Activating Basal Planes in Transition Metal Dichalcogenides for CO2 Reduction to CO through Alloying
Abstract
Transition metal dichalcogenides (TMDCs) have emerged as highly tunable platforms for electrocatalysis, particularly for the CO2 reduction reaction (CO2RR). While TMDC edge sites exhibit catalytic activity, the basal plane is typically inert, severely limiting the overall active site density. In this work, we show that sulfur vacancies activate the basal plane of 1H-TMDCs, while concurrent solid-solution alloying provides a mechanism to broadly tune intermediate adsorption energies. We evaluate a library of quasi-binary TMDC sulfide alloys comprising V, Nb, Ta, Mo, and W, screening them by stability, defect energetics, and competitive selectivity to identify the most effective catalysts for CO2RR. Electronic-structure analysis reveals that a d-band center closer to the Fermi energy weakens intermediate binding by leaving key bonding states unoccupied above the Fermi energy. Our calculations identify (Nb,Ta)S2 as a promising catalyst with low sulfur vacancy formation energies, near-optimal CO2RR intermediate binding, and selectivity against the hydrogen evolution reaction. Overall, this work establishes a rational design framework for TMDC alloy catalysts through the simultaneous use of defect engineering and alloying.
Related
- Photogalvanic effect in monolayers of transition metal dichalcogenides
- Higher order anharmonicity and polymorphism in the lattice thermal conductivity of transition metal dichalcogenides
- Interplay of Excitonic Charge Density Wave and Superconductivity in Transition Metal Dichalcogenides
- Ab initio exploration of hydrogen-intercalated transition metal dichalcogenides: From identifying stable structures to emergent superconductivity
- Density Functional Theory for 2D Transition-Metal Dichalcogenides with Extended Hubbard Parameters
BibTeX
@misc{montufarmorales2026activating,
title = {{Activating Basal Planes in Transition Metal Dichalcogenides for CO2 Reduction to CO through Alloying}},
author = {Eric Montufar-Morales and Daniel Rinder and Pravan Omprakash and Rohan Mishra and Gwan Yeong Jung},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.30432},
eprint = {2609.30432},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.30432},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Activating Basal Planes in Transition Metal Dichalcogenides for CO2 Reduction to CO through Alloying
AU - Eric Montufar-Morales
AU - Daniel Rinder
AU - Pravan Omprakash
AU - Rohan Mishra
AU - Gwan Yeong Jung
PY - 2026
DA - 2026/09/24
PB - arXiv
DO - 10.48550/arxiv.2609.30432
UR - https://arxiv.org/abs/2609.30432
AB - Transition metal dichalcogenides (TMDCs) have emerged as highly tunable platforms for electrocatalysis, particularly for the CO2 reduction reaction (CO2RR). While TMDC edge sites exhibit catalytic activity, the basal plane is typically inert, severely limiting the overall active site density. In this work, we show that sulfur vacancies activate the basal plane of 1H-TMDCs, while concurrent solid-solution alloying provides a mechanism to broadly tune intermediate adsorption energies. We evaluate a library of quasi-binary TMDC sulfide alloys comprising V, Nb, Ta, Mo, and W, screening them by stability, defect energetics, and competitive selectivity to identify the most effective catalysts for CO2RR. Electronic-structure analysis reveals that a d-band center closer to the Fermi energy weakens intermediate binding by leaving key bonding states unoccupied above the Fermi energy. Our calculations identify (Nb,Ta)S2 as a promising catalyst with low sulfur vacancy formation energies, near-optimal CO2RR intermediate binding, and selectivity against the hydrogen evolution reaction. Overall, this work establishes a rational design framework for TMDC alloy catalysts through the simultaneous use of defect engineering and alloying.
ER -