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A series of CuO/Ce1-xZrxO2 catalysts (x =0.2,0.4,0.6 and 0.8) are applied to elaborate the effect of the Zr/Ce ratio on the catalytic performance of CO2 hydrogenation to CH3OH.The best catalytic performance is achieved with CuO/Ce0.4Zr0.6O2,exhibiting XCO2 =13.2％ and YCH3OH =9.47％ (T =280 ℃,P =3 MPa).The formation of dispersed surface CuO species and larger number of oxygen vacancies are detected over CuO/Ce0.4Zr0.6O2 due to stronger interaction between CuO and Ce0.4Zr0.6O2,resulting in the superior activation ability for H2 and CO2 respectively.Additionally,the evidence is provided by in situ DRIFTS under the activity test pressure (3 MPa) that bi/m-HCOO* species are preferable for accumulating over ceria-rich (CuO/Ce0.6Zr0.4O2 and CuO/Ce0.8Zr02O2) catalysts while zirconia-rich (CuO/Ce0.4Zr0.6O2 and CuO/Ce0.2Zr0.8O2) catalysts are benefit to encourage the transformation of bi/m-HCOO* species to CH3OH.The abundant population and high activity of intermediate species over CuO/Ce0.4Zr0.6O2 give a strong positive effect on the catalytic performance.