Methanol Synthesis from CO2 Hydrogenation over a Potassium-Promoted Cux O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis

Liao, Wenjie; Liu, Ping

doi:10.1021/acscatal.9b05226

Methanol Synthesis from CO₂ Hydrogenation over a Potassium-Promoted Cu_x O/Cu(111) (x ≤ 2) Model Surface: Rationalizing the Potential of Potassium in Catalysis

Journal Article · Fri Mar 20 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b05226· OSTI ID:1608778

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State Univ. of New York (SUNY), Stony Brook, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Alkalis have been reported as a promotor in the heterogeneous catalysis, being able to enhance the activity and selectivity of catalysts. The effective utilization of alkalis in catalyst optimization requires the fundamental understanding of the underlying mechanism. In this work, we take a potassium (K)-modified Cu_xO/Cu(111) (x ≤ 2) model surface as a case study to rationalize the nature of K during the carbon dioxide hydrogenation using combined density functional theory (DFT) calculation and the kinetic Monte Carlo (KMC) simulation. Our result demonstrates the significant tuning of selectivity from carbon monoxide to methanol on going from Cu(111) to K-modified Cu_xO/Cu(111). The deposited K⁺ stabilizes the Cu_xO thin film under the reducing condition of carbon dioxide hydrogenation. More importantly, our study reveals that K⁺ acts as an active center for selective tuning in the binding, an accelerator for charge transfer, and a mediator for the electron tunneling. As a result, the K-modified Cu_xO/Cu(111) opens a methanediol [H₂C(OH)₂]-mediated formate pathway to facilitate the selective conversion of carbon dioxide to methanol. Our study develops the intrinsic rules of design to tune the catalytic performance using alkali metals.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1608778

Report Number(s):: BNL-213812-2020-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 10 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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