Efficient catalytic conversion of terminal/internal epoxides to cyclic carbonates by porous Co(ii) MOF under ambient conditions: structure–property correlation and computational studies

Abstract

Efficient CO2 capture/utilization by Co(ii) MOF as a heterogeneous catalyst in CO2–epoxide cycloaddition at ambient condition has been investigated and correlated with computational studies.

Combining In Situ Techniques (XRD, IR, and 13C NMR) and Gas Adsorption Measurements Reveals CO2-Induced Structural Transitions and High CO2/CH4 Selectivity for a Flexible Metal–Organic Framework JUK-8

“…Furthermore, the described observations clearly demonstrate the role of an acylhydrazone in the proposed catalytic mechanism for CO 2 cycloaddition that leads to terminal/internal epoxides, as described by Suresh and co-workers ( Figure S13 ). 40 …”

“… 24 In situ PXRD provides global information about two-step structural transformation, while in situ IR and NMR shed light on the interaction between carbon dioxide and acylhydrazone group (−C(O)=N–NH−). 39 , 40 Moreover, one-component (CO 2 , CH 4 , Ar, O 2 , and N 2 ) and multicomponent (CH 4 /CO 2 ) equilibrium adsorption studies in a broad temperature range have shown high selectivity of JUK-8 toward carbon dioxide.…”

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).…”

“…The difference between the relative energies of TS‐1 and IC as shown in Scheme 2 is 9.6 kcal mol −1 . Also, this energy barrier for the ring‐opening step is treated as the rate‐determining step in the CO 2 fixation with PO according to several other previously reported DFT energy profiles for cycloaddition reactions [15b, 27] . Next, the CO 2 insertion to the bromide‐substituted alkoxide species in TS‐1 occurs with a relative energy of 24.6 kcal mol −1 as the cycloaddition progresses.…”

Facile Green Synthesis of New Copper-Based Metal–Organic Frameworks: Experimental and Theoretical Study of the CO2 Fixation Reaction

“…[6][7][8][9][10][11][12] Additionally, the selective coupling between CO 2 and epoxides to produce cyclic carbonates has also attracted significant attention in this area because of its wide applications (Scheme 1). [13][14][15][16][17][18][19][20][21][22][23][24][25] However, the use of catalysts and co-catalysts under low temperature and pressure conditions is challenging for the cycloaddition reactions. One solution is to design catalytic systems that can easily attract and activate CO 2 , which will allow them to be used at low reaction temperatures and ambient pressures.…”