Identifying Active Sites of the Water–Gas Shift Reaction over Titania Supported Platinum Catalysts under Uncertainty

A comprehensive uncertainty quantification framework has been developed for integrating computational and experimental kinetic data and to identify active sites and reaction mechanisms in catalysis. Three hypotheses regarding the active site for the water–gas shift reaction on Pt/TiO2 catalysts, Pt(111), an edge interface site, and a corner interface site, are tested against experimental kinetic data from three research groups. Uncertainties associated with density functional theory (DFT) calculations and model errors of microkinetic models of the active sites are informed and verified using Bayesian inference and predictive validation. Significant evidence is found for the role of the oxide support in the mechanism. Positive evidence is found in support of the edge interface active site over the corner interface site. For the edge interface site, the CO-promoted redox mechanism is found to be the dominant pathway and only at temperatures above 573 K does the classical redox mechanism contribute significantly to the overall rate. At all reaction conditions, water and surface O–H bond dissociation steps at the Pt/TiO2 interface are the main rate controlling steps.