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Microscopic Investigation of H2 Reduced CuOx/Cu(111) and ZnO/CuOx/Cu(111) Inverse Catalysts: STM, AP-XPS, and DFT Studies

Journal Article · · ACS Catalysis
 [1];  [1];  [2];  [1];  [2];  [3];  [3];  [4];  [4]
  1. Brookhaven National Laboratory (BNL), Upton, NY (United States)
  2. Stony Brook Univ., NY (United States)
  3. Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  4. Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
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Understanding the reduction mechanism of ZnO/CuOx interfaces by hydrogen is of great importance for advancing the performance of industrial catalysts for CO2 hydrogenation to methanol. Here, the reduction of pristine and ZnO-modified CuOx/Cu(111) by H2 was investigated using ambient pressure scanning tunnelling microscopy (AP-STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT). The morphological changes and reaction rates seen for the reduction of CuOx/Cu(111) and ZnO/CuOx/Cu(111) are very different. On CuOx/Cu(111), perfect "44" and "29" structures displayed a very low reactivity towards H2 at room temperature. A long induction period associated with an autocatalytic process was observed to enable the reduction by the removal of chemisorbed non-lattice oxygen initially and lattice oxygen sequentially at the CuOx-Cu interface, which led to formation of oxygen deficient "5-7" hex and honeycomb structures. In the final stages of the reduction process, regions of residual oxygen species and metallic Cu were seen. The addition of ZnO particles to CuOx/Cu(111) opened new reaction channels. On the ZnO sites, the dissociation of H2 was fast and H adatoms easily migrated to adjacent regions of copper oxide. This hydrogen spillover substantially enhanced the rate of oxygen removal, resulting in the rapid reduction of the copper oxide located in the periphery of the zinc oxide islands with no signs for the reduction of ZnO. The deposited ZnO completely modified the dynamics for H2 dissociation and hydrogen migration, providing an excellent source for CO2 hydrogenation processes on the inverse oxide/metal system.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
SC0012704; AC02-05CH11231
OSTI ID:
1997931
Report Number(s):
BNL--224757-2023-JAAM
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 14 Vol. 13; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (9)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 hydrogenation
H spillover
H2 activation
copper oxide
dissociation
hydrogen
inverse ZnO/Cu catalysts
morphological studies
oxides
oxygen
redox reactions
scanning tunneling microscopy
zinc oxide