Accelerating the development of electrocatalysts for electrochemical nitrogen fixation through theoretical and computational approaches

Abstract

The discovery of the Haber–Bosch process in the early 20th century facilitated the industrial synthesis of ammonia, thereby making a substantial contribution to the evolution of human society. Currently, towards a carbon-free economy, the electrocatalytic reduction of nitrogen (NRR) offers a promising, alternative technology to produce ammonia under mild conditions, given that it is a clean process without discernible environmental impact. However, despite significant efforts to construct superior catalysts and efficient reaction systems, the reaction rate and faraday efficiency for ammonia production remain well below the industrial threshold, primarily due to the difficulty in breaking NN bonds. Theoretical studies provide important support for fundamental understanding of the catalytic mechanism and electrocatalytic process, so as to carry out more reasonable and orientated design of reaction systems. In the present review, we focus on the theoretical and computational research developments in electrocatalytic NRR systems from a theoretical perspective at multiple scales, including DFT studies at the electronic level, thermodynamics and dynamics at the molecular level and machine learning at the big-data level. Hopefully, the guiding significance for practical applications may help to comprehensively understand the NRR process and accelerate the improvement of NRR production efficiency.