Electrochemical Ammonia Synthesis via NO Reduction on 2D‐MOF
Bin Huang, Bibo Chen, Guoping Zhu, Jiahe Peng, Peng Zhang, Yong Qian, Neng Li
Abstract
Abstract Developing new catalysts that effectively promote electrocatalytic NO reduction (ENOR) is a very important industrial field. A two‐dimensional (2D) metal‐organic framework (MOF) with hexaaminobenzene (HAB) ligands (TM−HAB MOF, TM=Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh and Pd) as an electrocatalyst for ENOR was systematically explored in this work by means of well‐defined density functional theory (DFT) calculations. We predicted the impact of the coordination structure of different MOFs on its catalytic performance and found that the suitable candidates are Co− and Rh−HAB MOFs due to moderate binding strength between NO and substrates. Further calculations indicated that Co−HAB MOF has the best ENOR catalytic activity with a limiting potential of – 0.26 V toward NH 3 production at low NO coverage, yet NO reduction to N 2 O at high NO coverage was limited due to high limiting potential. The scaling relationship with a good correlation coefficient between several electronic properties and the adsorption Gibbs free energy change of *NO (ΔG *NO ) were found, which implies that ΔG *NO can be used as a simple descriptor for screening out suitable electrocatalysts. This work offers a new paradigm for ENOR toward NH 3 production under ambient conditions.