Graphical Abstract
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Enhancement of the light-absorption response and utilization of the photogenerated carriers represent a robust strategy for the design of high-performance photocatalyst. In this work, grafting CoxP nanoclusters onto S-scheme heterojunction of W18O49/ZnIn2S4 (WO/ZIS-CoxP) with strong response to the ultraviolet–visible–near infrared ray (UV–vis–NIR) region has been achieved, which possesses efficient electron-transfer-channel, and boosts charge-separation and transport kinetics. The as-prepared WO/ZIS-CoxP yields an impressive solar-driven hydrogen production rate of 45 mmol·g−1·h−1. The increased photocatalytic performance is attributed to the synergistic effect of the composite catalyst: (1) The local surface plasmon resonance-induced “hot electron” injection of W18O49 significantly increases the electron density; (2) the engineered S-scheme directional electron transfer promotes charge separation and enhances the reducing capability of photoexcited electrons; and (3) CoxP as electron-trap site for accelerating surface proton reduction reaction. This work provides a platform to impart nonprecious co-catalyst for engineering S-scheme heterojunction, serving a class of efficient solar-driven photocatalyst towards hydrogen production.
Zhou, P.; Navid, I. A.; Ma, Y. J.; Xiao, Y. X.; Wang, P.; Ye, Z. W.; Zhou, B. W.; Sun, K.; Mi, Z. T. Solar-to-hydrogen efficiency of more than 9% in photocatalytic water splitting. Nature 2023, 613, 66–70.
Liu, Y. N.; Liu, C. H.; Debnath, T.; Wang, Y.; Pohl, D.; Besteiro, L. V.; Meira, D. M.; Huang, S. Y.; Yang, F.; Rellinghaus, B. et al. Silver nanoparticle enhanced metal-organic matrix with interface-engineering for efficient photocatalytic hydrogen evolution. Nat. Commun. 2023, 14, 541.
Ruan, X. W.; Huang, C. X.; Cheng, H.; Zhang, Z. Q.; Cui, Y.; Li, Z. Y.; Xie, T. F.; Ba, K. K.; Zhang, H. Y.; Zhang, L. et al. A twin S-scheme artificial photosynthetic system with self-assembled heterojunctions yields superior photocatalytic hydrogen evolution rate. Adv. Mater. 2023, 35, 2209141.
Wu, L.; Su, F. H.; Liu, T.; Liu, G. Q.; Li, Y.; Ma, T.; Wang, Y. F.; Zhang, C.; Yang, Y.; Yu, S. H. Phosphorus-doped single-crystalline quaternary sulfide nanobelts enable efficient visible-light photocatalytic hydrogen evolution. J. Am. Chem. Soc. 2022, 144, 20620–20629.
Wang, L.; Xu, X.; Cheng, Q. F.; Dou, S. X.; Du, Y. Near-infrared-driven photocatalysts: Design, construction, and applications. Small 2021, 17, 1904107.
Yang, D.; Li, Z. G.; Zhang, X. H.; Ren, Z. H.; Lu, W. H.; Liu, H. N.; Guo, X. M.; Zhang, J. J.; Bu, X. H. Rational design of ZnCdS/TpPa-1-COF heterostructure photocatalyst by strengthening the interface connection in solar hydrogen production reactions. Nano Res. 2024, 17, 1027–1034.
Ma, D. D.; Shi, J. W.; Sun, L.; Sun, Y. X.; Mao, S. M.; Pu, Z. X.; He, C.; Zhang, Y. J.; He, D.; Wang, H. K. et al. Knack behind the high performance CdS/ZnS-NiS nanocomposites: Optimizing synergistic effect between cocatalyst and heterostructure for boosting hydrogen evolution. Chem. Eng. J. 2022, 431, 133446.
Zhang, G. R.; Li, X. J.; Li, N.; Wu, T. T.; Wang, L. Face-to-face heterojunctions within 2D/2D porous NiCo oxyphosphide/g-C3N4 towards efficient and stable photocatalytic H2 evolution. Nano Res. 2023, 16, 6568–6576.
Li, B. S.; Lai, C.; Lin, H. J.; Liu, S. Y.; Qin, L.; Zhang, M. M.; Zhou, M. Z.; Li, L.; Yi, H.; Chen, L. The promising NIR light-driven MO3− x (M = Mo, W) photocatalysts for energy conversion and environmental remediation. Chem. Eng. J. 2022, 431, 134044.
Gu, Y. F.; Guo, B. B.; Yi, Z.; Wu, X. W.; Zhang, J.; Yang, H. Synthesis of a self-assembled dual morphologies Ag-NPs/SrMoO4 photocatalyst with LSPR effect for the degradation of methylene blue dye. ChemistrySelect 2022, 7, e202201274.
Wang, Y.; Wang, Y.; Aravind, I.; Cai, Z.; Shen, L.; Zhang, B. X.; Wang, B.; Chen, J. H.; Zhao, B. F.; Shi, H. T. et al. In situ investigation of ultrafast dynamics of hot electron-driven photocatalysis in plasmon-resonant grating structures. J. Am. Chem. Soc. 2022, 144, 3517–3526.
Li, J.; Lou, Z. Z.; Li, B. J. Nanostructured materials with localized surface plasmon resonance for photocatalysis. Chin. Chem. Lett. 2022, 33, 1154–1168.
Wei, Z. J.; Ji, T.; Zhou, X. M.; Guo, J. W.; Yu, X.; Liu, H.; Wang, J. G. Synergistic enhancement of photocatalytic CO2 reduction by built-in electric field/piezoelectric effect and surface plasmon resonance via PVDF/CdS/Ag heterostructure. Small 2023, 19, 2304202.
Li, N.; Fan, H. K.; Zhao, W. W.; Gao, Y. Q.; Ge, L. 2D/0D plasmonic CuSe/CdS for efficient photocatalytic hydrogen activity via strong Vis–NIR light and interfacial effect. Appl. Surf. Sci. 2022, 590, 153028.
Chen, X.; Guo, R. T.; Pan, W. G.; Yuan, Y.; Hu, X.; Bi, Z. X.; Wang, J. A novel double S-scheme photocatalyst Bi7O9I3/Cd0.5Zn0.5S QDs/WO3− x with efficient full-spectrum-induced phenol photodegradation. Appl. Catal. B: Environ. 2022, 318, 121839.
Ren, Y. M.; Feng, D. S.; Yan, Z. M.; Sun, Z. X.; Zhang, Z. X.; Xu, D. W.; Qiao, C.; Chen, Z. H.; Jia, Y.; Chan Jun, S. et al. Interfacial coupled engineering of plasmonic amorphous MoO3− x nanodots/g-C3N4 nanosheets for photocatalytic water splitting and photothermal conversion. Chem. Eng. J. 2023, 453, 139875.
Manthiram, K.; Alivisatos, A. P. Tunable localized surface plasmon resonances in tungsten oxide nanocrystals. J. Am. Chem. Soc. 2012, 134, 3995–3998.
Bandi, S.; Srivastav, A. K. Review: Oxygen-deficient tungsten oxides. J. Mater. Sci. 2021, 56, 6615–6644.
Lu, Y.; Jia, X. F.; Ma, Z. Y.; Li, Y.; Yue, S.; Liu, X. F.; Zhang, J. Y. W5+–W5+ pair induced LSPR of W18O49 to sensitize ZnIn2S4 for full-spectrum solar-light-driven photocatalytic hydrogen evolution. Adv. Funct. Mater. 2022, 32, 2203638.
Zheng, N. N.; Zhang, S. H.; Wang, L.; Qi, Z. L.; Peng, Q.; Jian, L. R.; Bai, Y.; Feng, Y.; Shen, J. C.; Wang, R. X. et al. Boosting image-guiding radiation therapy through W18O49 nanospheres and the second near-infrared light irradiation. Nano Res. 2022, 15, 2315–2323.
Lu, N.; Zhang, Z. Y.; Wang, Y.; Liu, B. K.; Guo, L. J.; Wang, L.; Huang, J. D.; Liu, K. C.; Dong, B. Direct evidence of IR-driven hot electron transfer in metal-free plasmonic W18O49/Carbon heterostructures for enhanced catalytic H2 production. Appl. Catal. B: Environ. 2018, 233, 19–25.
Zhang, Z. Y.; Huang, J. D.; Fang, Y. R.; Zhang, M. Y.; Liu, K. C.; Dong, B. A nonmetal plasmonic Z-scheme photocatalyst with UV- to NIR-driven photocatalytic protons reduction. Adv. Mater. 2017, 29, 1606688.
Hong, I.; Chen, Y. A.; Hsu, Y. J.; Yong, K. Triple-channel charge transfer over W18O49/Au/g-C3N4 Z-scheme photocatalysts for achieving broad-spectrum solar hydrogen production. ACS Appl. Mater. Interfaces 2021, 13, 52670–52680.
Liu, T.; Li, Y. Z.; Lv, Y. H.; Qiu, P. Y.; Xiong, Y.; Tian, J. Three-dimensional S-scheme heterojunction by integration of purple tungsten oxide nanowires and cadmium sulfide nanospheres for effective photocatalytic hydrogen generation. J. Colloid Interface Sci. 2023, 640, 568–577.
Fu, J. W.; Xu, Q. L.; Low, J.; Jiang, C. J.; Yu, J. G. Ultrathin 2D/2D WO3/g-C3N4 step-scheme H2-production photocatalyst. Appl. Catal. B: Environ. 2019, 243, 556–565.
Gu, Y. P.; Li, Y. K.; Feng, H. Q.; Han, Y. N.; Li, Z. J. Built-in electric field induced S-scheme g-C3N4 homojunction for efficient photocatalytic hydrogen evolution: Interfacial engineering and morphology control. Nano Res. 2024, 17, 4961–4970.
Zhang, G. P.; Wu, H.; Chen, D. Y.; Li, N. J.; Xu, Q. F.; Li, H.; He, J. H.; Lu, J. M. A mini-review on ZnIn2S4-based photocatalysts for energy and environmental application. Green Energy Environ. 2022, 7, 176–204.
Dhakshinamoorthy, A.; Asiri, A. M.; García, H. Metal-organic framework (MOF) compounds: Photocatalysts for redox reactions and solar fuel production. Angew. Chem., Int. Ed. 2016, 55, 5414–5445.
Lu, X. W.; Quan, L. M.; Hou, H. J.; Qian, J. C.; Liu, Z. W.; Zhang, Q. F. Fabrication of 1D/2D Y-doped CeO2/ZnIn2S4 S-scheme photocatalyst for enhanced photocatalytic H2 evolution. J. Alloys Compd. 2022, 925, 166552.
Xi, Y. M.; Chen, W. B.; Dong, W. R.; Fan, Z. X.; Wang, K. F.; Shen, Y.; Tu, G. M.; Zhong, S. X.; Bai, S. Engineering an Interfacial facet of S-scheme heterojunction for improved photocatalytic hydrogen evolution by modulating the internal electric field. ACS Appl. Mater. Interfaces 2021, 13, 39491–39500.
Bai, J. X.; Chen, W. L.; Hao, L.; Shen, R. C.; Zhang, P.; Li, N.; Li, X. Assembling Ti3C2 MXene into ZnIn2S4-NiSe2 S-scheme heterojunction with multiple charge transfer channels for accelerated photocatalytic H2 generation. Chem. Eng. J. 2022, 447, 137488.
Yang, Z. F.; Xia, X. N.; Yang, W. W.; Wang, L. L.; Liu, Y. T. Photothermal effect and continuous hot electrons injection synergistically induced enhanced molecular oxygen activation for efficient selective oxidation of benzyl alcohol over plasmonic W18O49/ZnIn2S4 photocatalyst. Appl. Catal. B: Environ. 2021, 299, 120675.
Feng, C. Y.; Tang, L.; Deng, Y. C.; Wang, J. J.; Tang, W. W.; Liu, Y. N.; Chen, Z. M.; Yu, J. F.; Wang, J. J.; Liang, Q. H. Synthesis of branched WO3@W18O49 homojunction with enhanced interfacial charge separation and full-spectrum photocatalytic performance. Chem. Eng. J. 2020, 389, 124474.
Li, C. Q.; Du, X.; Jiang, S.; Liu, Y.; Niu, Z. L.; Liu, Z. Y.; Yi, S. S.; Yue, X. Z. Constructing direct Z-scheme heterostructure by enwrapping ZnIn2S4 on CdS hollow cube for efficient photocatalytic H2 generation. Adv. Sci. 2022, 9, 2201773.
Chen, S. B.; Hau Ng, Y.; Liao, J. H.; Gao, Q. Z.; Yang, S. Y.; Peng, F.; Zhong, X. H.; Fang, Y. P.; Zhang, S. S. FeCo alloy@N-doped graphitized carbon as an efficient cocatalyst for enhanced photocatalytic H2 evolution by inducing accelerated charge transfer. J. Energy Chem. 2021, 52, 92–101.
Chowdhury, A.; Balu, S.; Venkatesvaran, H.; Chen, S. W.; Yang, T. C. K. Facile construction of CuFe2O4/p-g-C3N4 p–n heterojunction with boosted photocatalytic activity and sustainability for organic degradation reactions under visible-light. Surf. Interfaces 2022, 34, 102329.
Bai, J. X.; Shen, R. C.; Jiang, Z. M.; Zhang, P.; Li, Y. J.; Li, X. Integration of 2D layered CdS/WO3 S-scheme heterojunctions and metallic Ti3C2 MXene-based Ohmic junctions for effective photocatalytic H2 generation. Chin. J. Catal. 2022, 43, 359–369.
Xue, W. H.; Sun, H. L.; Hu, X. Y.; Bai, X.; Fan, J.; Liu, E. Z. UV–VIS–NIR-induced extraordinary H2 evolution over W18O49/Cd0.5Zn0.5S: Surface plasmon effect coupled with S-scheme charge transfer. Chin. J. Catal. 2022, 43, 234–245
Guo, Z. R.; Zhang, X.; Li, X. Y.; Cui, C.; Zhang, Z. L.; Li, H. S.; Zhang, D. X.; Li, J. Y.; Xu, X. Y.; Zhang, J. T. Enhanced charge separation by incomplete calcination modified co-doped TiO2 nanoparticle for isothiazolinone photocatalytic degradation. Nano Res. 2024, 17, 4834–4843.
Wang, H. Y.; Niu, R. R.; Liu, J. H.; Guo, S.; Yang, Y. P.; Liu, Z. Y.; Li, J. Electrostatic self-assembly of 2D/2D CoWO4/g-C3N4 p–n heterojunction for improved photocatalytic hydrogen evolution: Built-in electric field modulated charge separation and mechanism unveiling. Nano Res. 2022, 15, 6987–6998.
Zhang, N.; Jalil, A.; Wu, D. X.; Chen, S. M.; Liu, Y. F.; Gao, C.; Ye, W.; Qi, Z. M.; Ju, H. X.; Wang, C. M. et al. Refining defect states in W18O49 by Mo doping: A strategy for tuning N2 activation towards solar-driven nitrogen fixation. J. Am. Chem. Soc. 2018, 140, 9434–9443.
Qi, Y.; Zhang, J. W.; Kong, Y.; Zhao, Y.; Chen, S. S.; Li, D.; Liu, W.; Chen, Y. F.; Xie, T. F.; Cui, J. Y. et al. Unraveling of cocatalysts photodeposited selectively on facets of BiVO4 to boost solar water splitting. Nat. Commun. 2022, 13, 484.
Luo, D.; Peng, L.; Wang, Y.; Lu, X. Y.; Yang, C.; Xu, X. S.; Huang, Y. C.; Ni, Y. H. Highly efficient photocatalytic water splitting utilizing a WO3− x /ZnIn2S4 ultrathin nanosheet Z-scheme catalyst. J. Mater. Chem. A 2021, 9, 908–914.
Zhou, Q.; Wang, X. Y.; Tan, X. J.; Zhang, Q. H.; Yang, H.; Xing, T.; Wang, M. Q.; Wu, M. B.; Wu, W. T. Selective photocatalytic oxidation of methane to C1 oxygenates by regulating sizes and facets over Au/ZnO. Nano Res. 2024, 17, 3810–3818.
Dang, X. Y.; Xie, M. S.; Dai, F. F.; Guo, J. N.; Liu, J.; Lu, X. Q. Ultrathin 2D/2D ZnIn2S4/g-C3N4 nanosheet heterojunction with atomic-level intimate interface for photocatalytic hydrogen evolution under visible light. Adv. Mater. Interfaces 2021, 8, 2100151.
Pu, Y. C.; Fan, H. C.; Liu, T. W.; Chen, J. W. Methylamine lead bromide perovskite/protonated graphitic carbon nitride nanocomposites: Interfacial charge carrier dynamics and photocatalysis. J. Mater. Chem. A 2017, 5, 25438–25449.
Ke, X. C.; Zhang, J. F.; Dai, K.; Fan, K.; Liang, C. H. Integrated S-scheme heterojunction of amine-functionalized 1D CdSe nanorods anchoring on ultrathin 2D SnNb2O6 nanosheets for robust solar-driven CO2 conversion. Sol. RRL 2021, 5, 2000805.
Guo, Y. C.; Mao, L.; Tang, Y.; Shang, Q. Q.; Cai, X. Y.; Zhang, J. Y.; Hu, H. L.; Tan, X.; Liu, L. Q.; Wang, H. Y. et al. Concentrating electron and activating H–OH bond of absorbed water on metallic NiCo2S4 boosting photocatalytic hydrogen evolution. Nano Energy 2022, 95, 107028.
Chen, W.; Chang, L.; Ren, S. B.; He, Z. C.; Huang, G. B.; Liu, X. H. Direct Z-scheme 1D/2D WO2.72/ZnIn2S4 hybrid photocatalysts with highly-efficient visible-light-driven photodegradation towards tetracycline hydrochloride removal. J. Hazard. Mater. 2020, 384, 121308.
Liu, H. Y.; Niu, C. G.; Guo, H.; Huang, D. W.; Liang, C.; Yang, Y. Y.; Tang, N.; Zhang, X. G. Integrating the Z-scheme heterojunction and hot electrons injection into a plasmonic-based Zn2In2S5/W18O49 composite induced improved molecular oxygen activation for photocatalytic degradation and antibacterial performance. J. Colloid Interface Sci. 2022, 610, 953–969.
Deng, Y. C.; Feng, C. Y.; Tang, L.; Zhou, Y. Y.; Chen, Z. M.; Feng, H. P.; Wang, J. J.; Yu, J. F.; Liu, Y. N. Ultrathin low dimensional heterostructure composites with superior photocatalytic activity: Insight into the multichannel charge transfer mechanism. Chem. Eng. J. 2020, 393, 124718.