Wan Jun, Wang Yu, Liu Jiaqing, Song Ru, Liu Lin, Li Yaping, Li Jiayi, Low Jingxiang, Fu Feng, Xiong Yujie
College of Chemistry & Chemical Engineering, Research Institute of Comprehensive Energy Industrial Technology, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an University, Yan'an, Shaanxi, 716000, China.
Hefei National Research Center for Physical Sciences at the Microscale, USTC Center for Micro- and Nanoscale Research and Fabrication, University of Science and Technology of China, Hefei, Anhui, 230026, China.
Adv Mater. 2024 Aug;36(31):e2405060. doi: 10.1002/adma.202405060. Epub 2024 May 27.
Integration of photocatalytic hydrogen (H) evolution with oxidative organic synthesis presents a highly attractive strategy for the simultaneous production of clean H fuel and high-value chemicals. However, the sluggish dynamics of photogenerated charge carriers across the photocatalysts result in low photoconversion efficiency, hindering the wide applications of such a technology. Herein, this work overcomes this limitation by inducing the full-space electric field via charge polarization engineering on a Mo cluster-decorated ZnInS (Mo-ZnInS) photocatalyst. Specifically, this full-space electric field arises from a cascade of the bulk electric field (BEF) and local surface electric field (LSEF), triggering the oriented migration of photogenerated electrons from [Zn-S] regions to [In-S] regions and eventually to Mo cluster sites, ensuring efficient separation of bulk and surface charge carriers. Moreover, the surface Mo clusters induce a tip enhancement effect to optimize charge transfer behavior by augmenting electrons and proton concentration around the active sites on the basal plane of ZnInS. Notably, the optimized Mo-ZnInS catalyst achieves exceptional H and benzaldehyde production rates of 34.35 and 45.31 mmol g h, respectively, outperforming pristine ZnInS by 3.83- and 4.15-fold. These findings mark a significant stride in steering charge flow for enhanced photocatalytic performance.
将光催化析氢与氧化有机合成相结合，为同时生产清洁氢燃料和高价值化学品提供了一种极具吸引力的策略。然而，光生载流子在光催化剂中的动力学迟缓导致光转换效率低下，阻碍了该技术的广泛应用。在此，这项工作通过在钼簇修饰的硫化锌铟（Mo-ZnInS）光催化剂上进行电荷极化工程诱导全空间电场，克服了这一限制。具体而言，这种全空间电场源于体电场（BEF）和局域表面电场（LSEF）的级联，触发光生电子从[Zn-S]区域向[In-S]区域并最终向钼簇位点的定向迁移，确保体电荷载流子和表面电荷载流子的有效分离。此外，表面钼簇通过增加硫化锌铟基面活性位点周围的电子和质子浓度，诱导尖端增强效应以优化电荷转移行为。值得注意的是，优化后的Mo-ZnInS催化剂实现了分别为34.35和45.31 mmol g h的出色产氢率和苯甲醛产率，比原始的ZnInS分别高出3.83倍和4.15倍。这些发现标志着在引导电荷流动以提高光催化性能方面迈出了重要一步。
