S-scheme CeO₂/Cd_7.23Zn_2.77S₁₀-DETA heterojunctions for superior cocatalyst-free visible-light photocatalytic hydrogen evolution

Abstract

The intensifying global energy crisis, coupled with environmental degradation from fossil fuels, highlights that photocatalytic hydrogen evolution technology offers a promising solution due to its efficiency and sustainability. In this study, we synthesized CeO₂/Cd_7.23Zn_2.77S₁₀-DETA (diethylenetriamine is abbreviated as DETA, and subsequently CeO₂ is referred to as EO, Cd_7.23Zn_2.77S₁₀-DETA is abbreviated as ZCS, and the composite with EO comprising 30% is abbreviated as EO/ZCS) nanocomposites with S-scheme heterojunctions. Under conditions without external co-catalysts and utilizing only visible light as the excitation source, EO/ZCS nanocomposites exhibited outstanding photocatalytic hydrogen evolution activity and remarkable stability, presenting significant advantages over conventional methods that rely on co-catalysts and ultraviolet light. The photocatalytic hydrogen evolution rate of EO/ZCS nanocomposites reached 4.11 mmol/(g·h), significantly surpassing that of EO (trace) and ZCS (2.78 mmol/(g·h)). This substantial enhancement is attributed to the S-scheme charge transfer mechanism at the heterojunctions in EO/ZCS nanocomposites, which effectively facilitates the efficient separation and transfer of photogenerated electron-hole pairs, thereby substantially enhancing photocatalytic hydrogen evolution activity. Through techniques such as X-ray photoelectron spectroscopy (XPS) and theoretical calculations, we confirmed the formation of S-scheme heterojunctions and elucidated their photocatalytic hydrogen evolution mechanism. The results underscore the potential of EO/ZCS nanocomposites as highly efficient and stable photocatalysts for hydrogen production under environmentally benign conditions.

References

[[1]] Deng A-x, Sun Y, Gao Z-q, et al.. Internal electric field in carbon nitride-based heterojunctions for photocatalysis [J]. Nano Energy, 2023, 108: 108228.

[[2]] Chu X-z, Sathish C I, Li M-y, et al.. Anti-Stoke effect induced enhanced photocatalytic hydrogen production [J]. Battery Energy, 2023, 2(2): 20220041.

[[3]] Hemmati-Eslamlu P, Habibi-Yangjeh A. A review on impressive Z- and S-scheme photocatalysts composed of g-C₃N₄ for detoxification of antibiotics [J]. FlatChem, 2024, 43: 100597.

[[4]] He H-w, Wang Z-l, Zhang J-f, et al.. Interface chemical bond enhanced ions intercalated carbon nitride/CdSe-diethylenetriamine S-scheme heterojunction for photocatalytic H₂O₂ synthesis in pure water [J]. Advanced Functional Materials, 2024, 34(24): 2315426.

[[5]] WANG Jing, WANG Zhong-liao, ZHANG Jin-feng, et al. Two-dimensional high-entropy selenides for boosting visible-light-driven photocatalytic performance [J]. ACS Nano, 2024: 0740–20750. DOI: https://doi.org/10.1021/acsnano.4c06954.

[[6]] Li T, Tsubaki N, Jin Z-liang. S-scheme heterojunction in photocatalytic hydrogen production [J]. Journal of Materials Science & Technology, 2024, 169: 82-104.

[[7]] Yang T-t, Wang J, Wang Z-l, et al.. Ipolymer Cd₃(C₃N₃S₃)₂/Zn₃(C₃N₃S₃)₂ S-scheme heterojunction enhances photocatalytic H₂ production [J]. Chinese Journal of Catalysis, 2024, 58: 157-167.

[[8]] Liu L-z, Wang Z-l, Zhang J-f, et al.. Tunable interfacial charge transfer in a 2D - 2D composite for efficient visible-light-driven CO₂ conversion [J]. Advanced Materials, 2023, 35(26): 2300643.

[[9]] Lu J-n, Gu S-n, Li H-d, et al.. Review on multidimensional assembled S-scheme heterojunction photocatalysts [J]. Journal of Materials Science & Technology, 2023, 160: 214-239.

[[10]] Sharma K, Hasija V, Malhotra M, et al.. A review of CdS-based S-scheme for photocatalytic water splitting: Synthetic strategy and identification techniques [J]. International Journal of Hydrogen Energy, 2024, 52: 804-818.

[[11]] Zhao Z-w, Wang Z-l, Zhang J-f, et al.. Interfacial chemical bond and oxygen vacancy-enhanced In₂O₃/CdSe-DETA S-scheme heterojunction for photocatalytic CO₂ conversion [J]. Advanced Functional Materials, 2023, 33(23): 2214470.

[[12]] Song X-l, Chen L, Gao L-j, et al.. Engineering g-C₃N₄ based materials for advanced photocatalysis: Recent advances [J]. Green Energy & Environment, 2024, 9(2): 166-197.

[[13]] WANG Zhong-liao, WANG Jing, ZHANG Jin-feng, et al. Overall utilization of photoexcited charges for simultaneous photocatalytic redox reactions [J]. Acta Physico Chimica Sinica, 2022: 2209037. DOI: https://doi.org/10.3866/pku.whxb202209037.

[[14]] Wu X-h, Chen G-q, Li L-t, et al.. ZnIn₂S₄-based S-scheme heterojunction photocatalyst [J]. Journal of Materials Science & Technology, 2023, 167: 184-204.

[[15]] Su B, Zheng M, Lin W, et al.. S-scheme Co₉S₈@Cd_0.8 Zn_0.2S-DETA hierarchical nanocages bearing organic CO₂ activators for photocatalytic syngas production [J]. Advanced Energy Materials, 2023, 13(15): 2203290.

[[16]] WU Xin-he, CHEN Guo-qiang, WANG Juan, et al. Review on S-scheme heterojunctions for photocatalytic hydrogen evolution [J]. Acta Physico Chimica Sinica, 2023: 2212016. DOI: https://doi.org/10.3866/pku.whxb202212016.

[[17]] Zhang B-l, Sun B, Liu F-x, et al.. TiO₂-based S-scheme photocatalysts for solar energy conversion and environmental remediation [J]. Science China Materials, 2024, 67(2): 424-443.

[[18]] Su B, Kong Y-h, Wang S-b, et al.. Hydroxyl-bonded Ru on metallic TiN surface catalyzing CO₂ reduction with H₂O by infrared light [J]. Journal of the American Chemical Society, 2023, 145(50): 27415-27423.

[[19]] Cai M-j, Liu Y-p, Dong K-x, et al.. Floatable S-scheme Bi₂WO₆/C₃N₄/carbon fiber cloth composite photocatalyst for efficient water decontamination [J]. Chinese Journal of Catalysis, 2023, 52: 239-251.

[[20]] Chen G-j, Zhou Z-r, Li B-f, et al.. S-scheme heterojunction of crystalline carbon nitride nanosheets and ultrafine WO₃ nanoparticles for photocatalytic CO₂ reduction [J]. Journal of Environmental Sciences, 2024, 140: 103-112.

[[21]] Chen R-y, Xia J-z, Chen Y-g, et al.. S-scheme-enhanced PMS activation for rapidly degrading tetracycline using CuWO_4−x/Bi₁₂O₁₇Cl₂ heterostructures [J]. Acta Physico Chimica Sinica, 2023, 39: 2209012

[[22]] Dutta V, Sonu, Sudhaik A, et al.. Emergence of S-scheme-derived Ag decorated CuBi₂O₄/CNTs/(BiO)₂CO₃ photocatalyst with enhanced visible light photocatalytic performance [J]. Journal of the Taiwan Institute of Chemical Engineers, 2024, 156: 105319.

[[23]] Habibi-Yangjeh A, Pournemati K. A review on emerging homojunction photocatalysts with impressive performances for wastewater detoxification [J]. Critical Reviews in Environmental Science and Technology, 2024, 54(4): 290-320.

[[24]] Huang K-h, Feng B-n, Wen X-h, et al.. Effective photocatalytic hydrogen evolution by Ti₃C₂-modified CdS synergized with N-doped C-coated Cu₂O in S-scheme heterojunctions [J]. Chinese Journal of Structural Chemistry, 2023, 42(12): 100204.

[[25]] Jin F, Yang B-l, Wang X-p, et al.. Facilitating efficient photocatalytic hydrogen evolution via enhanced carrier migration at MOF-on-MOF S-scheme heterojunction interfaces through a graphdiyne (C_nH_2n−2) electron transport layer [J]. Chinese Journal of Structural Chemistry, 2023, 42(12): 100198.

[[26]] Kumar R, Sudhaik A, Sonu, et al.. Graphene oxide modified K, P Co-doped g-C₃N₄ and CoFe₂O₄ composite for photocatalytic degradation of antibiotics [J]. Journal of the Taiwan Institute of Chemical Engineers, 2023, 150: 105077.

[[27]] Sun K-q, Yuan H, Yan Y-j, et al.. Visible-light-response 2D/2D Bi₂Fe₄O₉/ZnIn₂S₄ van der Waals S-scheme heterojunction with efficient photocatalysis-self-Fenton degradation of antibiotics [J]. Journal of Water Process Engineering, 2024, 58: 104803.

[[28]] SUN Tao, LI Chen-xi, BAO Yu-peng, et al. S-scheme MnCo₂S₄/g-C₃N₄ heterojunction photocatalyst for H₂ production [J]. Acta Physico Chimica Sinica, 2023: 2212009. DOI: https://doi.org/10.3866/pku.whxb202212009.

[[29]] Xie K-f, Xu S-y, Xu K, et al.. BiOCl Heterojunction photocatalyst: Construction, photocatalytic performance, and applications [J]. Chemosphere, 2023, 317: 137823.

[[30]] Wang C-c, Rong K, Liu Y-p, et al.. Carbon quantum dots-modified tetra (4-carboxyphenyl) porphyrin/BiOBr S-scheme heterojunction for efficient photocatalytic antibiotic degradation [J]. Science China Materials, 2024, 67(2): 562-572.

[[31]] ZAN Zhong-qi, LI Xi-bao, GAO Xiao-ming, et al. 0D/2D carbon nitride quantum dots (CNQDs)/BiOBr S-scheme heterojunction for robust photocatalytic degradation and H₂O₂ production [J]. Acta Physico Chimica Sinica, 2022: 2209016. DOI: https://doi.org/10.3866/pku.whxb202209016.

[[32]] Zhang H-b, Wang Z-l, Zhang J-f, et al.. Metal-sulfide-based heterojunction photocatalysts: Principles, impact, applications, and in situ characterization [J]. Chinese Journal of Catalysis, 2023, 49: 42-67.

[[33]] Zhang X, Yang Ping. Role of graphitic carbon in g-C₃N₄ nanoarchitectonics towards efficient photocatalytic reaction kinetics: A review [J]. Carbon, 2024, 216: 118584.

[[34]] Cheng C, Zhang J-j, Zhu B-c, et al.. Verifying the charge-transfer mechanism in S-scheme heterojunctions using femtosecond transient absorption spectroscopy [J]. Angewandte Chemie (International Ed), 2023, 62(8): e202218688.

[[35]] Cheng C, Zhu B-c, Cheng B, et al.. Catalytic conversion of styrene to benzaldehyde over S-scheme photocatalysts by singlet oxygen [J]. ACS Catalysis, 2023, 13(1): 459-468.

[[36]] Shi Y-x, Li L-l, Xu Z, et al.. Construction of full solar-spectrum available S-scheme heterojunction for boosted photothermal-assisted photocatalytic H₂ production [J]. Chemical Engineering Journal, 2023, 459: 141549.

[[37]] Xia L-h, Zhang K-s, Wang X-d, et al.. 0D/2D Schottky junction synergies with 2D/2D S-scheme heterojunction strategy to achieve uniform separation of carriers in 0D/2D/2D quasi CNQDs/TCN/ZnIn₂S₄ towards photocatalytic remediating petroleum hydrocarbons polluted marine [J]. Applied Catalysis B: Environmental, 2023, 325: 122387.

[[38]] Sun X-h, He K-l, Chen Z-z, et al.. Construction of visible-light-response photocatalysis-self-Fenton system for the efficient degradation of amoxicillin based on industrial waste red mud/CdS S-scheme heterojunction [J]. Separation and Purification Technology, 2023, 324: 124600.

[[39]] Li Z, Liu W, Chen C-x, et al.. Transforming the charge transfer mechanism in the In₂O₃/CdSe-DETA nanocomposite from type-I to S-scheme to improve photocatalytic activity and stability during hydrogen production [J]. Acta Physico Chimica Sinica, 2023, 39: 2208030

[[40]] Wang J, Niu X-y, Hao Q, et al.. Promoting charge separation in CuInS₂/CeO₂ photocatalysts by an S-scheme heterojunction for enhanced photocatalytic H₂ production [J]. Chemical Engineering Journal, 2024, 493: 152534.

[[41]] Li Z, Li W, Zhai L-g, et al.. Oxygen defects and S-scheme heterojunctions synergistically promote the photocatalytic hydrogen evolution activity and stability of WO_2.72/Zn_0.5Cd_0.5S-DETA nanocomposites [J]. Journal of Colloid and Interface Science, 2023, 646: 834-843.

[[42]] Li Z, Jin D, Wang Z-hua. WO₃(H₂O)_0.333/CdSe-diethylenetriamine nanocomposite as a step-scheme photocatalyst for hydrogen production [J]. Surfaces and Interfaces, 2022, 29: 101702.