Title: Atomic Structure and Dynamics of Single Platinum Atom Interactions with Monolayer MoS₂

Abstract

In this work, we have studied atomic level interactions between single Pt atoms and the surface of monolayer MoS₂ using aberration-corrected annular dark field scanning transmission electron microscopy at an accelerating voltage of 60 kV. Strong contrast from single Pt atoms on the atomically resolved monolayer MoS₂ lattice enables their exact position to be determined with respect to the MoS2 lattice, revealing stable binding sites. In regions of MoS₂ free from surface contamination, the Pt atoms are localized in S vacancy sites and exhibit dynamic hopping to nearby vacancy sites driven by the energy supplied by the electron beam. However, in areas of MoS₂ contaminated with carbon surface layers, the Pt atoms appear at various positions with respect to the underlying MoS₂ lattice, including on top of Mo and in off-axis positions. These variations are due to the Pt bonding with the surrounding amorphous carbon layer, which disrupts the intrinsic Pt–MoS₂ interactions, leading to more varied positions. Density functional theory (DFT) calculations reveal that Pt atoms on the surface of MoS₂ have a small barrier for migration and are stabilized when bound to either a single or double sulfur vacancies. DFT calculations have been used to understand how the catalyticmore » activity of the MoS₂ basal plane for hydrogen evolution reaction is influenced by Pt dopants by variation of the hydrogen adsorption free energy. Finally, this strong dependence of catalytic effect on interfacial configurations is shown to be common for a series of dopants, which may provide a means to create and optimize reaction centers.« less

Authors:

Li, Huashan  ^[1];

• Search DOE PAGES for author "Li, Huashan"
• Search DOE PAGES for ORCID "0000-0002-3439-3864"

Wang, Shanshan  ^[2];

• Search DOE PAGES for author "Wang, Shanshan"
• Search DOE PAGES for ORCID "0000-0003-3750-6737"

Sawada, Hidetake ^[3]; Han, Grace G. D. ^[1]; Samuels, Thomas ^[2]; Allen, Christopher S. ^[4]; Kirkland, Angus I. ^[4]; Grossman, Jeffrey C. ^[1]; Warner, Jamie H.  ^[2]

• Search DOE PAGES for author "Warner, Jamie H."
• Search DOE PAGES for ORCID "0000-0002-1271-2019"

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+ Show Author Affiliations

1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
2. Univ. of Oxford (United Kingdom)
3. Univ. of Oxford (United Kingdom); JEOL Ltd., Akishima, Tokyo (Japan); Diamond Light Source Ltd, Didcot, Oxfordshire (United Kingdom)
4. Univ. of Oxford (United Kingdom); Diamond Light Source Ltd, Didcot, Oxfordshire (United Kingdom)

Publication Date:

Fri Mar 03 00:00:00 EST 2017

Research Org.:

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:

USDOE Office of Science (SC)

OSTI Identifier:

1487447

Grant/Contract Number:  

AC02-05CH11231

Resource Type:

Accepted Manuscript

Journal Name:

ACS Nano

Additional Journal Information:

Journal Volume: 11; Journal Issue: 3; Journal ID: ISSN 1936-0851

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Pt dopants; MoS2; ADF-STEM; 2D materials; catalysts; dopants