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Title: Wet Chemical Growth and Thermocatalytic Activity of Cu-Based Nanoparticles Supported on TiO2 Nanoparticles/HOPG: In Situ Ambient Pressure XPS Study of the CO2 Hydrogenation Reaction

Journal Article · · ACS Catalysis
ORCiD logo [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Irvine, CA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
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The present study examines the synthesis of unique Cu nanostructured model catalysts and their catalytic activity toward CO2 hydrogenation under moderate temperature and pressure reaction conditions. Cu-based nanoparticles (NPs) were synthesized by two chemical deposition methods: (1) 5 nm spherical Cu(OH)2 NPs deposited on highly oriented pyrolytic graphite (HOPG) by exposing the HOPG substrate to a colloidal solution of copper, and (2) photocatalytic reduction of [Cu(H2O)6]2+ onto a high density of 15 nm TiO2 NPs grown on HOPG by physical vapor deposition. This photocatalytic reduction results in the deposition of mixed Cu(OH)2 and Cu2O films, while few-nm sized Cu-based NPs are formed on the TiO2 NPs upon subsequent reduction. The chemistry, structure, and morphology of the resulting samples were characterized using X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The thermocatalytic activity for the CO2 reduction reaction (CO2RR) under H2 was evaluated with synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and temperature-programmed desorption (TPD) experiments. Several intermediates, including CO2δ–, HCOO, O–CH3, CO32–, CHx, and CO, were observed using AP-XPS. The TiO2 NPs show activity toward the formation of methanol (CH3OH) that occurs mainly through an O–CH3 intermediate. The TiO2 NPs-core–carbon-shell (TiO2@C NPs) shows a clear selectivity toward methane (CH4).

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1569558
Report Number(s):
BNL-212139-2019-JAAM
Journal Information:
ACS Catalysis, Vol. 9, Issue 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 56 works
Citation information provided by
Web of Science

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Cited By (1)

Oriented assembly of copper metal–organic framework membranes as tandem catalysts to enhance C–H hydroxyalkynylation reactions with regiocontrol journal January 2020

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