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Title: Low Temperature Water-Gas Shift: Type and Loading of Metal Impacts Decomposition and Hydrogen Exchange Rates of Pseudo-stabilized Formate over Metal/ceria Catalysts

Journal Article · · Appl. Catal. A

In this investigation, a similar degree of surface shell reduction among a series of metal promoted ceria catalysts was established by diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) and X-ray absorption near-edge spectroscopy (XANES) measurements. Surface formate species were generated by reaction of CO with bridging OH groups associated with the Ce{sup 3+} defect sites. The thermal decomposition of the pseudo-stable formates was followed in the absence of H2O. Decomposition and exchange from H to D of the pseudo-stabilized formate was enhanced by changing the promoter from Au to Pt. Likewise, an increase was observed in both decomposition and exchange rates by increasing the promoter loading from 0.5 to 2.5 wt.%. The results suggest that C{single_bond}H bond breaking is facilitated during this thermal decomposition (i.e., reverse decomposition to CO and {single_bond}OH). Therefore, since the rate limiting step of the forward formate decomposition (i.e., the WGS reaction) is strongly suggested to be associated with C{single_bond}H bond cleaving in the formate intermediate (based on earlier kinetic isotope effect and isotopic tracer studies), the results can explain the promotion in the WGS rates as observed by changing from Au to Pt and by increased promoter loading.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
Sponsoring Organization:
Doe - Office Of Science
DOE Contract Number:
DE-AC02-98CH10886
OSTI ID:
914193
Report Number(s):
BNL-78761-2007-JA; ACAGE4; TRN: US200804%%588
Journal Information:
Appl. Catal. A, Vol. 302; ISSN 0926-860X
Country of Publication:
United States
Language:
English