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State‐of‐the‐Art Aluminum Porphyrin‐based Heterogeneous Catalysts for the Chemical Fixation of CO 2 into Cyclic Carbonates at Ambient Conditions
Author(s) -
Chen Yaju,
Luo Rongchang,
Xu Qihang,
Zhang Wuying,
Zhou Xiantai,
Ji Hongbing
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201601578
Subject(s) - porphyrin , catalysis , chemistry , aluminium , oxidation state , chemical state , heterogeneous catalysis , photochemistry , inorganic chemistry , materials science , chemical engineering , organic chemistry , x ray photoelectron spectroscopy , engineering
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 CO 2 /N 2 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 CO 2 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 % CO 2 and 85 % N 2 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.