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

作者：Xiaojuan Zhu, Haicai Huang, Huaifang Zhang, Yu Zhang, Peidong Shi, Kaiyu Qu, Shi‐Bo Cheng, An‐Liang Wang, Qipeng Lu · 发表于：ACS Applied Materials & Interfaces · 年份：2022 · DOI：10.1021/acsami.2c09241 · 被引用次数：86 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Advanced Photocatalysis Techniques、Metal-Organic Frameworks: Synthesis and Applications

The electrocatalytic nitrate reduction reaction (NO 3 – RR) to ammonia (NH 3 ) 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 in situ 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.e ., CuHHTP); meanwhile, CuHHTP with a porous structure provides an internal environment to limit the growth of metallic Cu clusters with an ultrasmall size ( i.e ., 1.5 ± 0.2 nm) and restrains their aggregation. The obtained Cu@CuHHTP exhibits superb performance for NO 3 – RR. In a neutral electrolyte with 500 ppm NO 3 –, Cu@CuHHTP shows a high NO 3 – conversion of 85.81% and a selectivity for NH 3 of 96.84%. 15 N isotope labeling experiments confirm that the formation of NH 3 originates from the process of NO 3 – 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.