A Full-Spectrum ZnS Photocatalyst with Gradient Distribution of Atomic Copper Dopants and Concomitant Sulfur Vacancies for Highly Efficient Hydrogen Evolution

作者：Linping Bao, Sajjad Ali, Chunhui Dai, Qing Zeng, Chao Zeng, Yushuai Jia, Xin Liu, Ping Wang, Xiaohui Ren, Teng Yang, M. Bououdina, Zhang‐Hui Lu, Yuechang Wei, Xuan Yu, Yingtang Zhou · 发表于：ACS Nano · 年份：2024 · DOI：10.1021/acsnano.3c12773 · 被引用次数：61 · 研究领域：Advanced Photocatalysis Techniques、Copper-based nanomaterials and applications、Perovskite Materials and Applications

A rarely discussed phenomenon in the realm of photocatalytic materials involves the presence of gradient distributed dopants and defects from the interior to the surface. This intriguing characteristic has been successfully achieved in the case of ZnS through the incorporation of atomic monovalent copper ions (Cu + ) and concurrent sulfur vacancies (V s ), resulting in a photocatalyst denoted as G-CZS 1– x . Through the cooperative action of these atomic Cu dopants and Vs, G-CZS 1– x significantly extends its photoabsorption range to encompass the full spectrum (200–2100 nm), which improves the solar utilization ability. This alteration enhances the efficiency of charge separation and optimizes Δ(H*) (free energy of hydrogen adsorption) to approach 0 eV for the hydrogen evolution reaction (HER). It is noteworthy that both surface-exposed atomic Cu and V s act as active sites for photocatalysis. G-CZS 1– x exhibits a significant H 2 evolution rate of 1.01 mmol h –1 in the absence of a cocatalyst. This performance exceeds the majority of previously reported photocatalysts, exhibiting approximately 25-fold as ZnS, and 5-fold as H-CZS 1– x with homogeneous distribution of equal content Cu dopants and Vs. In contrast to G-CZS 1– x, the H adsorption on Cu sites for H-CZS 1– x (Δ G (H*) = −1.22 eV) is excessively strong to inhibit the H 2 release, and the charge separation efficiency for H-CZS 1– x is relatively sluggish, revealing the positive role of a gradient distribution model ...