Cu+-ZrO2 interfacial sites with highly dispersed copper nanoparticles derived from Cu@UiO-67 hybrid for efficient CO2 hydrogenation to methanol

A series of Cu@ZrO 2 -U framework catalysts derived from Cu@UiO-67 precursors with adjustable copper loadings were constructed by the deposition-precipitation method, and the catalytic activities of methanol synthesis via CO 2 hydrogenation were investigated. The optimized 20-Cu@ZrO 2 -U catalyst showed the best catalytic activity. At 3 MPa and 260 °C, the space-time yield of CH 3 OH (STY CH3OH ) reached 2.28 mmol CH3OH /(g cat ·h), which was 3.5 times higher than that of 20-Cu/ZrO 2 . The catalyst of 20-Cu@ZrO 2 -U also showed good stability during the 100-h time on stream test. The catalysts were further characterized by XRD, N 2 sorption, TEM, XPS, H 2 -TPR, CO 2 /H 2 -TPD and in situ DRIFTS. The characterization results showed that the stable ZrO 2 framework derived from UiO-67 is propitious to the confine of copper nanoparticles and formation of Cu + -ZrO 2 interfacial sites, which should be responsible for the excellent performance of methanol synthesis. Moreover, in situ DRIFTS was used to probe that the methanol synthesis via CO 2 hydrogenation over 20-Cu@ZrO 2 -U follows a HCOO∗-intermediated reaction pathway. • A novel Cu@ZrO 2 -U framework catalyst was constructed by Cu@UiO-67 precursor strategy. • The optimized catalyst of 20-Cu@ZrO 2 -U was shown to form rich Cu + -ZrO 2 interfaces. • The methanol yield of 20-Cu@ZrO 2 -U was 3.5 times higher than 20-Cu/ZrO 2 catalyst. • The methanol productivity depends on the ratio of Cu + /Cu 0 regulated by Cu + -ZrO 2 interface. • The methanol synthesis mechanism of Cu@ZrO 2 -U follows a HCOO∗-intermediate pathway.