Two Ln-MOFs containing abundant Lewis acid sites as the efficient and heterogeneous catalyst to activate epoxides for cycloaddition of CO2

Abstract

The burning of a large number of fossil fuels leads to the increase of CO2 content in the air, causing environmental problems such as greenhouse effect and ocean acidification, which has attracted wide attention. It is of great significance to utilize microporous metal-organic frameworks (MOFs) for carbon dioxide conversion and utilization. Herein, two MOFs {[Ln(dppa)(H2O)2·2H2O]·dima·H2O·0.5O} (1: Sm-MOF; 2: Gd-MOF; H4dppa = 5-(3′ 4′-dicar- boxylphenoxy) isophthalic acid, dima = dimethylamine, which is decomposed by DMF hydrothermal reaction), and its structural characterization and CO2 catalytic conversion performance were studied. The BET test of MOFs 1–2 shows that it has good microporosity. At 273 K and 298 K, MOFs 1–2 showed lower adsorption capacity for CH4, but higher adsorption capacity for CO2. The adsorption enthalpy of CO2 was calculated by Virial equation, and the adsorption selectivity of CO2 at different separation ratios was discussed respectively. The heterogeneity of MOFs 1–2 was proved by thermal filtration experiments. The reproducibility test shows that the catalyst structure is still intact after five cycles, indicating that the catalyst still has good repeatability. In addition, the catalytic mechanism of cycloaddition reaction was discussed.