Key role of antibonding electron transfer in bonding on solid surfaces

Yu, Liping; Yan, Qimin; Ruzsinszky, Adrienn

doi:10.1103/PhysRevMaterials.3.092801

Key role of antibonding electron transfer in bonding on solid surfaces

Journal Article · Tue Sep 24 00:00:00 EDT 2019 · Physical Review Materials

DOI:https://doi.org/10.1103/PhysRevMaterials.3.092801· OSTI ID:1608431

^[1]; Yan, Qimin; Ruzsinszky, Adrienn

Temple University

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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; SC0012575

OSTI ID:: 1608431

Alternate ID(s):: OSTI ID: 1608625

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 9 Vol. 3; ISSN PRMHAR; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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