Cao Yun-Dong, Yin Di, Li Si, Dong Xi-Yan, Feng Y, Liu Hong, Fan Lin-Lin, Gao Guang-Gang, Zang Shuang-Quan
School of Materials Science and Engineering, University of Jinan, Jinan, 250022, China.
Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Angew Chem Int Ed Engl. 2023 Aug 7;62(32):e202307678. doi: 10.1002/anie.202307678. Epub 2023 Jul 4.
The propulsion of photocatalytic hydrogen (H ) production is limited by the rational design and regulation of catalysts with precise structures and excellent activities. In this work, the [MoOS ] unit is introduced into the Cu clusters to form a series of atomically-precise Mo -Cu bimetallic clusters of [Cu (MoOS ) (C H (CH )S) (P(C H -R) ) ] ⋅ xCH CN (R=H, CH , or F), which show high photocatalytic H evolution activities and excellent stability. By electron push-pull effects of the surface ligand, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of these Mo -Cu clusters can be finely tuned, promoting the resultant visible-light-driven H evolution performance. Furthermore, Mo -Cu clusters loaded onto the surface of magnetic Fe O carriers significantly reduced the loss of catalysts in the collection process, efficiently addressing the recycling issues of such small cluster-based catalyst. This work not only highlights a competitively universal approach on the design of high-efficiency cluster photocatalysts for energy conversion, but also makes it feasible to manipulate the catalytic performance of clusters through a rational substituent strategy.
光催化产氢的推进受到具有精确结构和优异活性的催化剂的合理设计和调控的限制。在这项工作中，将[MoOS]单元引入到铜簇中，形成了一系列原子精确的[Cuₓ(MoOS)ₙ(C₆H₄(CH₃)S)ₘ(P(C₆H₅-R)₃)ₖ]⋅xCH₃CN（R = H、CH₃或F）钼-铜双金属簇，这些簇表现出高光催化析氢活性和优异的稳定性。通过表面配体的电子推拉效应，可以精细调节这些钼-铜簇的最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）能级，从而提升可见光驱动的析氢性能。此外，负载在磁性Fe₃O₄载体表面的钼-铜簇显著减少了收集过程中催化剂的损失，有效解决了这种基于小簇的催化剂的回收问题。这项工作不仅突出了一种在设计用于能量转换的高效簇状光催化剂方面具有竞争力的通用方法，而且通过合理的取代基策略来操纵簇的催化性能也变得可行。
