Catalytic Space Engineering of Porphyrin Metal–Organic Frameworks for Combined CO₂ Capture and Conversion at a Low Concentration

Abstract

Porous porphyrin metal-organic frameworks (PMOFs) provide promising platforms for studying CO capture and conversion (C3) owing to their versatility in photoelectric, catalytic, and redox activities and porphyrin coordination chemistry. Herein, we report the C3 application of two PMOFs by engineering the coordination space through the introduction of two catalytic metalloporphyrins doped with rhodium or iridium, Rh-PMOF-1 and Ir-PMOF-1, both of which can serve as heterogeneous catalysts for the chemical fixation of CO into cyclic carbonates with yields of up to 99 %. Remarkably, the catalytic reactions can effectively proceed under low CO concentrations and high yields of 83 % and 73 % can be obtained under 5 % CO in the presence of Rh-PMOF-1 and Ir-PMOF-1, respectively. The synergistic effect of the metalloporphyrin ligand and the Zr O cluster, in combination with the CO concentration effect from the pore space, might account for the excellent catalytic performance of Rh-PMOF-1 under low CO concentration. Recycling tests of Rh-PMOF-1 show negligible loss of catalytic activity after 10 runs.

Hybrid Materials Based on Silica Matrices Impregnated with Pt-Porphyrin or PtNPs Destined for CO2 Gas Detection or for Wastewaters Color Removal

“…The capacity of these new hybrid materials to adsorb/detect carbon dioxide was investigated. The PtTAOPP-silica hybrid material, having suitable morphologic characteristics (Table 2), is able to adsorb the highest amount of CO 2 , that is, 0.025 mol CO 2 /g, representing the second best performance of CO 2 recovery, after that already reported [48]. The other investigated materials also have remarkable but lower adsorption capacities, namely: silica control 0.021 mol/g, (TAOPP-PtNPs)-silica hybrid 0.016 mol/g and PtNPs-silica hybrid 0.011 mol/g, respectively.…”

Conversion of CO2 into Chloropropene Carbonate Catalyzed by Iron (II) Phthalocyanine Hypercrosslinked Porous Organic Polymer

“…The catalytic activity of FePc-POP was compared with those reported for some heterogeneous porphyrin- [ 19 , 20 , 21 , 22 , 23 , 38 , 39 , 40 , 41 ] or phthalocyanine-based [ 42 , 43 ] catalysts in the cycloaddition of CO 2 to ECH ( Table 3 ). The Mg porphyrin based catalysts (entries 1 and 2) work with very high substrate/metal ratios which result in very high TON values but higher CO 2 pressures and temperatures are needed to achieve total conversion.…”

Cycloaddition Reactions of Epoxides and CO2 by the Novel Imidazolium‐Functionalized Metalloporphyrins: Optimization and Analysis using Response Surface Methodology

“…As mentioned above, the pressure had almost no influence on the reaction, while the reaction temperature and time were the major influencing factors. This led to the evaluation of the catalytic activity of 1 under atmospheric pressure, because the cycloaddition reaction of epoxides and CO 2 under mild conditions is a challenging and important task . PGE with high boiling point (245 °C) was chosen as the substrate for the exploration of the effects of temperature and time.…”