Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published December 1, 1999 | Supplemental Material
Journal Article Open

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

Abstract

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.

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.

Attached Files

Supplemental Material - ja9844074_s.pdf

Files

ja9844074_s.pdf
Files (92.8 kB)
Name Size Download all
md5:b7e6542e252dcc1802a8add9a7ba1286
92.8 kB Preview Download

Additional details

Created:
August 19, 2023
Modified:
October 18, 2023