Identification of reaction intermediates in the decomposition of formic acid on Pd†

Uncovering the role of reaction intermediates is crucial to developing an understanding of heterogeneous catalysis because catalytic reactions often involve complex networks of elementary steps. Identifying the reaction intermediates is often difficult because their short lifetimes and low concentrations make it difficult to observe them with surface sensitive spectroscopic techniques. In this paper we report a different approach to identify intermediates for the formic acid decomposition reaction on Pd(111) and Pd(332) based on accurate measurements of isotopologue specific thermal reaction rates. At low surface temperatures (∼400 K) CO₂ formation is the major reaction pathway. The CO₂ kinetic data show this occurs via two temporally resolved reaction processes. Thus, there must be two parallel pathways which we attribute to the participation of two intermediate species in the reaction. Isotopic substitution reveals large and isotopologue specific kinetic isotope effects that allow us to identify the two key intermediates as bidentate formate and carboxyl. The decomposition of the bidentate formate is substantially slower than that of carboxyl. On Pd(332), at high surface temperatures (643 K to 693 K) we observe both CO and CO₂ production. The observation of CO formation reinforces the conclusion of calculations that suggest the carboxyl intermediate plays a major role in the water–gas shift reaction, where carboxyl exhibits temperature dependent branching between CO₂ and CO.