3d signal peaks at low binding energies compared to CdS-S\u003csub\u003ev\u003c/sub\u003e, which may be attributed to the Cd-O bonds formed at the heterogeneous interface. The peaks located at 162.58 and 161.28 eV can correspond to S 2p\u003csub\u003e1/2\u003c/sub\u003e and S 2p\u003csub\u003e3/2\u003c/sub\u003e of CS/CO-40, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed). Compared to the S 2p high-resolution spectrum of CdS-S\u003csub\u003ev\u003c/sub\u003e, additional S species were also detected at the low binding energy (160.08 eV) of CS/CO-40. Combined with the EPR results, the presence of oxygen vacancies and sulfur vacancies would contribute to the formation of chemical bonds at the interface of CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. Based on this, the peaks at low binding energy of the high-resolution spectra of Cd 3d and S 2p of CS/CO-40 can be attributed to the presence of Cd-O and S-Co bonds, respectively [\u003cspan additionalcitationids=\"CR36\" citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. The Co 2p high-resolution spectra of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e and CS/CO-40 (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ee) show typical fitted peaks corresponding to Co\u003csup\u003e2+\u003c/sup\u003e 2p\u003csub\u003e1/2\u003c/sub\u003e, Co\u003csup\u003e3+\u003c/sup\u003e 2p\u003csub\u003e1/2\u003c/sub\u003e, Co\u003csup\u003e2+\u003c/sup\u003e 2p\u003csub\u003e3/2\u003c/sub\u003e, and Co\u003csup\u003e3+\u003c/sup\u003e 2p\u003csub\u003e3/2\u003c/sub\u003e, respectively. The O1s spectrum of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e was fitted to three peaks, which were attributed to lattice oxygen (~\u0026thinsp;529.48 eV, O\u003csub\u003eL\u003c/sub\u003e), oxygen vacancy (~\u0026thinsp;530.88 eV, O\u003csub\u003eV\u003c/sub\u003e) and chemisorbed oxygen (~\u0026thinsp;532.48 eV, O\u003csub\u003eabs\u003c/sub\u003e), respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ef). In contrast, the O1s spectrum of CS/CO-40 can identify four fitted peaks for O\u003csub\u003eL\u003c/sub\u003e (O-Cd), O\u003csub\u003eL\u003c/sub\u003e (O-Co), O\u003csub\u003eV\u003c/sub\u003e, and O\u003csub\u003eabs\u003c/sub\u003e. More importantly, the binding energies of both Cd 3d and S 2p in CS/CO-40 are negatively shifted compared with that of CdS-S\u003csub\u003ev\u003c/sub\u003e. On the contrary, the binding energies of both Co 2p and O1s in the composite photocatalyst are positively shifted compared with that of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e. This result indicates that when CdS-S\u003csub\u003ev\u003c/sub\u003e is in close contact with Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, the electrons on Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e are transferred to CdS-S\u003csub\u003ev\u003c/sub\u003e up to the Fermi energy level (E\u003csub\u003eF\u003c/sub\u003e) equilibrium, which induces energy band bending, and thus induces the formation of a IEF pointing from Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e to CdS-S\u003csub\u003ev\u003c/sub\u003e at the interface.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Photocatalytic performance and charge separation\u003c/h2\u003e \u003cp\u003eThe reactivity of the photocatalysts was evaluated under simulated sunlight using RCSP as a biomass reaction substrate. In contrast to some of the typical current photocatalytic research work on the use of raw biomass and biomass polymers as reaction substrates (Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e), we have innovatively achieved the one-step photocatalytic conversion of RCSP to high value-added C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases. The results of the photocatalytic reaction showed that CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e were the main C\u003csub\u003e1\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003e gas products, and almost no CO\u003csub\u003e2\u003c/sub\u003e was produced (Fig. S14). Firstly, we investigated the photocatalytic properties of CdS nanoparticles prepared with different CdCl\u003csub\u003e2\u003c/sub\u003e and TAA ratios (1:1, 1:2, and 1:3). In the normal reaction, CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e were detected in the photocatalytic reaction products of all CdS nanoparticles (Fig. S15). Further we also prepared CdS/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e with different Cd\u003csup\u003e2+\u003c/sup\u003e/S\u003csup\u003e2\u0026minus;\u003c/sup\u003e molar ratios and evaluated the photocatalytic properties. The results show that CS/CO-40 (Cd\u003csup\u003e2+\u003c/sup\u003e/S\u003csup\u003e2\u0026minus;\u003c/sup\u003e = 1:1) has a higher C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gas yield (Fig. S16). Based on these results, we further prepared CS/CO-x (x\u0026thinsp;=\u0026thinsp;20, 40, and 60) photocatalysts to evaluate the photocatalytic activity. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, the C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gas products evolution rates of CS/CO-x (x\u0026thinsp;=\u0026thinsp;20, 40, and 60) are significantly higher than those of CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, and this result further confirms that the heterostructure building can effectively improve the photocatalytic performance. CS/CO-40 exhibited the best photocatalytic activity with CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e evolution rates of 691.99, 2057.69, 202.93 and 187.29 \u0026micro;mol/g, respectively. And it reveals that the CO yield was increased by about 2.3 and 4.7 times, the CH\u003csub\u003e4\u003c/sub\u003e yield was increased by 5.4 and 7.2 times, the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e yield was increased by 3.1 and 4.0 times, and the C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e yield was increased by 2.9 and 3.3 times compared with CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, respectively. And among all the prepared photocatalysts, CS/CO-40 showed the highest CH\u003csub\u003e4\u003c/sub\u003e selectivity and total hydrocarbon (C\u003csub\u003ex\u003c/sub\u003eH\u003csub\u003ey\u003c/sub\u003e) gas selectivity of 65.53% and 77.96%, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). The results of time-dependent photocatalytic product yields of CdS-S\u003csub\u003ev\u003c/sub\u003e, Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e and CS/CO-x (x\u0026thinsp;=\u0026thinsp;20, 40, and 60) are displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec and Fig. S (17\u0026ndash;20).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eWe further explored the effect of photocatalytic reaction conditions on the activity. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed, when only DMSO was not added to the reaction system, only CO and CH\u003csub\u003e4\u003c/sub\u003e were detected in the photocatalytic products. Experimental group-3 demonstrated that small amounts of CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e could also be produced in the photoreactive system without a catalyst. Experimental group-4 further confirmed that small amounts of CO and CH\u003csub\u003e4\u003c/sub\u003e as well as trace amounts of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e could be detected in the absence of catalyst and NaOH. However, only a small amount of CO could be detected in the photoreactive system in the presence of only NaOH without catalyst and DMSO. All experimental control group results illustrate the important auxiliary roles of DMSO and NaOH for promoting the photocatalytic conversion of structurally complex natural polymers to C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases.\u003c/p\u003e \u003cp\u003eIn order to investigate the photogenerated charge separation efficiency of the photocatalysts, transient photocurrent and electrochemical impedance spectroscopy tests were performed. By continuously recording the transient photocurrent response for several on/off cycles under light irradiation, it was confirmed that the photocurrent of the photocatalysts exhibited high reproducibility and stability over multiple cycles (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea). The CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e composite photocatalysts showed stronger photocurrent intensity compared with CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, which further confirmed that the composite photocatalysts possessed higher photogenerated electron-hole separation efficiency. Similarly, electrochemical impedance spectroscopy (EIS) demonstrated that the composite photocatalysts have smaller charge transfer resistance and thus more efficient photogenerated charge separation efficiency (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb). In addition, the effect of heterogeneous structure building on photogenerated charge separation was further revealed by PL spectra. It is generally believed that a slower radiative recombination between photogenerated carriers will lead to a lower PL emission intensity [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. The PL emission intensity of the composite photocatalysts are weaker than that of CdS-S\u003csub\u003ev\u003c/sub\u003e (Fig. S21), which indicates that the successful construction of the heterojunction can effectively promote the charge separation efficiency. All of the above photoelectrochemical test results show that CS/CO-40 has a superior photogenerated charge separation ability, which is consistent with the photocatalytic reaction results.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eReactive radicals are essential for a deeper understanding of the photocatalytic reaction mechanism and play an important role in photocatalytic reactions. To further identify the main oxidatively active species during the photocatalytic reaction, we performed free radical trapping experiments using benzoquinone (BQ), isopropanol (IPA) and ethylenediaminetetraacetic acid (EDTA) as superoxide radicals (\u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e), hydroxyl radicals (\u0026middot;OH) and hole (h\u003csup\u003e+\u003c/sup\u003e) trapping agents, respectively. As shown in Fig. S22, the addition of all scavengers had a significant effect on product generation. In the experimental group with the addition of BQ, the production of C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e was suppressed while the evolution rate of CH\u003csub\u003e4\u003c/sub\u003e was significantly promoted. Interestingly, scavenging of \u0026middot;OH by isopropanol inhibited methane production while having less effect on the evolution rates of CO, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e. When the h\u003csup\u003e+\u003c/sup\u003e were captured by EDTA, the evolution rate of all products decreased. The analysis of the above results indicates that \u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e and \u0026middot;OH are the two major oxidatively active radicals, which play a key role in the production of C\u003csub\u003e2\u003c/sub\u003e products and CH\u003csub\u003e4\u003c/sub\u003e, respectively.\u003c/p\u003e \u003cp\u003eThe \u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e and \u0026middot;OH enerated during the reaction were determined using ESR tests with DMPO as the trapping agent, and the results are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(c, d). Under dark conditions, neither DMPO-\u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e nor DMPO-\u0026middot;OH ESR signals were detected. Under light, the photocatalyst exhibited strong DMPO-\u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e and DMPO-\u0026middot;OH ESR signal peaks. And the DMPO-\u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e and DMPO-\u0026middot;OH ESR signal intensities are enhanced with the increase of irradiation time. The ability of the VB of CdS-S\u003csub\u003ev\u003c/sub\u003e and the CB of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e to satisfy the standard potentials of H\u003csub\u003e2\u003c/sub\u003eO/\u0026middot;OH (1.99 V vs. NHE) and O\u003csub\u003e2\u003c/sub\u003e/\u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e (\u0026minus;\u0026thinsp;0.33 V vs. NHE), respectively, demonstrates that the charge transfer between CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e follows the Z-scheme pathway [\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e]. The above results also indicate that \u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e and \u0026middot;OH are the main active radicals produced during the photocatalytic reaction.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e3.3 DFT calculation and photocatalytic mechanism\u003c/h2\u003e \u003cp\u003eInterfacial interactions and built-in electric fields between CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e interfaces in CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e heterojunctions are crucial to promote efficient photogenerated charge transfer. It is well known that when two semiconductors with different E\u003csub\u003eF\u003c/sub\u003e and work functions (Φ) are in close contact, a IEF will be formed at the interface [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e, \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e]. The interfacial interactions and charge transfer mechanisms in CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e heterojunctions are further revealed by DFT calculations. The structures of CdS-S\u003csub\u003ev\u003c/sub\u003e, Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, and CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e heterojunctions model were successfully established (Fig. S23). The crystal structure models of CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e from different views are shown in Fig. S24 and S25. The Φ and E\u003csub\u003eF\u003c/sub\u003e of CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e were simulated with first principles (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb). The Φ of CdS is significantly larger than that of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, which implies that the electrons of the latter are more likely to escape. When the heterogeneous interface is in contact, the difference in E\u003csub\u003eF\u003c/sub\u003e will result in the transfer of electrons from Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e to CdS-S\u003csub\u003ev\u003c/sub\u003e. The electron density distribution at the heterojunction interface was further simulated with charge density difference to visualize the inter-interface electron transfer (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed) [\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]. The results confirm the coupled connection of chemical bonds between the interfaces of the two materials and the presence of strong interfacial interactions. A spontaneous interfacial charge transfer pathway from Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e to CdS-S\u003csub\u003ev\u003c/sub\u003e is theorized to exist when the two materials are in close contact, and the interfacial chemical bonding can act as a channel to facilitate inter-interfacial charge transfer. The results of the above analysis are consistent with the XPS analysis.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eBased on these results, a charge transfer mechanism for heterojunction photocatalysts is proposed. The energy band structure was determined by UV-vis DRS and Mott Schottky tests. The energy band structure of the CdS-S\u003csub\u003ev\u003c/sub\u003e /Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e system before and after contact is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee. When CdS-S\u003csub\u003ev\u003c/sub\u003e is in contact with Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, the electrons in Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e are transferred to CdS-S\u003csub\u003ev\u003c/sub\u003e until the E\u003csub\u003eF\u003c/sub\u003e are balanced, resulting in the formation of a unique IEF. Under illumination, the IEF promotes the transfer of photoexcited electrons from CdS-S\u003csub\u003ev\u003c/sub\u003e to the VB in Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e, and the composite is realized through Z-scheme charge transfer. The photogenerated electrons in the CB of Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e reduce O\u003csub\u003e2\u003c/sub\u003e to \u0026middot;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e, while the holes generated in the VB of CdS-S\u003csub\u003ev\u003c/sub\u003e oxidize H\u003csub\u003e2\u003c/sub\u003eO to form \u0026middot;OH. The ESR results and DFT calculations further indicate that the current system should be a Z-scheme heterojunction rather than type-II heterojunction. In addition, the chemical bonds formed at the heterointerface between CdS and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e can act as interfacial charge transfer channels and also play an important role in accelerating the charge transfer between CdS-S\u003csub\u003ev\u003c/sub\u003e and Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e. Photocatalytic conversion of RCSP to high value-added C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases under the synergistic effect of photoactive radicals, DMSO and NaOH (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea). In a world, the CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e heterojunction has a high performance photocatalytic RCSP conversion performance due to its strong light absorption ability, follows a Z-scheme charge transfer pathway in order to retain a strong redox capacity, and is able to promote charge transfer through interfacial chemical bonding.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFor further in-depth analysis of the reaction mechanisms, glucose, fructose and xylose were further investigated as typical lignocellulose-derived monomers. The results of photocatalytic experiments using glucose, fructose and xylose as reaction substrates showed that gas-phase products such as CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e were detected, which is in agreement with the results of the RCSP photocatalytic experiments (Fig. S26). And liquid phase product analysis showed that organic acids such as lactic acid, acetic acid, propionic acid and formic acid were the main products, with lactic acid having the highest yield (Fig. S27). Combined with previous studies [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e], we propose possible reaction pathways for the conversion of glucose, fructose, and xylose to organic acids, as shown in Fig. S28 and Fig. S29. Glucose is oxidised by α- and β-oxidation to formic acid, intermediate-I, ethanedioic acid, and intermediate-II. Ethanedioic acid can produce acetic acid and formic acid by dehydration and C-C bond breaking, respectively. Formic acid can also be produced when the C-C bond of intermediate-I is broken. The isomerisation of glucose to fructose is further followed by retro-aldol condensation reaction to produce glyceraldehyde and 1,3-dihydroxyacetone. Lactic acid is then further produced by dehydration and 1,2-hydride shift. During the oxidation of xylose, xylose is first isomerised into intermediate I and intermediate II. And then Intermediate-I generates glyceraldehyde and ethanedioic acid by retro-aldol condensation reaction. Intermediate-II generates acetic acid and ethanedioic acid by α- and β-oxidation. The above products were further converted to lactic acid and formic acid, respectively. Lactic acid dehydrates to form propionic acid. We speculate that the production of products such as CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e may be attributed to the further oxidation of organic acids during photocatalysis.\u003c/p\u003e \u003cp\u003eIn order to verify the conjecture, the product distribution of photocatalysis was further evaluated using organic acids such as formic acid, lactic acid, propionic acid and acetic acid as reaction substrates. The results were as expected (Fig. S26), lactic acid, acetic acid, formic acid, and propionic acid showed high selectivity for the conversion of CH\u003csub\u003e4\u003c/sub\u003e, CO, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e, and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, respectively. Based on the above findings and previous studies, we propose a possible mechanism of transformation, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb. Typical lignocellulosic monomers such as glucose and xylose are oxidised in the presence of oxidatively active species to produce organic acids such as lactic, propionic and acetic acids as well as formic acid through cascade-by-cascade oxidation and C-C bond breaking, which are ultimately oxidised completely to form methane.\u003c/p\u003e \u003c/div\u003e"},{"header":"4 Conclusion","content":"\u003cp\u003eIn conclusion, we have successfully constructed an efficient Z-scheme reaction system for the photocatalytic conversion of corn stover meal to C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases. In terms of material design, a CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e Z-scheme heterojunction with excellent light-absorbing ability was successfully designed. The IEF in the CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e heterojunction effectively promotes photogenerated charge transfer, while the interfacial chemical bonds can act as additional electronic bridges to accelerate electron transfer. Both XPS and ESR results have demonstrated that the CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e heterojunction follows a Z-scheme charge transfer mechanism. DFT calculations simulate the work functions, Fermi energy levels, and charge density variations at the heterojunction interface, which further validates the creation of an IEF. Under simulated solar irradiation, RCSP can be efficiently and directly converted into high value-added C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases. The CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e yields of this reaction system could reach up to 691.99, 2057.69, 202.93 and 187.29 \u0026micro;mol/g, respectively, and the selectivities of CH\u003csub\u003e4\u003c/sub\u003e and C\u003csub\u003ex\u003c/sub\u003eH\u003csub\u003ey\u003c/sub\u003e were as high as 65.53% and 77.96%, respectively. Combining the analysis of the series of characterisation data and the results of the photocatalysis experiments, we further discuss the possible photocatalytic mechanisms and conversion pathways. This work provides new ideas for high-value utilization of agroforestry waste through green conversion technology, which has a positive effect on accelerating the process of carbon neutrality.\u003c/p\u003e"},{"header":"Declarations","content":" \u003cp\u003e \u003cstrong\u003eCompeting interests\u003c/strong\u003e \u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eFunding\u003c/h2\u003e \u003cp\u003eThis work was financially supported by the National Natural Science Foundation of China (No. 32071713) and the Outstanding Youth Foundation Project of Heilongjiang Province (No. JQ2019C001).\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eGuoyang Gao: conceptualization, methodology, formal analysis, investigation, validation, and writing. Yuxin Dai and Ying Lin: formal analysis, investigation, and writing. Houjuan Qi: methodology, formal analysis and supervision. Zhanhua Huang: conceptualization, project administration, funding acquisition, editing, and supervision. All authors reviewed the manuscript.\u003c/p\u003e\u003ch2\u003eData availability\u003c/h2\u003e \u003cp\u003eNo datasets were generated or analysed during the current study.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eSun Z, Bottari G, Afanasenko A, Stuart M, Deuss P, Fridrich B, Barta K (2018) Complete lignocellulose conversion with integrated catalyst recycling yielding valuable aromatics and fuels. Nat Catal 1:82\u0026ndash;92\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePark J, Mushtaq U, Sugiarto J, Verma D, Kim J (2022) Total chemocatalytic cascade conversion of lignocellulosic biomass into biochemicals. 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Green Chem 24:5894\u0026ndash;5903\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"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":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"corn stover photo-conversion, Z-scheme heterojunction, internal electric field, sulfur/oxygen dual-vacancies","lastPublishedDoi":"10.21203/rs.3.rs-5122454/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5122454/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe direct conversion of corn stover into high value-added C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases using photocatalysis is a challenging and prospective endeavor. In this work, a sulfur/oxygen dual-vacancies CdS/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e) Z-scheme heterojunction was designed for direct raw corn stover powder (RCSP) conversion in a photoreactive system. The internal electric field (IEF) formed in CdS-S\u003csub\u003ev\u003c/sub\u003e/Co\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-O\u003csub\u003ev\u003c/sub\u003e can effectively promote the photogenerated charge separation and transfer, and the chemical bond formed at the heterogeneous interface can be used as a channel for the directional migration of photogenerated charges to accelerate the inter-interface charge transfer. Experimental results combined with DFT calculations confirmed the formation of Z-scheme heterojunction and IEF. The results of the photocatalytic RCSP reaction showed that the CO, CH\u003csub\u003e4\u003c/sub\u003e, C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003e, and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e production rates of the proposed catalytic system were as high as 691.99, 2057.69, 202.93 and 187.29 \u0026micro;mol/g, with the corresponding CH\u003csub\u003e4\u003c/sub\u003e selectivity and total hydrocarbon selectivity of 65.53% and 77.96%, respectively. What\u0026rsquo;s more, we propose a photocatalytic reaction mechanism in which raw biomass undergoes depolymerization and cascading oxidation to high value-added products. This study provides a new idea for high-performance photocatalytic direct conversion of RCSP into high-value-added C\u003csub\u003e1\u003c/sub\u003e/C\u003csub\u003e2\u003c/sub\u003e gases through the rational design of photocatalysts and reaction systems.\u003c/p\u003e","manuscriptTitle":"Efficient charge separation in Z-scheme heterojunctions induced by chemical bonding-enhanced internal electric field for promoting photocatalytic conversion of corn stover to C1/C2 gases","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-11-04 14:35:59","doi":"10.21203/rs.3.rs-5122454/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-10-09T10:42:38+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-10-06T20:23:00+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-10-06T04:32:39+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"219193540081927145696999988664740514775","date":"2024-09-30T18:01:54+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"115018810355451254878906328352001980610","date":"2024-09-27T02:37:03+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-09-26T15:52:44+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-09-26T15:51:21+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-09-25T15:52:42+00:00","index":"","fulltext":""},{"type":"submitted","content":"Advanced Composites and Hybrid Materials","date":"2024-09-20T09:26:48+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"bf18d69e-3c5c-4121-96a7-b3b7038df41f","owner":[],"postedDate":"November 4th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-11-25T16:11:20+00:00","versionOfRecord":{"articleIdentity":"rs-5122454","link":"https://doi.org/10.1007/s42114-024-01073-4","journal":{"identity":"advanced-composites-and-hybrid-materials","isVorOnly":false,"title":"Advanced Composites and Hybrid Materials"},"publishedOn":"2024-11-19 15:58:04","publishedOnDateReadable":"November 19th, 2024"},"versionCreatedAt":"2024-11-04 14:35:59","video":"","vorDoi":"10.1007/s42114-024-01073-4","vorDoiUrl":"https://doi.org/10.1007/s42114-024-01073-4","workflowStages":[]},"version":"v1","identity":"rs-5122454","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5122454","identity":"rs-5122454","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}