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Title: Key role of antibonding electron transfer in bonding on solid surfaces

Abstract

The description of the chemical bond between a solid surface and an atom or a molecule is the fundamental basis for understanding surface reactivity and catalysis. Despite considerable research efforts, the physics that rules the strength of such chemical bonds remains elusive, especially on semiconductor surfaces. Widespread understandings are mostly based on the degree of filling of antibonding surface-adsorbate states that weaken the surface adsorption. The unoccupied antibonding surface-adsorbate states are often considered to have no effects on surface bonding. Here in this paper, we show that the energy levels of unoccupied antibonding surface-adsorbate states relative to the Fermi-level play a critical role in determining the trends in variations of surface adsorption energies. The electrons that would occupy those high-energy antibonding states are transferred to the Fermi-level, leading to an energy gain that largely controls surface bonding. To illustrate this picture, as a validating case, we study the hydrogen evolution reaction (HER) catalyzed by MoS2 from density functional theory calculations. We find that the majority of antibonding surface-hydrogen states are positioned well above the Fermi-energy. A clear linear relationship between the energy gain from antibonding electron transfer and the adsorption energy is identified for hydrogen binds to either molybdenum ormore » sulfur atoms at different sites. The antibonding-electron transfer energy can thus serve as a primary catalytic activity descriptor. The emerging picture identifies the origin of HER on MoS2, which is related to the empty in-gap states induced by sulfur vacancies or edges. Under this picture, the effects of surface inhomogeneity (e.g., defects, step edges) on surface bonding strength can be understood. This antibonding electron transfer picture also offers a physically different explanation for the well-known d-band theory for hydrogen adsorption on transition metal surfaces. The results provide guidelines for understanding and optimizing catalyst performance and designing new solid catalysts.« less

Authors:
ORCiD logo [1];  [2];  [2]
  1. Temple Univ., Philadelphia, PA (United States); Univ. of Maine, Orono, ME (United States)
  2. Temple Univ., Philadelphia, PA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1608625
Alternate Identifier(s):
OSTI ID: 1608431
Grant/Contract Number:  
SC0012575; AC02-05CH11231; CNS- 09-58854
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 9; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Yu, Liping, Yan, Qimin, and Ruzsinszky, Adrienn. Key role of antibonding electron transfer in bonding on solid surfaces. United States: N. p., 2019. Web. https://doi.org/10.1103/PhysRevMaterials.3.092801.
Yu, Liping, Yan, Qimin, & Ruzsinszky, Adrienn. Key role of antibonding electron transfer in bonding on solid surfaces. United States. https://doi.org/10.1103/PhysRevMaterials.3.092801
Yu, Liping, Yan, Qimin, and Ruzsinszky, Adrienn. Tue . "Key role of antibonding electron transfer in bonding on solid surfaces". United States. https://doi.org/10.1103/PhysRevMaterials.3.092801. https://www.osti.gov/servlets/purl/1608625.
@article{osti_1608625,
title = {Key role of antibonding electron transfer in bonding on solid surfaces},
author = {Yu, Liping and Yan, Qimin and Ruzsinszky, Adrienn},
abstractNote = {The description of the chemical bond between a solid surface and an atom or a molecule is the fundamental basis for understanding surface reactivity and catalysis. Despite considerable research efforts, the physics that rules the strength of such chemical bonds remains elusive, especially on semiconductor surfaces. Widespread understandings are mostly based on the degree of filling of antibonding surface-adsorbate states that weaken the surface adsorption. The unoccupied antibonding surface-adsorbate states are often considered to have no effects on surface bonding. Here in this paper, we show that the energy levels of unoccupied antibonding surface-adsorbate states relative to the Fermi-level play a critical role in determining the trends in variations of surface adsorption energies. The electrons that would occupy those high-energy antibonding states are transferred to the Fermi-level, leading to an energy gain that largely controls surface bonding. To illustrate this picture, as a validating case, we study the hydrogen evolution reaction (HER) catalyzed by MoS2 from density functional theory calculations. We find that the majority of antibonding surface-hydrogen states are positioned well above the Fermi-energy. A clear linear relationship between the energy gain from antibonding electron transfer and the adsorption energy is identified for hydrogen binds to either molybdenum or sulfur atoms at different sites. The antibonding-electron transfer energy can thus serve as a primary catalytic activity descriptor. The emerging picture identifies the origin of HER on MoS2, which is related to the empty in-gap states induced by sulfur vacancies or edges. Under this picture, the effects of surface inhomogeneity (e.g., defects, step edges) on surface bonding strength can be understood. This antibonding electron transfer picture also offers a physically different explanation for the well-known d-band theory for hydrogen adsorption on transition metal surfaces. The results provide guidelines for understanding and optimizing catalyst performance and designing new solid catalysts.},
doi = {10.1103/PhysRevMaterials.3.092801},
journal = {Physical Review Materials},
number = 9,
volume = 3,
place = {United States},
year = {2019},
month = {9}
}

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