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The pH effect and the H/D kinetic isotope effect (KIE) for the oxidation of formic acid/formate anions (FOR) on Pt(111) have been studied. The pH-dependent FOR activity displays a volcano shape with a maximum at a pH close to the pKa of HCOOH. The H/D KIE factors for HCOOH/DCOOH or HCOO−/DCOO− are ca. 5, 2, and 1 in solutions with pH=1.1, 3.6, and 13, respectively. These findings reveal that HCOOH→rdsCOOad−+2H++e...
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