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Fast charge transfer kinetics in Sv-ZnIn2S4/Sb2S3 S-scheme heterojunction photocatalyst for enhanced photocatalytic hydrogen evolution

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Abstract

Constructing a S-scheme heterojunction with tight interface contact and fast charge transfer is beneficial to improving the photocatalytic hydrogen evolution performance. Herein, a unique one-dimensional (1D)/two-dimensional (2D) S-scheme heterojunction containing 1D Sb2S3 nanorods and 2D ZnIn2S4 with affluent sulfur vacancies (denoted as Sv-ZnIn2S4@Sb2S3) was designed. The introduced sulfur vacancy can promote the effective adsorption of H+ for the following interfacial hydrogen-evolution reaction. Furthermore, the larger contact area and stronger electron interaction between Sb2S3 and ZnIn2S4 effectively inhibits the recombination of photo-generated electron–hole pairs and abridges the migration distance of charges. As a result, the optimal Sv-ZnIn2S4@Sb2S3 sample achieves H2 evolution activity of 2741.3 mol·h−1·g−1, which is 8.6 times that of pristine ZnIn2S4 and 3.0 times that of the Sv-ZnIn2S4 samples. Based on the experimental result, the photo-reactivity S-scheme mechanism of hydrogen evolution from water splitting with Sv-ZnIn2S4@Sb2S3 is proposed. This work provides an effective method for developing S-scheme heterojunction composites of transition metal sulfide with high hydrogen evolution performance.

摘要

近年来, 过渡金属硫化物如MoS2、CdS、Cu2S、WS2等因其合适的带隙和和较高的吸收系数而备受关注, 适合作为可见光响应光催化剂。然而, 由于硫原子的化学状态不稳定, 二元金属硫化物, 比如Sb2S3, CdS等容易被光腐蚀, 从而导致其光催化活性不稳定。相比之下, 三元金属硫化物如ZnIn2S4等表现出良好的结构稳定性, 不过由于较快的电子-空穴复合速率及较低的量子效率, 其光催化性能还有待提高。基于上述考虑, 在最近提出的 S 型异质结的基础思想上, 我们首先确定了将 Sb2S3作为与ZnIn2S4复合的还原型光催化剂。本工作中, 我们首先通过低温溶剂热法制备了1D Sb2S3纳米纤维, 在此基础之上, 以油浴的方法制备获得 1D/2D 分等级且具有丰富硫空位的ZnIn2S4@Sb2S3 (Sv-ZIS@Sb2S3) S 型 (S-scheme) 异质结复合材料, 引入硫空位不仅可以有效地拓宽光吸收范围, 还能促进载流子的转移和分离。研究发现: 1D Sb2S3纳米纤维和2D的ZnIn2S4纳米片之间具有较大的接触面积和较强的电子相互作用, 可有效抑制光生电子-空穴对的复合。稳态光致发光光谱、瞬态光致发光光谱、光电流-时间响应谱和电化学阻抗谱等实验结果表明Sv-ZIS@Sb2S3复合材料相比于对应的单体具有更高的载流子传输和分离效率。最优比的Sv-ZIS@Sb2S3复合材料的析氢活性为2741.3 mol·h−1·g−1, 分别是是原始ZnIn2S4样品的8.6倍, 是Sv-ZnIn2S4样品的3.0倍。利用 X 射线光电子能谱 (XPS) 以及DFT计算等表征手段证实了半导体接触后内建电场的存在, 以及光照后载流子的移动方向, 这些都表明所制备的异质结是 S 型机理而不是传统的II型机理。 本工作为开发出具有高效析氢性能的过渡金属硫化物S型异质结复合材料提供了一种有效的方法。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 12075174 and 91963207) and the National Key Research and Development Program of China (No. 2022YFA1602701).

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Authors and Affiliations

  1. Key Laboratory of Artificial Micro- and Nano-Structures of Ministry of Education, School of Physics and Technology, Wuhan University, Wuhan, 430072, China

    Wei Li, Jia-Jun Li, Zhi-Fei Liu, Hong-Yu Ma, Peng-Fei Fang, Rui Xiong & Jian-Hong Wei

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Li, W., Li, JJ., Liu, ZF. et al. Fast charge transfer kinetics in Sv-ZnIn2S4/Sb2S3 S-scheme heterojunction photocatalyst for enhanced photocatalytic hydrogen evolution. Rare Met. 43, 533–542 (2024). https://doi.org/10.1007/s12598-023-02419-5

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