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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

Abstract

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. The inverse oxide/metal configuration favors strong metal-oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.

Authors:
 [1];  [2];  [1];  [1];  [1];  [3];  [4];  [4];  [1];  [2];  [5]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
  2. Central Univ. of Venezuela, Caracas (Venezuela). Faculty of Science
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept. ; SUNY Stony Brook, Stony Brook, NY (United States). Dept. of Chemistry
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Brookhaven National Lab. (BNL). Chemistry Dept. , Upton, NY (United States); SUNY Stony Brook, Stony Brook, NY (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1246804
Alternate Identifier(s):
OSTI ID: 1456931
Report Number(s):
BNL-111983-2016-JA
Journal ID: ISSN 1932-7447; R&D Project: CO009; KC0302010
Grant/Contract Number:  
SC00112704; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 3; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Senanayake, Sanjaya D., Ramirez, Pedro J., Waluyo, Iradwikanari, Kundu, Shankhamala, Mudiyanselage, Kumudu, Liu, Zongyuan, Liu, Zhi, Axnanda, Stephanus, Stacchiola, Dario J., Evans, Jaime, and Rodriguez, Jose A. 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. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.jpcc.5b12012.
Senanayake, Sanjaya D., Ramirez, Pedro J., Waluyo, Iradwikanari, Kundu, Shankhamala, Mudiyanselage, Kumudu, Liu, Zongyuan, Liu, Zhi, Axnanda, Stephanus, Stacchiola, Dario J., Evans, Jaime, & Rodriguez, Jose A. 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. United States. https://doi.org/10.1021/acs.jpcc.5b12012
Senanayake, Sanjaya D., Ramirez, Pedro J., Waluyo, Iradwikanari, Kundu, Shankhamala, Mudiyanselage, Kumudu, Liu, Zongyuan, Liu, Zhi, Axnanda, Stephanus, Stacchiola, Dario J., Evans, Jaime, and Rodriguez, Jose A. Wed . "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". United States. https://doi.org/10.1021/acs.jpcc.5b12012. https://www.osti.gov/servlets/purl/1246804.
@article{osti_1246804,
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},
author = {Senanayake, Sanjaya D. and Ramirez, Pedro J. and Waluyo, Iradwikanari and Kundu, Shankhamala and Mudiyanselage, Kumudu and Liu, Zongyuan and Liu, Zhi and Axnanda, Stephanus and Stacchiola, Dario J. and Evans, Jaime and Rodriguez, Jose A.},
abstractNote = {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. The inverse oxide/metal configuration favors strong metal-oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.},
doi = {10.1021/acs.jpcc.5b12012},
journal = {Journal of Physical Chemistry. C},
number = 3,
volume = 120,
place = {United States},
year = {2016},
month = {1}
}

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