Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

CeO2/Au(110) inverse model catalysts were prepared and their activity toward the adsorption and co-adsorption of O2, CO, CO2 and water was studied by means of X-ray photoelectron spectroscopy, low energy electron diffraction, thermal desorption spectra and temperature-programmed reaction spectra. The Au surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs CO, CO2 and water, and the polycrystalline CeO2 surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs O2, and molecularly and reactively adsorbs CO, CO2 and water. By controllably preparing co-adsorbed surface species on CeO2/Au(110) inverse model catalysts, we successfully identified various surface reaction pathways of CO oxidation to produce CO2 with different barriers both on the CeO2 surface and at the Au-CeO2 interface, including CO oxidation by various oxygen species, and water/hydroxyl group-involved CO oxidation. These results establish a surface reaction network of CO oxidation catalyzed by Au/CeO2 catalysts, greatly advancing the fundamental understandings of catalytic CO oxidation reactions.

Methanol Conversion into Dimethyl Ether on the Anatase TiO2(001) Surface.

Exploring reactions of methanol on TiO2 surfaces is of great importance in both C1 chemistry and photocatalysis. Reported herein is a combined experimental and theoretical calculation study of methanol adsorption and reaction on a mineral anatase TiO2(001)-(1×4) surface. The methanol-to-dimethyl ether (DME) reaction was unambiguously identified to occur by the dehydration coupling of methoxy species at the fourfold-coordinated Ti(4+) sites (Ti(4c)), and for the first time confirms the predicted higher reactivity of this facet compared to other reported TiO2 facets. Surface chemistry of methanol on the anatase TiO2(001)-(1×4) surface is seldom affected by co-chemisorbed water. These results not only greatly deepen the fundamental understanding of elementary surface reactions of methanol on TiO2 surfaces but also show that TiO2 with a high density of Ti(4c) sites is a potentially active and selective catalyst for the important methanol-to-DME reaction.

Hydrogen spillover enhanced hydroxyl formation and catalytic activity toward CO oxidation at the metal/oxide interface.

H2-promoted catalytic activity of oxide-supported metal catalysts in low-temperature CO oxidation is of great interest but its origin remains unknown. Employing an FeO(111)/Pt(111) inverse model catalyst, we herewith report direct experimental evidence for the spillover of H(a) adatoms on the Pt surface formed by H2 dissociation to the Pt-FeO interface to form hydroxyl groups that facilely oxidize CO(a) on the neighboring Pt surface to produce CO2. Hydroxyl groups and coadsorbed water play a crucial role in the occurrence of hydrogen spillover. These results unambiguously identify the occurrence of hydrogen spillover from the metal surface to the noble metal/metal oxide interface and the resultant enhanced catalytic activity of the metal/oxide interface in low-temperature CO oxidation, which provides a molecular-level understanding of both H2-promoted catalytic activity of metal/oxide ensembles in low-temperature CO oxidation and hydrogen spillover.

A near-ambient pressure flow reactor coupled with polarization-modulation infrared reflection absorption spectroscopy for operando studies of heterogeneous catalytic reactions over model catalysts.

The model catalyst approach is often used for fundamental investigations of complex heterogeneous catalysis, in which operando characterizations are critical. A flow reactor is usually adopted for gas-solid heterogeneous catalytic reactions. Herein, we report a home-designed near-ambient pressure (NAP) flow reactor coupled with polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) and an online quadrupole mass spectrometer for operando studies of heterogeneous catalytic reactions over model catalysts. A unique gas supply system is designed and manufactured to enable a stable gas inlet to the NAP flow reactor at pressures up to ∼100 mbar. An ultrahigh vacuum chamber equipped with the facilities for x-ray photoelectron spectroscopy, low-energy electron diffraction, thermal desorption spectroscopy, E-beam evaporation source, and ion sputtering gun is connected to the NAP flow reactor via a gate valve for preparations and routine characterizations of model catalysts. The functions of the system are demonstrated by in situ PM-IRAS characterization of CO adsorption on Pt(111) and operando characterizations of CO oxidation on Pt(111) under NAP conditions.