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The stability of surface formates generated by reaction of bridging OH groups with CO is an important first criterion supporting the idea that the rate limiting step of WGS involves formate decomposition. The second important factor is that, in the presence of water, shown directly by the measurements obtained during this steady state isotope switching study, the forward decomposition of surface formates to CO 2 and H 2 is strongly auto-catalyzed by H 2 O, in agreement with the findings of Shido and Iwasawa. Based on a normal kinetic isotope effect previously observed with H 2 O:D 2 O switching and the response of surface formate coverages to the WGS rate under steady state conditions when a high H 2 O:CO ratio is employed, the conclusion is drawn that a surface formate mechanism is likely operating for the low temperature water gas shift reaction.

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