Folic Acid Self-Assembly Enabling Manganese Single-Atom Electrocatalyst for Selective Nitrogen Reduction to Ammonia

HighlightsA manganese single-atom catalyst is developed via a facile folic acid self-assembly strategy.The catalyst exhibits outstanding activity and selectivity for electrochemical reduction of nitrogen to ammonia (NRR).Electrocatalytic mechanism of Mn-N3 site for NRR is unveiled by a combination of experimental and computational study. AbstractEfficient and robust single-atom catalysts (SACs) based on cheap and earth-abundant elements are highly desirable for electrochemical reduction of nitrogen to ammonia (NRR) under ambient conditions. Herein, for the first time, a Mn-N-C SAC consisting of isolated manganese atomic sites on ultrathin carbon nanosheets is developed via a template-free folic acid self-assembly strategy. The spontaneous molecular partial dissociation enables a facile fabrication process without being plagued by metal atom aggregation. Thanks to well-exposed atomic Mn active sites anchored on two-dimensional conductive carbon matrix, the catalyst exhibits excellent activity for NRR with high activity and selectivity, achieving a high Faradaic efficiency of 32.02% for ammonia synthesis at -0.45 V versus reversible hydrogen electrode. Density functional theory calculations unveil the crucial role of atomic Mn sites in promoting N-2 adsorption, activation and selective reduction to NH3 by the distal mechanism. This work provides a simple synthesis process for Mn-N-C SAC and a good platform for understanding the structure-activity relationship of atomic Mn sites.

Automated summary

A manganese single-atom catalyst was developed using a simple folic acid self-assembly strategy, showing outstanding activity and selectivity for electrochemical nitrogen reduction to produce ammonia. Experimental and computational study revealed the electrocatalytic mechanism of the Mn-N3 site for the nitrogen reduction process.