Substituent Effect to Fine-Tune Energy Levels of Atom-Precise [MoOS 3 ] 2- Modified Copper(I) Thiolate Clusters Boosting Recyclable Photocatalysis.

The propulsion of photocatalytic hydrogen (H ₂ ) production is limited by the rational design and regulation of catalysts with precise structures and excellent activities. In this work, the [MoOS ₃ ] ^2- unit is introduced into the Cu ^I clusters to form a series of atomically-precise Mo ^VI -Cu ^I bimetallic clusters of [Cu ₆ (MoOS ₃ ) ₂ (C ₆ H ₅ (CH ₂ )S) ₂ (P(C ₆ H ₄ -R) ₃ ) ₄ ] ⋅ xCH ₃ CN (R=H, CH ₃ , or F), which show high photocatalytic H ₂ 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 ^VI -Cu ^I clusters can be finely tuned, promoting the resultant visible-light-driven H ₂ evolution performance. Furthermore, Mo ^VI -Cu ^I clusters loaded onto the surface of magnetic Fe ₃ O ₄ 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.
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