Abstract
Electrocatalytic reduction of the pollutant nitrate to ammonia (NO(3)RR) using clean energy is being considered as a viable alternative to the Haber-Bosch process for producing industrially valuable ammonia. However, the multi-electron-proton transfer process of the NO(3)RR to ammonia usually leads to poor selectivity and low current density, which still cannot meet the industrial requirements. Stabilizing the key intermediates during the reaction is particularly important for achieving high selectivity in the NO(3)RR towards the production of NH(3). Herein, we develop a hydrogen bonding strategy to stabilize the key intermediates of the NO(3)RR, which involves the design and synthesis of trinuclear copper(i) cluster-based metal-organic frameworks (MOFs). The methyl groups in the copper-based MOFs (DiMe-Cu(3)-MOF) can regulate the electron density around the Cu(3) site and stabilize the key intermediates, *NO(2), through hydrogen bonding interaction with methyl groups. Thus, the DiMe-Cu(3)-MOF electrocatalyst delivers a high NH(3) faradaic efficiency (95%) for the NO(3)RR with a high ammonia production of 401 μg cm(-2) h(-1), and the partial current density of ammonia reaches an industrial level value of -950.6 mA cm(-2). Control experiments and theoretical studies demonstrated that the introduction of methyl groups into the DiMe-Cu(3)-MOF can facilitate atypical hydrogen bonding with the intermediates of the NO(3)RR and thus enhance the adsorption of intermediates and reduce the energy barrier of the conversion of NO(3) (-) to NH(3). This work highlights the vital importance of adjusting the microenvironment through hydrogen bonding for enhancing the NO(3)RR performance.