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The water-gas shift (WGS) reaction (H 2 O + CO f H 2 + CO 2 ) is regarded as a key catalytic process in a future hydrogen economy. In this report, first-principles density functional theory (DFT) calculations have been utilized to identify the WGS mechanism over a Cu/oxide model catalyst, Cu/ZrO 2 . The catalytic reaction is found to occur at the Cu sites that are in the vicinity of Cu/oxides interfaces, where the Cu electronic structure is markedly modified by the oxygen-rich Cu/oxides interface. DFT-based microkinetic modeling further shows that a COOH-involved mechanism is responsible for the WGS reaction, with the H 2 O dissociation step being rate-controlling. By comparing the reaction thermodynamics and kinetics over three systems, namely, Cu/ZrO 2 , unsupported Cu strip, and Cu(111), we demonstrate that positively charged Cu clusters afford much enhanced catalytic activity in H 2 O dissociation. The ZrO 2 support acts as a charge buffer to accept/release electrons from/to the Cu particle. The oxygen-rich metal-oxide interface, although not directly involved in catalysis, acts as a key promoter in enhancing catalytic activity in Cu-based catalysis.

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A complete understanding of the carbon dioxide (CO 2 ) interaction with zinc oxide (ZnO) is a basis for the development of new ZnO-containing materials for catalytic fixation of CO 2 into useful chemicals such as methanol. In this work, the density functional theory plus U (DFT+U) method coupled with periodic boundary conditions has been employed to investigate the adsorption of CO 2 molecules on five relevant exposed surfaces of ZnO in an effort to capture the surface chemistry of the adsorbed molecules. Through our calculations, we demonstrated that the CO 2 adsorption is sensitive to the oxide surface structure. The activation of CO 2 by ZnO via the carbonate-ion formation requires the presence of empty surface Zn−O pairs. It was found that the binding strength of CO 2 follows the order of ZnO(0001̅ ) ≤ ZnO(0001) < ZnO(112̅ 1) < ZnO(112̅ 0) ≤ ZnO(101̅ 0), which is, surprisingly, different from the decreasing stability sequence of these surfaces (ZnO(101̅ 0) > ZnO(112̅ 0) > ZnO(0001̅ )/ZnO(0001) > ZnO(112̅ 1)). The counterintuitive difference was discussed in detail on the basis of the adsorption energy decomposition into two antagonistic effects: adsorbate−substrate interaction and their deformation energies. The bonding nature of CO 2 to the oxide substrates was analyzed, and the 2p states of CO 2 were verified to be able to mix both with the 4s orbital of surface zinc and with the 2p orbitals of surface oxygen. Our calculations indicate that different from the previous viewpoint CO 2 , as an electronegative adsorbate, may also be positively charged by certain ZnO surfaces, like the stepped (112̅ 1) facet presented here. Interestingly, the stronger the electron transfer between the two interacting moieties, the stronger their interaction, and the stronger the CO bond activation. Also, it has been observed that the change in the surface work function upon the adsorption of CO 2 does not completely depend on the sign of charge transferred.