A Physical Model for Understanding the Activation of MoS 2 Basal‐Plane Sulfur Atoms for the Hydrogen Evolution Reaction

Liu, Mingjie; Hybertsen, Mark S.; Wu, Qin

doi:10.1002/anie.202003091

Title: A Physical Model for Understanding the Activation of MoS ₂ Basal‐Plane Sulfur Atoms for the Hydrogen Evolution Reaction

Journal Article · 14 June 2020 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202003091 · OSTI ID:1633381

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Center for Functional Nanomaterials Brookhaven National Laboratory Upton NY 11973 USA

Abstract Weak binding of hydrogen atoms to the 2H‐MoS ₂ basal plane renders MoS ₂ inert as an electrocatalyst for the hydrogen evolution reaction. Transition‐metal doping can activate neighboring sulfur atoms in the MoS ₂ basal plane to bind hydrogen more strongly. Our theoretical studies show strong variation in the degree of activation by dopants across the 3d transition‐metal series. To understand the trends in activation, we propose a model based on the electronic promotion energy required to partially open the full valence shell of a local S atom and therefore enable it to bond with a H atom. In general, the promotion is achieved through an electron transfer from the S to neighboring metal‐atom sites. Furthermore, we demonstrate a specific, electronic‐structure‐based descriptor for the hydrogen‐binding strength: Δ _dp , the local interband energy separation between the lowest empty d‐states on the dopant metal atoms and occupied p‐states on S. This model can be used to provide guidelines for chalcogen activation in future catalyst design based on doped transition‐metal dichalcogenides.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0012704

OSTI ID:: 1633381

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 35 Vol. 59; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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