ZnO Supported on a Zr-Based Metal–Organic Framework for Selective CO₂ Hydrogenation to Methanol

ZnO supported on ZrO2 is active in hydrogenating CO2 to methanol. The local structure at the ZnO/ZrO2 interface must play an important role in catalysis. Here, we support ZnO on Zr-based metal–organic framework (MOF) nanoplates to construct an active catalyst for CO2 hydrogenation to methanol. Compared to ZrO2, the Zr-based MOF has a better-defined local structure on the surface. The Zr-based MOF contains Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6 clusters connected by linear biphenyldicarboxylate (bpdc) linkers. No aggregation of the ZnO nanoparticles was observed after the catalysis of 100 h at 250 °C. The resulting ZnO/Zr12-bpdc catalysts show a space time yield of up to 110 mgMeOH gcatalyst–1 h–1 or 440 mgMeOH gZn–1 h–1 and more than 95% selectivity for methanol. This work replaces the ZnO/ZrO2 interface with the contact between ZnO and a Zr12 cluster in a MOF to obtain an active catalyst, providing insights into the chemical structure of the active sites in ZnO/ZrO2 catalysts.