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Facile defect engineering in ZnIn2S4 nanosheets for enhanced NIR-driven H2 evolution

缺陷工程调控ZnIn2S4纳米片用于增强近红外驱动制氢

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Abstract

Near-infrared (NIR) light-driven water splitting to produce hydrogen (H2) has long been of great interest in photocatalysis, but it remains a formidable challenge so far due to both kinetic and thermodynamic shortcomings. To break through this limitation, we demonstrate a noble metal-free two-dimensional ZnIn2S4-based photocatalyst rich in sulfur vacancies via a facile hydrothermal method and firstly realized NIR-driven H2 production beyond 800 nm using single component ZnIn2S4-based materials. We disclosed the existence of an efficient Urbach tail transition to absorb long-wavelength NIR light according to the valence-band spectra, ultraviolet-visible-NIR diffuse reflectance spectra, steady-state photoluminescence spectra, transient photocurrent response, and electron paramagnetic resonance measurements. The successful construction of sulfur vacancies in ZnIn2S4 nanosheets not only extends the spectral absorption range but also has an excellent carrier diffusion property as well as an abundance of active sites. Therefore, our findings may provide an effective and promising perspective for the future development of NIR-responsive ZnIn2S4-based photocatalysts for highly efficient H2 production.

摘要

近红外(NIR)光驱动水分解产生氢气(H2)一直以来都是光催化领 域备受关注的问题, 但由于其动力学和热力学方面的缺陷, 迄今为止仍 是一项艰巨的挑战. 为了突破这一限制, 我们通过简便的水热法设计出 了富含硫空位的无贵金属二维(2D) ZnIn2S4-基光催化剂, 并首次使用 单组分ZnIn2S4-基材料实现了波长大于800 nm的近红外驱动制氢性能. 根据价带光谱、紫外-可见-近红外DRS光谱、稳态PL光谱、瞬态光电 流响应和EPR表征, 我们揭示了存在一个高效的Urbach带尾吸收用于 捕获近红外光. 硫空位在ZnIn2S4纳米片中的成功构建不仅扩展了光谱 吸收范围, 而且具有出色的载流子扩散特性和丰富的活性位点. 因此, 我们的研究结果可能会为未来开发近红外响应的ZnIn2S4-基光催化剂 用于实现高效近红外驱动制氢提供一定的指导.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22225808), the Sino-German Cooperation Group Project (GZ1579), Jiangsu Province Innovation Support Program International Science and Technology Cooperation Project (BZ2022045), and the Special Scientific Research Project of School of Emergency Management, Jiangsu University (KY-A-02).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, 212003, China

    Yuanyong Huang  (黄元勇), Xinyu Lu  (陆欣宇) & Weidong Shi  (施伟东)

  2. School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013, China

    Yuanyong Huang  (黄元勇), Hong Yang  (杨洪), Shuo Feng  (冯硕), Changwen Ma  (马畅文), Peiyi Cao  (曹佩一), Feifei Li  (李菲菲) & Weidong Shi  (施伟东)

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  1. Yuanyong Huang  (黄元勇)
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  2. Hong Yang  (杨洪)
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Contributions

Author contributions Huang Y, Yang H, and Shi W conceived the project and designed the experiments; Huang Y, Yang H, Feng S, Ma C, Cao P, Li F, and Lu X performed data analysis and characterization; Huang Y, Yang H, and Shi W contributed to the project discussions, wrote the manuscript, and corrected the article draft; Shi W supervised this research Huang Y and Yang H contributed equally to this paper All authors read and approved the manuscript.

Corresponding author

Correspondence to Weidong Shi  (施伟东).

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

Additional information

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

Yuanyong Huang is currently a PhD student under the tutelage of Professor Weidong Shi at Jiangsu University, Zhenjiang, China. He is mainly interested in the design and synthesis of NIR-responsive photocatalysts for solar energy conversion.

Hong Yang is currently a Master student under the tutelage of Professor Weidong Shi at Jiangsu University, Zhenjiang, China. At present, his research mainly focuses on the design and synthesis of ZnIn2S4-based nano-materials and their applications on NIR-driven H2 production.

Weidong Shi (College of Environmental and Chemical Engineering, Jiangsu University of Science and Technology) received his PhD degree from Changchun Institute of Applied Chemical, National Key Laboratory of Rare Earth Resources Utilization, Chinese Academy of Sciences in 2007. He then conducted postdoctoral research at the University of Glasgow in UK and University of Cologne in Germany. His research interests currently focus on new materials and energy photocatalysis, electrocatalysis with emphasis on the design of new catalysts and control of morphology, microstructure and reaction mechanism for hydrogen production, and environmental pollutants degradation.

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Huang, Y., Yang, H., Feng, S. et al. Facile defect engineering in ZnIn2S4 nanosheets for enhanced NIR-driven H2 evolution. Sci. China Mater. 67, 1812–1819 (2024). https://doi.org/10.1007/s40843-024-2844-8

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