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This content will become publicly available on January 6, 2017

Title: Hydrogenation of CO2 to methanol on CeOx/Cu(111) and ZnO/Cu(111) catalysts: Role of the metal-oxide interface and importance of Ce3+ sites

The role of the interface between a metal and oxide (CeOx–Cu and ZnO–Cu) is critical to the production of methanol through the hydrogenation of CO2 (CO2 + 3H2 → CH3OH + H2O). The deposition of nanoparticles of CeOx or ZnO on Cu(111), θoxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeOx/Cu(111). The apparent activation energy for the CO2 → CH3OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111) and 13 kcal/mol on CeOx/Cu(111). The surface chemistry of the highly active CeOx–Cu(111) interface was investigated using ambient pressure X-ray photoemission spectroscopy (AP-XPS) and infrared reflection absorption spectroscopy (AP-IRRAS). Both techniques point to the formation of formates (HCOO) and carboxylates (CO2δ–) during the reaction. Our results show an active state of the catalyst rich in Ce3+ sites which stabilize a CO2δ– species that is an essential intermediate for the production of methanol. Furthermore, the inverse oxide/metal configuration favors strong metal–oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.
;  [1] ;  [2] ;  [2] ;  [2] ;  [3] ;  [4] ;  [4] ;  [2] ;  [1] ;  [3]
  1. Univ. Central de Venezuela, Caracas (Venezuela)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); SUNY Stony Brook, Stony Brook, NY (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 1932-7447; R&D Project: CO009; KC0302010
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 3; Journal ID: ISSN 1932-7447
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States