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Oxidation of Methanol on 2nd and 3rd Row Group VIII Transition Metals (Pt, Ir, Os, Pd, Rh, and Ru): Application to Direct Methanol Fuel Cells

Kua, Jeremy and Goddard, William A., III (1999) Oxidation of Methanol on 2nd and 3rd Row Group VIII Transition Metals (Pt, Ir, Os, Pd, Rh, and Ru): Application to Direct Methanol Fuel Cells. Journal of the American Chemical Society, 121 (47). pp. 10928-10941. ISSN 0002-7863. doi:10.1021/ja9844074.

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Using first principles quantum mechanics [nonlocal density functional theory (B3LYP)], we calculated the 13 most likely intermediate species for methanol oxidation on clusters of all 2nd and 3rd row Group VIII transition metals for all three likely binding sites (top, bridge, and cap). This comprehensive set of binding energies and structures allows a detailed analysis of possible reaction mechanisms and how they change for different metals. This illustrates the role in which modern quantum chemical methods can be used to provide data for combinatorial strategies for discovering and designing new catalysts. We find that methanol dehydrogenation is most facile on Pt, with the hydrogens preferentially stripped off the carbon end. However, water dehydrogenation is most facile on Ru. These results support the bifunctional mechanism for methanol oxidation on Pt−Ru alloys in direct methanol fuel cells (DMFCs). We find that pure Os is capable of performing both functionalities without cocatalyst. We suggest that pure Os be examined as a potential catalyst for low overpotential, highly dispersed catalyst DMFCs. Pathways to form the second C−O bond differ between the pure metals (Pt and Os) in which (CO)_(ads) is probably activated by (OH)_(ads) and the Pt−Ru binary system in which (COH)_(ads) is probably activated by O_(ads). For all cases we find that formation of (COOH)_(ads) is an important precursor to the final dehydrogenation to desorb CO_2 from the surface.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 1999 American Chemical Society. Received December 22, 1998. Revised Manuscript Received September 24, 1999. We thank Professor Eugene Smotkin for helpful comments. This research was initiated with funding from NSF (CHE 95-22179) and continued with funding from ARO (in collaboration with Illinois Institute of Technology and Schrodinger Inc.). The facilities of the MSC are also supported by grants from DOE-ASCI, ARO/DURIP, ARO/MURI, BP Chemical, Beckman Institute, Seiko-Epson, Exxon, Owens-Corning, Avery-Dennison, Asahi Chemical, Chevron Petroleum Technology Co., Chevron Chemical Co., Chevron Research, and Technology Corp.
Funding AgencyGrant Number
NSFCHE 95-22179
Army Research Office (ARO)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Chevron Petroleum Technology Co.UNSPECIFIED
Chevron Chemical Co.UNSPECIFIED
Chevron Research and Technology Co.UNSPECIFIED
Issue or Number:47
Record Number:CaltechAUTHORS:20180413-135159498
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Official Citation:Oxidation of Methanol on 2nd and 3rd Row Group VIII Transition Metals (Pt, Ir, Os, Pd, Rh, and Ru):  Application to Direct Methanol Fuel Cells Jeremy Kua and William A. Goddard III Journal of the American Chemical Society 1999 121 (47), 10928-10941 DOI: 10.1021/ja9844074
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85843
Deposited By: George Porter
Deposited On:13 Apr 2018 21:00
Last Modified:15 Nov 2021 20:32

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