Understanding Methanol Synthesis on Inverse ZnO/CuOx/Cu Catalysts: Stability of CH3O Species and Dynamic Nature of the Surface

Orozco, Ivan; Huang, Erwei; Mahapatra, Mausumi; Kang, Jindong; Shi, Rui; Nemšák, Slavomír; Tong, Xiao; Senanayake, Sanjaya D.; Liu, Ping; Rodríguez, José A.

doi:10.1021/acs.jpcc.1c00392

Title: Understanding Methanol Synthesis on Inverse ZnO/CuO_x/Cu Catalysts: Stability of CH₃O Species and Dynamic Nature of the Surface

Journal Article · Fri Mar 19 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c00392· OSTI ID:1785112

Orozco, Ivan ^[1];

^[1]; Mahapatra, Mausumi ^[2]; Kang, Jindong ^[1]; Shi, Rui ^[1]; Nemšák, Slavomír ^[3]; Tong, Xiao ^[4];

^[2];

^[5];

^[5]

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)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Inverse ZnO/Cu catalysts are key systems in the conversion of CO₂, a common atmospheric pollutant, into methanol, a high-value chemical and fuel. The chemistry of methanol and methoxy groups over inverse ZnO/Cu₂O/Cu(111) catalysts was investigated employing Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS), Scanning Tunneling Microscopy (STM) and calculations based on Density Functional Theory (DFT). The results of AP-XPS show that the adsorption of methanol on the binary oxide substrate at 300 K leads to formation of *CH₃O and *HCOO species with a minor amount of *CH_x. Furthermore, most of the methoxy groups disappeared from the surface after heating to 450 K, the onset temperature for the formation of methanol during the hydrogenation of CO₂. The results of AP-XPS, STM and DFT point to preferential adsorption of methoxy on the ZnO regions of the binary oxide. On the supported ZnO or on a ZnO-Cu₂O interface, the breaking of the O-H bond in methanol is an exothermic process with a negligible (1-2 kcal/mol) or non-existent energy barrier depending on the size and shape of the ZnO islands. STM

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

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

Grant/Contract Number:: SC0012704; AC02-05CH11231; 1531492

OSTI ID:: 1785112

Report Number(s):: BNL-221535-2021-JAAM

Journal Information:: Journal of Physical Chemistry. C, Vol. 125, Issue 12; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Understanding Methanol Synthesis on Inverse ZnO/CuOx/Cu Catalysts: Stability of CH3O Species and Dynamic Nature of the Surface

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Title: Understanding Methanol Synthesis on Inverse ZnO/CuO_x/Cu Catalysts: Stability of CH₃O Species and Dynamic Nature of the Surface