Filling Mesopores of Conductive Metal–Organic Frameworks with Cu Clusters for Selective Nitrate Reduction to Ammonia

Abstract

The electrocatalytic nitrate reduction reaction (NO₃^-RR) to ammonia (NH₃) under ambient conditions not only has the benefit of lowering energy consumption, but also helps remove nitrate contamination. Inspired by the unique structure of nitrate/nitrite reductase with the active spheroproteins encapsulated by larger enzymes, herein, we develop an <i>in situ</i> synthetic strategy for the construction of metal cluster-conductive metal-organic framework (MOF) composite electrocatalysts. The metallic Cu clusters are filled into the mesopores of a conductive copper-based MOF (<i>i.e</i>., CuHHTP); meanwhile, CuHHTP with a porous structure provides an internal environment to limit the growth of metallic Cu clusters with an ultrasmall size (<i>i.e</i>., 1.5 ± 0.2 nm) and restrains their aggregation. The obtained Cu@CuHHTP exhibits superb performance for NO₃^-RR. In a neutral electrolyte with 500 ppm NO₃^-, Cu@CuHHTP shows a high NO₃^- conversion of 85.81% and a selectivity for NH₃ of 96.84%. ¹⁵N isotope labeling experiments confirm that the formation of NH₃ originates from the process of NO₃^-RR. Theoretical calculations confirm that Cu clusters are the active sites in the composite electrocatalysts, in which the proper d-band center and the "accept-donate" mechanism in charge transfer are the key factors for the improvement of the electrocatalytic performance.