Liu Sibi, Zhang Youzi, Wang Maohuai, Wei Yanping, Wang Yijin, Chen Weizhe, Mao Siman, Guo Peng, Ghasemi Jahan B, Zhou Junchao, Zhang Shujie, Li Xuanhua
State Key laboratory of Solidification Processing, Center for Nano Energy Materials, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an, 710072, P. R. China.
Research and Development Institute of Northwestern Polytechnical University, Shenzhen, 518057, P. R. China.
Adv Mater. 2025 Aug 25:e08693. doi: 10.1002/adma.202508693.
Loading the cocatalyst, e.g., Pt, is a promising strategy for photocatalytic overall water splitting, in which metallic state Pt° facilitates proton reduction and positive valence state Pt inhibits H/O recombination. However, simultaneously leveraging the advantages of Pt and Pt in Pt-photocatalyst hybrids for photocatalytic water splitting is challenging. Herein, a universal strategy is demonstrated for modulating Pt valence state, obtaining a spatially oriented distribution of Pt/Pt and a close to zero proton reduction barrier, along with isolated O adsorption. As a proof of concept, Pt undergoes electron transfer to ZnInS, accompanied by partial oxidation from Pt to Pt through the introduction of electron-deficient centers in ZnInS via vanadium doping and sulfur vacancy (V-Sv-ZIS). Reverse electron transfer induces Pt dominating 83% of the region near the Pt/V-Sv-ZIS interface and Pt dominating in the remaining 17% near the Pt cluster center, which can be extended to other Pt-based catalyst systems. The dominant Pt inhibits O adsorption and induces the lowest H/O recombination rate of 4%, and the minimal Pt obtains a 152.2-fold increase in photogenerated electron density, ultimately realizing a 45.4-fold increase in photocatalytic activity. A 10 m large-area photocatalytic system is fabricated, producing 6.4 L of H per day under natural sunlight.
负载助催化剂，例如铂，是光催化全水分解的一种有前景的策略，其中金属态的Pt°促进质子还原，而正价态的Pt抑制氢/氧复合。然而，在用于光催化水分解的Pt光催化剂杂化物中同时利用Pt和Pt的优势具有挑战性。在此，展示了一种通用策略来调节Pt的价态，获得Pt/Pt的空间定向分布以及接近零的质子还原势垒，同时实现孤立的氧吸附。作为概念验证，通过钒掺杂和硫空位（V-Sv-ZIS）在ZnInS中引入缺电子中心，Pt向ZnInS发生电子转移，同时伴随着从Pt到Pt的部分氧化。反向电子转移导致在Pt/V-Sv-ZIS界面附近83%的区域中Pt占主导，而在Pt簇中心附近其余17%的区域中Pt占主导，这一策略可扩展到其他基于Pt的催化剂体系。占主导的Pt抑制氧吸附并诱导出低至4%的氢/氧复合率，而占比极小的Pt使光生电子密度提高了152.2倍，最终实现光催化活性提高45.4倍。制备了一个10平方米的大面积光催化系统，在自然阳光下每天产生6.4升氢气。
