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Synergistically regulating d-band centers of heterojunction redox sites by ligand effect for photocatalytic H2 evolution

基于配体效应协同调控异质结氧化还原位点的d带中 心用于光解水制氢

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Abstract

Stiff transportation behaviors in kinetics for photo-excited charges from their generation sites to corresponding redox sites as well as subsequent large reaction overpotential of these charges with intermediates during splitting H2O have not been solved yet, which extremely hinders solar photon energy conversion into H2 (STH). Herein, CeO2 nanowires-anchored Ni2P nanoparticles were built to solve the above dynamical issues by synchronously modifying d-band centers (εd) with ligand effect. Photon-excited electrons and holes were separately propelled to Ni2P as the reductive site and CeO2 as the oxidative site within the spontaneously formed localized electric field for the dehydrogenation and coupling of active oxyhydrogen intermediates, respectively, characterized by in situ diffuse reflectance infrared Fourier transform spectroscopy and Hall effect tests. Consequently, a STH of 1.13% was achieved at room temperature under AM 1.5G irradiation. The study supplies a unique insight to enhance STH over heterojunction photocatalysts by synchronously tunning εd.

摘要

光催化水解离制氢过程中, 光生载流子由生成位点向氧化还原 位点艰难的动力学迁移及随后与中间产物反应大的过电位问题还没有 被解决, 严重阻碍了太阳光子转化为氢能的效率(STH). 本文基于配体 效应协同调控材料d带中心构建了CeO2 纳米线负载Ni2 P异质结光催化 剂, 继而解决上述动力学瓶颈. 原位漫反射傅里叶变换红外光谱、霍尔 效应等表征揭示光生电子和空穴在自发局域电场推动下, 分别迁移至 Ni2 P还原位点和CeO2 氧化位点, 接着促使吸附在此的活性中间产物发 生脱氢和氧耦合反应. 性能测试显示, 在AM 1.5G模拟太阳光辐照下, 室温下的STH值达到了1.13%. 本研究为通过协同调节d带中心提高异 质结光催化剂的STH提供了独特的策略.

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Acknowledgements

The work was supported by the National Natural Science Foundation of China (51972177 and 22372084), the Key Project of Zhejiang Province (2023C3016), and the Natural Science Foundation of Ningbo City (2021J067).

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Authors and Affiliations

  1. School of Materials Science & Chemical Engineering, Ningbo University, Ningbo, 330013, China

    Yuanxiao Wu  (吴园霄), Mengru Qu  (曲梦茹) & Shujuan Jiang  (姜淑娟)

  2. School of New Energy, Ningbo University of Technology, Ningbo, 315336, China

    Shaoqing Song  (宋少青)

  3. Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan, 430078, China

    Jianjun Zhang  (张建军)

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  1. Yuanxiao Wu  (吴园霄)
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  2. Mengru Qu  (曲梦茹)
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  3. Shujuan Jiang  (姜淑娟)
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  4. Jianjun Zhang  (张建军)
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Contributions

Author contributions Wu Y performed the experiments and wrote the original draft with the support from Qu M; Jiang S revised the manuscript and discussed the results; Zhang J performed the key characterizations and discussed the results; Song S designed the idea and revised the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Shujuan Jiang  (姜淑娟), Jianjun Zhang  (张建军) or Shaoqing Song  (宋少青).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Yuanxiao Wu received her BSc degree from the Department of Chemistry, Gannan Normal University. She is currently pursuing her Master’s degree at Ningbo University. Her research interest focuses on the band structure regulation for semiconductor materials according to the requirement of solar energy conversion.

Shujuan Jiang is currently a Yongjiang Professor at the School of Materials Science and Chemical Engineering, Ningbo University. Her research interest includes the construction of semiconductor photocatalysts and the study on the photocatalytic mechanism.

Jianjun Zhang received his BSc and PhD degrees in materials science from Wuhan University of Technology in 2017 and 2021, respectively. He worked as an International Exchange Research Fellow at Nanyang Technological University from 2022 to 2023. He is now a postdoctoral researcher working at the Laboratory of Solar Fuel, China University of Geosciences. His current research focuses on the electron transfer dynamics in heterojunction photocatalysts and perovskite solar cells.

Shaoqing Song is a full professor (the third grade) and dean in charge of academic affairs at the School of New Energy, Ningbo University of Technology. His research focuses on the construction and charge regulation of the localized heterojunction photocatalysts for H2O splitting into H2 fuel.

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Synergistically regulating d-band centers of heterojunction redox sites by ligand effect for photocatalytic H2 evolution

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Wu, Y., Qu, M., Jiang, S. et al. Synergistically regulating d-band centers of heterojunction redox sites by ligand effect for photocatalytic H2 evolution. Sci. China Mater. 67, 524–531 (2024). https://doi.org/10.1007/s40843-023-2760-1

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