Atomically Precise Integration of Multiple Functional Motifs in Catalytic Metal-Organic Frameworks for Highly Efficient Nitrate Electroreduction.

Abstract

Ammonia production plays a central role in modern industry and agriculture with a continuous surge in its demand, yet the current industrial Haber-Bosch process suffers from low energy efficiency and accounts for high carbon emissions. Direct electrochemical conversion of nitrate to ammonia therefore emerges as an appealing approach with satisfactory sustainability while reducing the environmental impact from nitrate pollution. To this end, electrocatalysts for efficient conversion of eight-electron nitrate to ammonia require collective contributions at least from high-density reactive sites, selective reaction pathways, efficient multielectron transfer, and multiproton transport processes. Here, we report a catalytic metal-organic framework (two-dimensional (2D) In-MOF In8) catalyst integrated with multiple functional motifs with atomic precision, including uniformly dispersed, high-density, single-atom catalytic sites, high proton conductivity (efficient proton transport channel), high electron conductivity (promoted by the redox-active ligands), and confined microporous environments. These eventually lead to a direct and efficient electrochemical reduction of nitrate to ammonia and record high yield rate, FE, and selectivity for NH3 production. A novel "dynamic ligand dissociation" mechanism provides an unprecedented working principle that allows for the use of a high-quality MOF crystalline structure to function as highly ordered, high-density, single-atom catalyst (SAC)-like catalytic systems and ensures the maximum utilization of the metal centers within the MOF structure. Further, the atomically precise assembly of multiple functional motifs within a MOF catalyst offers an effective and facile strategy for the future development of framework-based enzyme-mimic systems.