Water-gas shift activity of Cu surfaces and Cu nanoparticles supported on metal oxides

Oxide supported Cu catalysts show significant activity for the water-gas shift reaction (WGS, CO + H2O → H2 + CO2) but their performance is not fully understood and is highly dependent on the synthesis conditions or the nature of the oxide support. This article describes a series of new studies examining the water-gas shift activity of Cu/MgO(1 0 0) surfaces and compares it to the activities found for pure copper systems, Cu nanoparticles in contact with well-defined surfaces of TiO2, ZnO, MoO2 and CeO2, and Cu cations present in mixed-metal oxides. Catalytic tests performed over CuFe2O4, Ce1−xCuxO2 or CuMoO4 show significant WGS activity only when the Cu cations in the mixed-metal oxide are reduced to metallic copper. Thus, Cu nanoparticles were deposited on different oxide surfaces and their WGS activity was measured in a batch reactor (PCO = 20 Torr; PH2OPH2O = 10 Torr; T = 575–650 K). The WGS activity of the Cu nanoparticles supported on MgO(1 0 0) was 2–3 times larger than that of Cu(1 0 0). Even better WGS catalysts were obtained when Cu was deposited on CeO2(1 1 1) or TiO2(1 1 0). An apparent activation energy of 13.8 kcal/mol was found for the WGS on Cu/MgO(1 0 0). This is smaller than the value of 15.2 kcal/mol observed on Cu(1 0 0), and substantially larger than the values of 7–9 kcal/mol seen for the apparent activation energies of the Cu/CeO2(1 1 1) and Cu/TiO2(1 1 0) catalysts. Post-reaction surface characterization pointed to the lack of O vacancies in the Cu/MgO(1 0 0) catalysts. This is in contrast to results found for Cu/CeO2(1 1 1) and Cu/TiO2(1 1 0), where the oxide support exhibits a significant concentration of O vacancies as a consequence of the WGS reaction. The oxygen vacancies present in Cu/CeO2(1 1 1) and Cu/TiO2(1 1 0) help in the dissociation of the water molecule and reduce the apparent activation energy for the WGS process. Such a phenomenon cannot occur on the Cu/MgO(0 0 1) catalysts, and the main steps of the WGS probably take place on the Cu nanoparticles.