Low-Temperature Water Gas Shift Reaction over Highly Dispersed Ir on TiO2─Influence of the Ir Dispersed State and the Metal–Support Interface

Abstract

Oxide-supported iridium (Ir) metal catalysts exhibit superior activity for the low-temperature water gas shift (WGS) reaction. In this study, highly dispersed Ir supported on anatase TiO2 shows a relatively high turnover frequency and a relatively low activation energy for the WGS reaction compared to that reported in the literature. Catalyst characterization reveals the presence of small clusters and single atoms (SAs). Density functional theory (DFT) calculations show that the WGS reaction proceeds preferentially via a carboxyl mechanism with carboxyl formation as the rate-determining step on both TiO2-supported Ir clusters and SAs, which can be supported by experimental observations. In situ diffuse reflectance infrared Fourier transform spectroscopy, corroborated by DFT calculations, indicates that CO co-adsorbed with H2O at the interface between the Ir cluster and TiO2 plays the key role in low-temperature WGS starting from room temperature. DFT calculations show that the energy barrier of carboxyl formation over the Ir cluster is lower than that over Ir SAs, indicating that the Ir clusters may have contributed more to the low-temperature WGS activity. The excellent catalytic activity of the Ir/a-TiO2 catalyst reveals its potential application for low-temperature WGS.