Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites

作者：Eamonn Murphy, Yuanchao Liu, Ivana Matanović, Martina Rüscher, Ying Huang, Alvin Ly, Shengyuan Guo, Wenjie Zang, Xingxu Yan, Andrea Martini, Janis Timoshenko, Beatriz Roldán Cuenya, Iryna V. Zenyuk, Xiaoqing Pan, Erik David Spoerke, Plamen Atanassov · 发表于：Nature Communications · 年份：2023 · DOI：10.1038/s41467-023-40174-4 · 被引用次数：279 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Advanced Photocatalysis Techniques、Caching and Content Delivery

Abstract Electrocatalytic reduction of waste nitrates (NO 3 − ) enables the synthesis of ammonia (NH 3 ) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate a high catalytic activity and uniquely favor mono-nitrogen products. However, the reaction fundamentals remain largely underexplored. Herein, we report a set of 14; 3 d -, 4 d -, 5 d - and f -block M-N-C catalysts. The selectivity and activity of NO 3 − reduction to NH 3 in neutral media, with a specific focus on deciphering the role of the NO 2 − intermediate in the reaction cascade, reveals strong correlations (R=0.9) between the NO 2 − reduction activity and NO 3 − reduction selectivity for NH 3 . Moreover, theoretical computations reveal the associative/dissociative adsorption pathways for NO 2 − evolution, over the normal M-N 4 sites and their oxo-form (O-M-N 4 ) for oxyphilic metals. This work provides a platform for designing multi-element NO 3 RR cascades with single-atom sites or their hybridization with extended catalytic surfaces.