Optimizing hydrogen evolution reaction: Computational screening of single metal atom impurities in 2D MXene Nb₄C₃O₂

Abstract

MXenes, a novel class of 2D transition metal carbides and nitrides, have recently emerged as a promising candidate in the quest for efficient catalysts for the hydrogen evolution reaction. To enhance the performance of 2D MXenes with modest or poor catalytic efficiency, a particularly prosperous strategy involves doping with transition and noble metal atoms. Taking the Nb₄C₃O₂ monolayer as a model, we explore substitutional metallic impurities, which serve as single-atom catalysts embedded within the Nb₄C₃O₂ surface. Our findings demonstrate the ability to finely tune the atomic H binding energy within a 0.6 eV range, showing the potential for precise control in catalytic applications. Across different transition and noble metals, the single atoms integrated into Nb₄C₃O₂ effectively adjust the free energy of H adsorption at nearby O atoms, achieving values comparable to or superior to Pt catalysts. A comprehensive examination of the electronic properties around the impurities reveals a correlation between changes in local reactivity and charge transfer to neighboring O atoms, where H atoms bind.

Graphical abstract

Keywords

hydrogen evolution reaction / MXenes / DFT / single-atom catalysts

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Acknowledgements

This work has been supported by the Serbian Academy of Sciences and Arts under Grant No. F-18. We thank the Advanced Scientific Computing Center of the Texas A&M University at Qatar for providing us access to the RAAD supercomputer.

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