State‐of‐the‐Art Aluminum Porphyrin‐based Heterogeneous Catalysts for the Chemical Fixation of CO₂ into Cyclic Carbonates at Ambient Conditions

Abstract

A series of metalloporphyrin‐based hyper‐crosslinked polymers (M‐HCPs: M=Al, Co, Fe, Mn) has been directly synthesized through Friedel–Crafts alkylation reactions. The M‐HCPs afforded abundant permanent nanopores, high Brunauer–Emmett–Teller (BET) surface area, and exceptional CO2/N2 adsorptive selectivity. The experimental results suggested that the hollow tubular Al‐HCP exhibited extraordinary catalytic performance in the solvent‐free synthesis of cyclic carbonates from epoxides and CO2 by using tetrabutylammonium bromide as a cocatalyst under mild conditions, which was clearly superior to the corresponding homogeneous analogue. Surprisingly, a high turnover frequency (TOF) value of 14 880 h−1 was achieved with propylene oxide at 100 °C and 3.0 MPa, which was a promising result for industrial production compared with previously reported heterogeneous catalysts. More interestingly, Al‐HCP could smoothly catalyze the cycloaddition reaction, producing the corresponding cyclic carbonates by using simulated flue gas (15 % CO2 and 85 % N2 in volume) as the raw material under ambient conditions. Moreover, Al‐HCP could be readily recycled and efficiently reused more than ten times, exhibiting excellent stability.

Rational Design of a 3D MnII‐Metal–Organic Framework Based on a Nonmetallated Porphyrin Linker for Selective Capture of CO2 and One‐Pot Synthesis of Styrene Carbonates

“…MnCl 2 ⋅ 6H 2 O, pyrrole, methyl 4‐formylbenzoate, propionic acid, and 1‐nitronaphthalene were obtained from TCI Chemicals. The H 4 TCPP ligand was synthesized by following the previously reported procedure . All reagents (epoxides) and internal standards used for catalytic reactions were purchased from TCI Chemicals and used without further purification.…”

Porous Organic Polymers for CO2 Storage and Conversion Reactions

“…Ji and co‐workers have synthesized a series of metalloporphyrin based hyper‐crosslinked microporous polymers M‐HCPs (M=Al, Co, Fe, Mn) in this context, which displayed turn over frequency as high as 14880 h −1 in the CO 2 fixation on epoxides in the presence of flue gas mixture (15 % CO 2 , 85 % N 2 ) at 100 °C and moderate reaction pressure of 3.0 Mpa. Ahn et al.…”

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO2 under Ambient Conditions

“…The cycloadditionr eaction of PO with CO 2 to yield the corresponding PC was chosen as am odel reaction to evaluate the catalytic activities of our materials (Table 1). From ar eview of our previous work on POP-based catalysts, [12] aluminum porphyrin-based hypercrosslinked polymers (Al-HCP) exhibited an extraordinary catalytic performance by using TBAB as ac ocatalyst at 40 8Ca nd 1.0 MPa. The catalytic activity of the simple ILfree catalyst Al-POPw as also investigated under identical conditions.F irst, if we used Al-TBPP or Al-POP as the sole catalyst, ad esirable yield of PC could not be detectede ven if we increasedt he reactiont ime (Table 1, entries 1-3).…”

“…For example, our group reported that aluminum porphyrin-based hypercrosslinked polymers could exhibit extraordinary catalytic performances with ah igh turnover frequency( TOF) of 14 480 h À1 in this reaction. [12] Nevertheless, this binary catalytic system still required an additional cocatalyst as an ucleophile (e.g.,t etrabutylammoniumb romide;T BAB), which implemented the catalytic cyclea nd increased the overall efficiency.M oreover,i nspired by the design of bifunctional catalysts, as eries of hierarchical POPs with multiple active sites, which included metallosalenc omplexes and ionic liquid (IL) units, were also synthesized and employed as efficient catalysts in the chemicalc onversion of CO 2 into valuable chemicals withoutt he use of cocatalysts. [13] Regrettably,ahigher reaction temperature (> 100 8C) was often required to obtain the excellent catalytic properties, which was undesirablei ns ome applications.…”