Sun Mengmiao, Wu Guanzheng, Jiang Jiadi, Yang Yidong, Du Aijun, Dai Lei, Mao Xin, Qin Qing
The Key Laboratory of Functional Molecular Solids, Ministry of Education, The Key Laboratory of Electrochemical Clean Energy of Anhui Higher Education Institutes, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, 241002, China.
School of Chemistry and Physics and Centre for Material Science, Faculty of Science, Queensland University of Technology, Gardens Point Campus, Brisbane, QLD-4001, Australia.
Angew Chem Int Ed Engl. 2023 May 2;62(19):e202301957. doi: 10.1002/anie.202301957. Epub 2023 Apr 4.
The electrochemical NO reduction and its coupling with CO can provide novel and clean routes to synthesize NH and urea, respectively. However, their practical application is still impeded by the lack of efficient catalysts with desirable Faradaic efficiency (FE) and yield rate. Herein, we report the synthesis of molybdenum oxide nanoclusters anchored on carbon black (MoO /C) as electrocatalyst. It affords an outstanding FE of 98.14 % and NH yield rate of 91.63 mg h mg in NO reduction. Besides, the highest FE of 27.7 % with a maximum urea yield rate of 1431.5 μg h mg toward urea is also achieved. The formation of electron-rich MoO nanoclusters with highly unsaturated metal sites in the MoO /C heterostructure is beneficial for enhanced catalytic performance. Studies on the mechanism reveal that the stabilization of *NO and *CO NOOH intermediates are critical for the NH and urea synthesis, respectively.
电化学NO还原及其与CO的耦合反应分别为合成NH₃和尿素提供了新颖且清洁的途径。然而，由于缺乏具有理想法拉第效率（FE）和产率的高效催化剂，它们的实际应用仍然受到阻碍。在此，我们报道了一种负载在炭黑上的氧化钼纳米团簇（MoOₓ/C）作为电催化剂的合成方法。在NO还原反应中，它具有98.14%的出色法拉第效率和91.63 mg h⁻¹ mg⁻¹的NH₃产率。此外，在尿素合成方面，还实现了高达27.7%的最高法拉第效率和1431.5 μg h⁻¹ mg⁻¹的最大尿素产率。MoOₓ/C异质结构中具有高度不饱和金属位点的富电子MoOₓ纳米团簇的形成有利于提高催化性能。机理研究表明，NO和CONOOH中间体的稳定分别对NH₃和尿素的合成至关重要。
