Xu Dan, Zhai Li, Mu Zhangyan, Tao Chen-Lei, Ge Feiyue, Zhang Han, Ding Mengning, Cheng Fang, Wu Xue-Jun
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University Nanjing 210023 China
Department of Chemistry, City University of Hong Kong Tat Chee Avenue, Kowloon Hong Kong China.
Chem Sci. 2023 Sep 1;14(37):10167-10175. doi: 10.1039/d3sc02493h. eCollection 2023 Sep 27.
Branched metal chalcogenide nanostructures with well-defined composition and configuration are appealing photocatalysts for solar-driven organic transformations. However, precise design and controlled synthesis of such nanostructures still remain a great challenge. Herein, we report the construction of a variety of highly symmetrical metal sulfides and heterostructured icosapods based on them, in which twenty branches were radially grown in spatially ordered arrangement, with a high degree of structure homogeneity. Impressively, the as-obtained CdS-PdS icosapods manifest a significantly improved photocatalytic activity for the selective oxidation of biomass-relevant alcohols into corresponding aldehydes coupled with H evolution under visible-light irradiation (>420 nm), and the apparent quantum yield of the benzyl alcohol reforming can be achieved as high as 31.4% at 420 nm. The photoreforming process over the CdS-PdS icosapods is found to be directly triggered by the photogenerated electrons and holes without participation of radicals. The enhanced photocatalytic performance is attributed to the fast charge separation and abundant active sites originating from the well-defined configuration and spatial organization of the components in the branched heterostructures.
具有明确组成和构型的分支金属硫族化物纳米结构是用于太阳能驱动有机转化的有吸引力的光催化剂。然而，此类纳米结构的精确设计和可控合成仍然是一个巨大的挑战。在此，我们报告了基于它们构建的各种高度对称的金属硫化物和异质结构二十面体，其中二十个分支以空间有序排列径向生长，具有高度的结构均匀性。令人印象深刻的是，所获得的CdS-PdS二十面体在可见光照射（>420 nm）下对与生物质相关的醇选择性氧化为相应醛并伴有析氢表现出显著提高的光催化活性，并且在420 nm下苯甲醇重整的表观量子产率可高达31.4%。发现CdS-PdS二十面体上的光重整过程由光生电子和空穴直接触发，而无自由基参与。光催化性能的增强归因于分支异质结构中组分明确的构型和空间组织所带来的快速电荷分离和丰富的活性位点。
