Pd Nanoparticle Size-Dependent H* Coverage for Cu-Catalyzed Nitrate Electro-Reduction to Ammonia in Neutral Electrolyte.

Abstract

Electrochemical conversion of nitrate (NO3 -) to ammonia (NH3) is an effective approach to reduce nitrate pollutants in the environment and also a promising low-temperature, low-pressure method for ammonia synthesis. However, adequate H* intermediates are highly expected for NO3 - hydrogenation, while suppressing competitive hydrogen evolution. Herein, the effect of H* coverage on the NO3RR for ammonia synthesis by Cu electrocatalysts is investigated. The H* coverage can be adjusted by changing Pd nanoparticle sizes. The optimized Pd@Cu with an average Pd size of 2.88nm shows the best activity for NO3RR, achieving a maximum Faradaic efficiency of 97% (at -0.8V vs RHE) and an NH3 yield of 21mg h-1 cm- 2, from an industrial wastewater level of 500ppm NO3 -. In situ electrochemical experiments indicate that Pd particles with 2.88nm can promote NO3 - hydrogenation to NH3 via well-modulated coverage of adsorbed H* species. Coupling the anodic glycerol oxidation reaction, ammonium and formate are successfully obtained as value-added products in a membrane electrode assembly electrolyzer. This work provides a feasible strategy for obtaining size-dependent H* intermediates for hydrogenation.