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1D/2D CeO2/ZnIn2S4 Z-scheme heterojunction photocatalysts for efficient H2 evolution under visible light

1D/2D CeO2/ZnIn2S4 Z-scheme异质结光催化剂实现高效可见光分解水制氢

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Abstract

The development of a high-efficiency photocatalyst having favorable charge transfer has become an important scientific approach for solar-to-fuel conversion. In this study, the one-dimensional (1D)/2D CeO2/ZnIn2S4 (ZIS) photocatalyst having a Z-scheme heterojunction has been successfully fabricated using the in situ growth of ZIS nanosheets on the CeO2 nanorod surfaces. The optimal H2 production rate of 3.29 mmol g−1 h−1 was achieved with the 15% CeO2/ZIS sample under visible light without any cocatalyst; furthermore, this value was 2.7 and 92.6 times higher than those of pristine ZIS and CeO2, respectively. The remarkable photocatalytic activity can be attributed to the efficient separation of photogenerated carriers as well as the formation of the Z-scheme heterojunction, which maintained the strong reduction of electrons in ZIS for H2 production. The presence of an internal electric field between CeO2 and ZIS has been demonstrated by both density functional theory calculations and Kelvin probe force microscopy. The Z-scheme transfer of photogenerated carriers in the CeO2/ZIS heterojunction has been confirmed by electron paramagnetic resonance spectroscopy and in situ irradiated X-ray photoelectron spectroscopy. This study presents certain insights into the development of efficient Z-scheme photocatalysts for H2 evolution from solar water splitting.

摘要

开发具有高效电荷转移效率的光催化剂已成为太阳能-氢能转换的关键科学方法. 本研究通过在CeO2纳米棒表面原位生长ZnIn2S4纳米片, 成功制备了具有Z-scheme异质结的1D/2D CeO2/ZnIn2S4光催化剂. 在无助催化剂的情况下, 15 wt% CeO2/85 wt% ZnIn2S4样品在可见光下实现了3.29 mmol g−1 h−1的最佳H2产量, 该值分别比原始ZnIn2S4和CeO2分别高2.7倍和92.6倍. 优异的光催化活性可能是由于光生载流子的有效分离和Z-scheme异质结的形成保留了ZnIn2S4中用于产氢的强还原电子. 密度泛函理论计算和开尔文探针力显微镜证明了CeO2和ZnIn2S4之间存在内部电场. 此外, 电子顺磁共振光谱以及原位辐照X射线光电子能谱证实了CeO2/ZnIn2S4异质结中的光生载流子按照Zscheme路径转移. 这项工作可为开发用于太阳能水分解制氢的高效Zscheme光催化剂提供一些见解.

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Acknowledgements

This work was supported by the Fundamental Research Funds for the Central Universities (2019XKQYMS11).

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Authors and Affiliations

  1. School of Materials Science and Physics, China University of Mining and Technology, Xuzhou, 221116, China

    Renqian Jiang  (姜人倩), Liang Mao  (毛梁), Yulong Zhao  (赵宇龙), Yanwei Sui  (隋艳伟), Xiuquan Gu  (顾修全) & Xiaoyan Cai  (蔡晓燕)

  2. Jiangsu Province Engineering Laboratory of High Efficient Energy Storage Technology and Equipment, Xuzhou, 221116, China

    Renqian Jiang  (姜人倩), Liang Mao  (毛梁), Yulong Zhao  (赵宇龙), Yanwei Sui  (隋艳伟), Xiuquan Gu  (顾修全) & Xiaoyan Cai  (蔡晓燕)

  3. School of Physics, Beihang University, Beijing, 100191, China

    Junying Zhang  (张俊英)

  4. Micro- and Nanoelectronics Department, Belarusian State University of Informatics and Radioelectronics, Minsk, 220013, Belarus

    Eugene B. Chubenko & Vitaly Bondarenko

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  1. Renqian Jiang  (姜人倩)
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  2. Liang Mao  (毛梁)
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  3. Yulong Zhao  (赵宇龙)
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  4. Junying Zhang  (张俊英)
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  5. Eugene B. Chubenko
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  6. Vitaly Bondarenko
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  7. Yanwei Sui  (隋艳伟)
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  8. Xiuquan Gu  (顾修全)
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  9. Xiaoyan Cai  (蔡晓燕)
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Contributions

Jiang R performed the experiments and wrote the paper with support from Chubenko EB and Bondarenko V; Mao L and Zhao Y designed and engineered the samples; Zhang J and Cai X contributed to the theoretical analysis; Sui Y, Gu X, and Cai X performed the data analysis. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Xiuquan Gu  (顾修全) or Xiaoyan Cai  (蔡晓燕).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Renqian Jiang received her BS degree from Central South University. She is currently studying for her MS degree under the supervision of Professor Xiuquan Gu at the University of Mining and Technology. Her research interest focuses on photocatalytic hydrogen production.

Xiuquan Gu received his BS degree in physics from Anhui Normal University and his PhD degree from Zhejiang University in 2009. He is currently an assistant professor at the University of Mining and Technology. His current research interests include semiconductor photocatalysis, photocatalytic hydrogen production, and photoelectrocatalysis.

Xiaoyan Cai received her PhD degree from Beihang University in 2018. She is currently a faculty member at the School of Materials Science and Physics, China University of Mining and Technology. Her research interests are photocatalytic and electrocatalytic materials for energy conversion and environmental remediation.

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Jiang, R., Mao, L., Zhao, Y. et al. 1D/2D CeO2/ZnIn2S4 Z-scheme heterojunction photocatalysts for efficient H2 evolution under visible light. Sci. China Mater. 66, 139–149 (2023). https://doi.org/10.1007/s40843-022-2132-8

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