Rui Yu, Zhaorui Liu, Dominik Legut, Junwei Sun, Qianfan Zhang, Joseph S. Francisco and Ruifeng Zhang*,
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Highly Efficient and Selective Nitrogen Reduction Reaction Catalysis of Cluster-Modified MXene Nanosheets
The electrocatalytic synthesis of NH3 holds immense significance for energy conservation in industrial and agricultural production. Herein, an efficient solution is proposed for MXene-based high-activity nitrogen reduction reaction (NRR) catalysts that are modified using tetranuclear non-noble 3d transition metal clusters (M4). The thorough exploration of M4/Ti2CO2 candidates reveals that the thermodynamically and kinetically stable Cr4/Ti2CO2 possesses the lowest overpotential (0.35 V) and high selectivity, comparable to those of well-known NRR catalysts such as Ru(0001) (0.43 V) and Au(310) (1.91 V). In addition, the doping of Fe into Cr4 clusters can further reduce the overpotential and kinetic barriers by 31 and 46%, respectively. The analysis of the complicated bonding nature reveals the mechanism of the catalytic activity, which demonstrates the role of clusters pulling π/σ electrons from N2 while simultaneously back-donating d orbital electrons to the π* orbital. A descriptor (φ), related to intrinsic transferred charges (Δe) of the cluster, is proposed to accurately determine the NRR catalytic activity using simple calculations, and the linear correlation between them can reach 0.98. This work provides guidance for designing promising cluster-modified MXene catalysts for NRR and an elucidation of the electronic factors governing catalytic activity.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.