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

The assembly of mixed [1,1';3',1'']terphenyl-4,5',4''-tricarboxylic acid (H₃TPTC) and [1,1'-biphenyl]-4,4'-dicarboxylic acid (H₂BPDC), 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid (H₂BPDC-NH₂), or 6-oxo-6,7-dihydro-5H-dibenzo[ d, f][1,3]diazepine-3,9-dicarboxylic acid (H₂BPDC-Urea) with Cu²⁺ ion generated the corresponding copper-paddlewheel-based metal-organic framework (MOF) [Cu₅(TPTC)₃(BPDC)_0.5(H₂O)₅] (1), [Cu₅(TPTC)₃(BPDC-NH₂)_0.5(H₂O)₅] (1-NH₂), or [Cu₅(TPTC)₃(BPDC-Urea)_0.5(H₂O)₅] (1-Urea). 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-NH₂, and for 1-Urea, respectively. Thermogravimetric measurements suggested 53, 51, and 48 wt % guest molecules in 1, 1-NH₂, and 1-Urea, respectively. 1-NH₂ 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 CO₂ 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 CO₂ chemical conversion under ambient conditions.