Boosting Activity and Selectivity of UiO‐66 through Acidity/Alkalinity Functionalization in Dimethyl Carbonate Catalysis

The acid–base properties of supports have an enormous impact on catalytic reactions to regulate the selectivity and activity of supported catalysts. Herein, a train of Pd‐X‐UiO‐66 (X = NO2, NH2, and CH3) catalysts with different acidity/alkalinity functional groups and encapsulated Pd(II) species is first developed, whose activities in dimethyl carbonate (DMC) catalysis are then investigated in details. Thereinto, the Pd‐NO2‐UiO‐66 catalyst with acidity functionalization exhibits the best catalytic behavior: the DMC selectivity stemmed from methyl nitrite (MN) is up to 68%, the conversion of CO is 73.4%. The obtained experimental results demonstrate that the NO2 group not only affected the interaction between X‐UiO‐66 and Pd(II) active sites but also play an indispensable role in the adsorption and activation of MN and CO, which remarkably promote the formation of the COOCH3* intermediate and DMC product. Acidity/alkalinity functionalized MOFs into dimethyl carbonate catalysis are first introduced, and the Lewis acidic Pd‐NO2‐UiO‐66 exhibits excellent catalytic performance. In addition to affecting the interaction of Pd(II) and support, the NO2 group has a dominant role in the chemisorption of MN and CO for generating the intermediates COOCH3*, leading to higher catalytic performance.