华东师范大学刘超团队报道了具有增强活性氢供应的S型异质结光催化剂上的高效固氮。相关研究成果发表在2024年3月9日出版的《国家科学评论》。

光催化N₂固定是合成氨（NH₃）的一种很有前途的策略，但由于难以设计具有高电荷转移效率和所需N₂吸附/活化能力的光催化剂，因此氨产率相对较低。

该文设计了一种具有双活性位点的S型CoSx/ZnS异质结作为有效的N₂固定光催化剂。CoSx/ZnS异质结表现出独特的口袋状纳米结构，小的ZnS纳米晶体粘附在单孔CoSx中空十二面体上。

在异质结内，ZnS和CoSx之间的电子相互作用产生了具有增强的N₂化学吸附的缺电子Zn位点，和具有用于N₂氢化的活性氢供应的缺电子Co位点，共同降低了N₂活化的能垒。结合S型异质结的光生电子空穴分离和口袋状纳米结构的传质，获得了优异的N₂固定性能，NH₃产率高达1175.37μmol g^-1 h^-1。

该项研究为用于N₂固定的异质结光催化剂的设计提供了新的见解。

附：英文原文

Title: Highly efficient nitrogen fixation over S-scheme heterojunction photocatalysts with enhanced active hydrogen supply

Author: Bao, Tong, Xi, Yamin, Zhang, Chaoqi, Du, Peiyang, Xiang, Yitong, Li, Jiaxin, Yuan, Ling, Yu, Chengzhong, Liu, Chao

Issue&Volume: 2024-03-09

Abstract: Photocatalytic N2 fixation is a promising strategy for ammonia (NH3) synthesis, however suffering from relatively low ammonia yield due to the difficulty in the design of photocatalysts with both high charge transfer efficiency and desirable N2 adsorption/activation capability. Herein, a S-scheme CoSx/ZnS heterojunction with dual active sites is designed as an efficient N2 fixation photocatalyst. The CoSx/ZnS heterojunction exhibits a unique pocket-like nanostructure with small ZnS nanocrystals adhered on single-hole CoSx hollow dodecahedron. Within the heterojunction, the electronic interaction between ZnS and CoSx creates electron-deficient Zn sites with enhanced N2 chemisorption and electron-sufficient Co sites with active hydrogen supply for N2 hydrogenation, cooperatively reducing the energy barrier for N2 activation. In combination with the promoted photogenerated electron-hole separation of S-scheme heterojunction and facilitated mass transfer by pocket-like nanostructure, an excellent N2 fixation performance with a high NH3 yield of 1175.37 μmol g1 h1 is achieved. This study provides new insights into the design of heterojunction photocatalysts for N2 fixation.

DOI: 10.1093/nsr/nwae093

Source: https://dx.doi.org/10.1093/nsr/nwae093