Formation of CX Bonds in CO₂ Chemical Fixation Catalyzed by Metal−Organic Frameworks

Abstract

Transformation of CO2 based on metal−organic framework (MOF) catalysts is becoming a hot research topic, not only because it will help to reduce greenhouse gas emission, but also because it will allow for the production of valuable chemicals. In addition, a large number of impressive products have been synthesized by utilizing CO2. In fact, it is the formation of new covalent bonds between CO2 and substrate molecules that successfully result in CO2 solidly inserting into the products, and only four types of new CX bonds, including CH, CC, CN, and CO bonds, are observed in this exploration. An overview of recent progress in constructing CX bonds for CO2 conversion catalyzed by various MOF catalysts is provided. The catalytic mechanism of generating different CX bonds is further discussed according to both structural features of MOFs and the interactions among CO2, substrates, as well as MOFs. The future opportunities and challenges in this field are also tentatively covered.

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

“…In this study,r elativelym ildc onditions are designed in the presenceo ft etra-n-butyl ammonium bromide (TBAB) as the co-catalyst to access the catalytic ability of the four MOFs for the production of five-membered cyclic carbonates by the coupling of epoxidesw ith CO 2 (Table 1), and the reaction was performed in aS chlenk tube by using epoxides with CO 2 under solvent-free conditions. [34][35][36][37][38] The formation of the desired carbonatewas confirmed by 1 HNMR spectroscopy.…”

CO2-Fixation Strategies in Energy Extremophiles: What Can We Learn From Acetogens?

“…The few applicable chemical processes allowing its unfavorable fixation (like the Monsanto and Cativa processes) require high temperatures and pressures as well as expensive and polluting catalysts while only exhibiting moderate catalytic rates (Appel et al, 2013;Fujita et al, 2013;Schuchmann and Müller, 2013). New alternative chemistry based on metal-organic framework (Hou et al, 2019) or transition metal-free catalysis (Cherubini-Celli et al, 2018) are upcoming and might be applied in the near future. Nevertheless, none of these artificial processes matches the efficiency of their biological counterpart.…”

Hydroxylamino‐Anchored Poly(Ionic Liquid)s for CO2 Fixation into Cyclic Carbonates at Mild Conditions

“…[ 2–9 ] The use of fixation of CO 2 with epoxides as an absolutely economical methodology to realize conversion of thermodynamics of inert CO 2 and generate valuable cyclic carbonates. [ 10–17 ] In addition, cyclic carbonates are well established as important chemicals and widely applied in several industrial fields. [ 18,19 ]…”