A Noble‐Metal‐Free Metal–Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO₂ with Propargylic Alcohols

Abstract

Cyclization of propargylic alcohols with CO 2 is an important reaction in industry,a nd noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions.H erein ap orous noblemetal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability,a nd is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO 2 without any solvents under mild conditions,a nd the turnover number (TON) can reach to arecord value of 14 400. Furthermore,t his MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as as ubstrate.M echanistic studies reveal that the synergistic catalytic effect between Cu I and In III plays ak ey role in the conversion of CO 2 .

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO2 Conversion

“…The design and synthesis of mixed d-f heterometallic-organic frameworks (HMOFs) is currently attracting greata ttention,t he driving force of which originatesn ot only from their fascinating structural diversities but also from their potentiala pplications. [1][2][3][4][5][6][7][8][9] Thec oordination preference of different metal ions and ligands have an immense influence on the construction of functional MOF materials. [1] Among them, metali ons of silver and lanthanide have the differentcoordination affinities with O and Nd onors according to the theory of hard and soft acids and bases (HSABp rinciple).…”

Recent progress in materials development for CO2conversion: issues and challenges

“…Zhao and co-workers proposed noble-metal-free MOFs for solvent-free cyclization of propargylic alcohols and CO 2 under mild conditions with large of turnover number (TON) yield. 240 More recently, a series of ruthenium complexes immobilized on azolium-based MOFs have been reported for CO 2 to formic acid conversion with convenient yield and superior recyclability. 241 Tshuma et al also prepared efficient lanthanum (La)-based MOFs for catalytic hydrogenation of CO 2 to formate under optimized reaction conditions.…”

The Active Sites Engineering of Catalysts for CO2 Activation and Conversion

“…In contrast, the cyclization reaction occurred only when the triethanolamine (TEA) and catalyst were added together by monitoring the 1 H NMR spectroscopy (Figure 6c), which indicated the important role of Lewis acidic sites in activating propargylic alcohol with the assistance of TEA. [ 121 ]…”