A Stable Mesoporous Zr-Based Metal Organic Framework for Highly Efficient CO₂ Conversion

Abstract

With the help of modulator synthesis method, a mesoporous Zr-based metal–organic framework, [Zr6O4(OH)8(H2O)4­(TADIBA)4]·24DMF·45H2O (DMF = N,N-dimethylformamide, H2TADIBA = 4,4′-(2H-1,2,4-triazole-3,5-diyl) dibenzoic acid), namely, JLU-MOF58, was successfully constructed. JLU-MOF58 having reo topology is constructed by the bent ligands with Lewis basic sites and 8-connected Zr6 clusters with Lewis and Brønsted acid sites. It not only possesses two types of mesoporous cages: octahedral and cuboctahedral (2.76 and 4.10 nm), with a pore volume of 1.76 cm3 g–1, but also displays excellent chemical stability in acid and base aqueous phase. Benefiting from the Brønsted and Lewis acid sites, Lewis basic sites, excellent chemical stability, and the mesoporous cages incorporated in the framework, JLU-MOF58 can be regarded as a remarkably efficient heterogeneous catalyst that exhibits excellent catalytic efficiency for CO2 conversion.

Rational Design of a ZnII MOF with Multiple Functional Sites for Highly Efficient Fixation of CO2 under Mild Conditions: Combined Experimental and Theoretical Investigation

“…The excellent catalytic activity of HbMOF 1 for cycloaddition of various terminal epoxides motivated us to study the catalytic activity for the cycloaddition of internal epoxides, which are known to be less reactive than the terminal epoxides [15b, 22, 23] . Therefore, normally higher reaction temperature and/or pressure with prolonged reaction time are employed for the conversion of internal epoxides [15b, 22–24] . On the contrary, our catalyst HbMOF 1 catalyzes the cycloaddition of cyclopentene oxide (CPO) to the corresponding cyclic carbonate with about 70 % conversion with a turnover number (TON) of 700 under mild reaction conditions (1 bar CO 2 and RT; Table 1 and Figure S25).…”

A Double-Walled Porous Metal–Organic Framework as a Highly Efficient Catalyst for Chemical Fixation of CO2 with Epoxides

“…According to MOF 1 ’s framework and previous similar reports, − the assumptive catalytic mechanism may contain four steps. As seen in Figure , the catalytic process is first caused and activated by an O atom in the epoxide ring by synergistic interaction with Zn II Lewis acid and Brønsted acid (−OH) centers on the ligand.…”

MIL-101(Cr) for CO2 Conversion into Cyclic Carbonates, Under Solvent and Co-Catalyst Free Mild Reaction Conditions

“…According to previous reports, based on the theoretical calculations (DFT) of the catalytic mechanism, the ring-opening process of the epoxide is the rate-limiting step of this reaction [49]. Also, it was observed that the Lewis acid sites played a main role in the ring-opening process by binding the oxygen atom of the epoxide [50]. A well-known technique to analyze the amount of acid and basic sites on MOFs is temperature program desorption (TPD), which makes use of gas probe molecules (NH 3 and CO 2 to determine the acid and basic amounts, respectively) [48].…”