Nie Zhongfen, Zhang Linlin, Ding Xin, Cong Meiyu, Xu Fanfan, Ma Lehui, Guo Mingxia, Li Mingzhu, Zhang Lixue
College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong, 266071, P. R. China.
State Key Laboratory of Fine Chemicals, Dalian University of Technology (DUT), Dalian, Liaoning, 116024, P. R. China.
Adv Mater. 2022 Apr;34(14):e2108180. doi: 10.1002/adma.202108180. Epub 2022 Feb 24.
Electrochemical N oxidation reaction (NOR), using water and N in the atmosphere, represents a sustainable approach for nitric production to replace the conventional industrial synthesis with high energy consumption and greenhouse gas emission. Meanwhile, owing to chemical inertness of N and sluggish kinetics for 10-electron transfer, emerging electrocatalysts remain largely underexplored. Herein, Ru-nanoclusters-coupled Mn O catalysts decorated with atomically dispersed Ru atoms (Ru-Mn O ) are designed and explored as an advanced electrocatalyst for ambient N oxidation, with an excellent Faraday efficiency (28.87%) and a remarkable NO yield (35.34 µg h mg ), respectively. Experiments and density functional theory calculations reveal that the outstanding activity is ascribed to the coexistence of Ru clusters and single-atom Ru. The synergistic effect between the Ru clusters and Mn O can effectively activate the chemically inert N , lowering the kinetic barrier for the vital breakage of N≡N. The intensive *OH supply and enhanced conductivity are used to regulate the catalytic kinetics for optimized performance. This work provides brand-new ideas for the rational design of electrocatalysts in complicated electrocatalytic reactions with multiple dynamics-different steps.
利用水和大气中的氮进行的电化学氮氧化反应（NOR），是一种可持续的制硝酸方法，可替代传统的高能耗和温室气体排放的工业合成方法。同时，由于氮的化学惰性和10电子转移的缓慢动力学，新型电催化剂在很大程度上仍未得到充分探索。在此，设计并探索了用原子分散的钌原子修饰的钌纳米团簇耦合的MnO催化剂（Ru-MnO）作为用于环境氮氧化的先进电催化剂，其法拉第效率优异（28.87%），NO产率显著（35.34 µg h mg ）。实验和密度泛函理论计算表明，优异的活性归因于钌团簇和单原子钌的共存。钌团簇与MnO之间的协同效应可有效激活化学惰性的氮，降低N≡N重要断裂的动力学势垒。密集的*OH供应和增强的导电性用于调节催化动力学以实现优化性能。这项工作为在具有多个不同动力学步骤的复杂电催化反应中合理设计电催化剂提供了全新思路。
