Copper cluster size effect in methanol synthesis from CO 2
Here, size-selected Cu n catalysts ( n = 3, 4, 20) were synthesized on Al 2O 3 thin films using mass-selected cluster deposition. A systematic study of size and support effects was carried out for CO 2 hydrogenation at atmospheric pressure using a combination of in situ grazing incidence X-ray absorption spectroscopy, catalytic activity measurement, and first-principles calculations. The catalytic activity for methanol synthesis is found to strongly vary as a function of the cluster size; the Cu 4/Al 2O 3 catalyst shows the highest turnover rate for CH 3OH production. With only one atom less than Cu 4, Cu 3 showed less than 50% activity. Density functional theory calculations predict that the activities of the gas-phase Cu clusters increase as the cluster size decreases; however, the stronger charge transfer interaction with Al 2O 3 support for Cu 3 than for Cu 4 leads to remarkably reduced binding strength between the adsorbed intermediates and supported Cu 3, which subsequently results in a less favorable energetic pathway to transform carbon dioxide to methanol.
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- Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Grant/Contract Number:
- AC02-06CH11357
- Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 19; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Research Org:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
- OSTI Identifier:
- 1372481
- Free Publicly Accessible Full Text
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Accepted Manuscript (DOE)
- Publisher's Version of Record
- https://doi.org/10.1021/acs.jpcc.7b01835