In Situ Studies of Methanol Decomposition Over Cu(111) and Cu2O/Cu(111): Effects of Reactant Pressure, Surface Morphology, and Hot Spots of Active Sites

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

doi:10.1021/acs.jpcc.0c09572

In Situ Studies of Methanol Decomposition Over Cu(111) and Cu2O/Cu(111): Effects of Reactant Pressure, Surface Morphology, and Hot Spots of Active Sites

Journal Article · Thu Dec 24 00:00:00 EST 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c09572· OSTI ID:1755148

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

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)

The dissociative adsorption of methanol was investigated on Cu(111) and ultrathin Cu₂O films. We employed synchrotron-based Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Scanning Tunneling Microscopy (STM) to study the dynamics of gas–solid interactions, and calculations based on Density Functional Theory (DFT) were used to examine the reaction path. C 1s XPS spectra revealed that methanol underwent dissociative adsorption on plain Cu(111) to form methoxy (CH₃O), formaldehyde (H₂CO), and formate (HCOO) at a pressure range of 0.5–10 mTorr, with these species remaining on the surface after evacuation. This was accompanied by the appearance of a low coverage (~0.05 ML) of O_ads in the O 1s which can be considered a highly active site for methanol activation. The high activity is apparent by a coverage of 0.8 ML of methoxy at room temperature. STM was unable to image these species at room temperature as they were highly mobile on metallic copper. In contrast, for CH₃OH on Cu₂O/Cu(111), STM showed clear hot spots for reaction and a complex array of adsorption structures. On the oxide substrate, there was decomposition of methanol to H₂CO, CH₃O, HCOO, and hydrocarbon species (CH_x) due to the subsequent interactions of methanol with lattice oxygen. Cu(111) remained entirely saturated with decomposition products under 10 mTorr of methanol (θ ≈ 0.97 ML), whereas the Cu₂O overlayer was saturated at a much lower coverage (θ ≈ 0.30 ML). STM revealed rows and step edges of Cu₂O decorated with decomposition products and metallic Cu islands ~5 nm in size. The difference in activity between Cu(111) and Cu₂O/Cu(111) is attributed to the significant amount of O present on the oxide surface. Additionally, Density Functional theory (DFT) calculations described the XPS measurements well, showing a likely methanol dissociation to *CH₃O and therefore a surface reduction. More importantly, the DFT results revealed that it was the chemisorbed oxygen on Cu₂O/Cu(111) which oxidized the dissociated *CH₃O to *HCOO and eventually CO₂, while the reaction only involving upper oxygen on the Cu₂O hexagonal ring led to the formation of H₂CO.

View Accepted Manuscript (DOE)

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

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

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

OSTI ID:: 1755148

Report Number(s):: BNL--220753-2020-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 1 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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