Atomically precise silver-based bimetallic clusters for electrocatalytic urea synthesis  

作　　者：Hong Chen Lin Liu Xiao-Hong Ma Su-Jun Zheng Xiao-Yu Dong Ren-Wu Huang Zhao-Yang Wang Jinmeng Cai Shuang-Quan Zang 

机构地区：[1]Henan Key Laboratory of Crystalline Molecular Functional Materials,College of Chemistry,Zhengzhou University,Zhengzhou 450001,China

出　　处：《National Science Review》2025年第2期140-148,共9页国家科学评论(英文版)

基　　金：supported by the National Natural Science Foundation of China(92061201,92356304 and 22205213);the Joint Fund of Science and Technology Research Program of Henan Province(242301420046);Thousand Talents(Zhongyuan Scholars)Program of Henan Province(234000510007).

摘　　要：Electrocatalytic urea synthesis from CO_(2) and nitrate holds immense promise as a sustainable strategy,but its complicated synthesis steps and controversial C-N coupling mechanism restrict the design of efficient catalysts.Atomically precise metal cluster materials are ideal model catalysts for investigating the C-N coupling issues.Here we synthesize two atomically precise bimetallic clusters,Ag_(14) Pd(PTFE)_(6)(TPP)_(8) and Ag_(13) Au_(5)(PTFE)_(10)(DPPP)_(4),both with icosahedral cores and similar ligands.We demonstrate that both clusters have good performance for electrocatalytic urea synthesis,with the production rates at the maximum Faradaic efficiency of 143.3 and 82.3 mg h^(−1) g_(cat)^(−1),respectively.Bimetallic structures can induce charge polarization at the active sites of metal clusters,thereby influencing the selectivity.In mechanistic investigations,we propose that*NOH and*COOH are the rate-limiting steps for the reduction of nitrate and CO_(2),respectively,and that the key intermediates formed thereafter can significantly affect the C-N coupling process.This approach offers a deep understanding into C-N coupling through the utilization of atomically precise metal clusters.

关 键 词：atomically precise bimetallic clusters ELECTROCATALYSIS C-N coupling urea synthesis 

分 类 号：O62[理学—有机化学]