Efficient Conversion of CO₂ via Grafting Urea Group into a [Cu₂(COO)₄]-Based Metal–Organic Framework with Hierarchical Porosity

Abstract

The assembly of mixed [1,1′;3′,1′′]terphenyl-4,5′,4′′-tricarboxylic acid (H 3 TPTC) and [1,1′-biphenyl]They are isostructural with hierarchical porosity, consisting of zero-dimensional cage (19.2 Å × 18.9 Å) and one-dimensional pillar channel (29.7 Å × 15.1 Å) in a manner of face sharing. Platon analyses revealed the porous volume ratios are 80.2%, 80.0%, and 77.8% for 1, 1-NH 2 , and for 1-Urea, respectively. Thermogravimetric measurements suggested 53, 51, and 48 wt % guest molecules in 1, 1-NH 2 , and 1-Urea, respectively. 1-NH 2 and 1-Urea were precisely functionalized via the introduction of amino and urea functional groups into the pillar channels. The constructed MOF 1-Urea, incorporating both exposed copper active sites and accessible urea functional groups to substrates, presents high efficiency on catalytic CO 2 cycloaddition with propene oxide to produce cyclic carbonate in the yield of 98% with a TOF value of 136 h −1 at 1 atm and room temperature. This synergic effect provides a new strategy for designing high-efficient catalysts for CO 2 chemical conversion under ambient conditions.

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).…”

Green Synthesis of Novel Polyesterurethane Materials from Epoxides and Carbon Dioxide by New Set of One-Dimensional Coordination Polymer Catalyst

“…Many metal–organic frameworks and coordination polymers are known to perform interesting catalytic activities. 40−43 A few 1D coordination polymers synthesized from benzimidazole- and triazole-based precyclophane ligands are reported to perform catalytic organic transformations. 44,45 By considering the catalytic potentials of the precyclophane type of ligands, we synthesized two new 1D coordination polymers based on the ligand 2,6-bis(1 H -benzotriazol-1-ylmethyl)pyridine ( L ).…”

Recent Advances on Metal‐Organic Frameworks in the Conversion of Carbon Dioxide

“…Also, a Cu 2 (COO) 4 cluster based MOF with urea group on the framework was studied in converting CO 2 to corresponding cyclic carbonate, which exhibited remarkable catalytic activity. [ 77 ]…”