Azo-Functionalized Zirconium-Based Metal-Organic Polyhedron as an Efficient Catalyst for CO Fixation with Epoxides.

Chemical fixation of CO as C1 source at ambient temperature and low pressure is an energy-saving way to make use of the green-house gas, but it still remains a challenge since efficient catalyst with high catalytic active sites is required. Here, a novel monoclinic azo-functionalized Zr-based metal-organic polyhedron (Zr-AZDA) has been prepared and applied in CO fixation with epoxides. The inherent azo groups not only endow Zr-AZDA with good solubilization, but also act as basic sites to enrich CO showing efficient synergistic catalysis as confirmed by TPD-CO analysis. XPS results demonstrate that the Zr active sites in Zr-AZDA possess suitable Lewis acidity, which satisfies both substrates activation and products desorption. DFT calculation indicates the energy barrier of the rate-determining step in CO cycloaddition could be reduced remarkably (by ca. 60.9 %) in the presence of Zr-AZDA, which may rationalize the mild and efficient reaction condition employed (80 °C and 1 atm of CO ). The work provides an effective multi-functional cooperative method for improvement of CO cycloaddition.