Highly Selective Methane to Methanol Conversion on Inverse SnO2/Cu2O/Cu(111) Catalysts: Unique Properties of SnO2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

Huang, Erwei; Rui, Ning; Rosales, Rina; Kang, Jindong; Nemšák, Slavomir; Senanayake, Sanjaya D.; Rodriguez, José A.; Liu, Ping

doi:10.1021/acscatal.2c03060

Title: Highly Selective Methane to Methanol Conversion on Inverse SnO₂/Cu₂O/Cu(111) Catalysts: Unique Properties of SnO₂ Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

Journal Article · 01 September 2022 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.2c03060 · OSTI ID:1897497

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^[2]; Rosales, Rina ^[1]; Kang, Jindong ^[1]; Nemšák, Slavomir ^[3];

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Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Direct methane to methanol (CH₄ → CH₃OH) conversion in heterogeneous catalysis has been a long-standing challenge due to the difficulties in equalizing the activation of methane and protection of the methanol product at the same reaction conditions. Here, we report an inverse catalyst, consisting of small structures of SnO₂ (0.5-1 nm in size) dispersed on Cu₂O/Cu(111), for highly selective CH₃OH production from CH₄. This system was investigated by combining theoretical [density functional theory calculations (DFT), kinetic Monte Carlo simulations (KMC)] and experimental methods [scanning tunneling microscopy (STM), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS)]. The DFT and AP-XPS studies showed that on SnO₂/Cu₂O/Cu(111) the conversion of CH₄ by oxygen (O₂) preferred complete combustion to carbon dioxide (CO₂). The addition of water (H₂O) enhanced the production of CH₃OH to nearly 100% selectivity in KMC simulations. This trend was consistent with results of AP-XPS. The presence of water in the reaction environment rendered an extremely high amount of methoxy species (*CH₃O), a precursor for CH₃OH production. Further, the high CH₃OH selectivity of SnO₂/Cu₂O/Cu(111) reflected the unique atomic and electronic structure of the supported SnO₂ nanoparticles. As a result, the O₂ adsorption and dissociation, and thus the full combustion of CH₄ to CO₂, was completely suppressed; while the H₂O dissociative adsorption was still feasible, providing active hydroxyl species for a truly selective CH₄ to CH₃OH conversion.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 1897497

Report Number(s):: BNL-223669-2022-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 18 Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Highly Selective Methane to Methanol Conversion on Inverse SnO2/Cu2O/Cu(111) Catalysts: Unique Properties of SnO2 Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane

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Title: Highly Selective Methane to Methanol Conversion on Inverse SnO₂/Cu₂O/Cu(111) Catalysts: Unique Properties of SnO₂ Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane