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Free keywords:
Hydrogen purification; Fuel cell; Preferential CO oxidation; PROX; Palladium; Palladium-hydride; Pd/CeO2; Ceria; High pressure XPS; In situ DRIFT; TDS; HRTEM
CO removal for fuel cell applications
Abstract:
The aim of the PROX reaction is to reduce the CO content of hydrogen feed to proton-exchange membrane fuel cells (PEMFCs) by selective oxidation of CO in the presence of excess hydrogen. Both Pt and Pd on ceria are active in CO oxidation (without hydrogen), whereas Pd is poorly active in the presence of hydrogen. In this paper we explore the reasons for such behavior, using the same techniques for Pd/CeO2 as used for Pt/CeO2 in Part I: catalytic tests, in situ DRIFTS, high-pressure XPS, HRTEM, and TDS. We also examine the reaction mechanism of CO oxidation (without hydrogen), which does not occur via exactly the same mechanism on Pt and Pd/CeO2 catalysts. In the presence of hydrogen (PROX) at low temperature (T = 350–380 K), the formation of Pd β-hydride was confirmed by high-pressure in situ XPS. Its formation greatly suppressed the possibility of CO oxidation, because oxygen both from gas-phase and support sites reacted rapidly with hydride H to form water,
which readily desorbed from Pd. Nevertheless, CO adsorption was not hampered here. These entities transformed mainly to surface formate and formyl (–CHO) species instead of oxidation as observed by DRIFTS. The participation of a low-temperature water–gas shift type reaction proposed for the platinum system (see Part I) was hindered. Increasing temperature led to decomposition of the hydride phase and a parallel increase in the selectivity toward CO oxidation. This still remained lower on Pd/CeO2 than on Pt/CeO2, however.
