Porous Polymeric Hollow Fibers As Bifunctional Catalysts for CO₂ Conversion to Cyclic Carbonates


In this study, development of cooperative catalyst is demonstrated whereby Lewis acid/base species and nucleophilic parts are immobilized in the pores of a polyamide-imide (PAI) hollow fiber support. The highly solvent-stable and porous Br/APS-grafted ZrO₂-PAI hollow fiber (Br/APS/Zr-PAIHF) catalyst was created by crosslinking of bare ZrO₂-PAIHF polymer with 3-aminopropyltrimethoxysilane (APS) followed by alkylation with 1,2-dibromoethane at 110°C. This bifunctional catalyst consists of a porous ZrO₂-PAIHF polymer crosslinked with APS that was further immobilized with nucleophilic bromide ions. Porous ZrO₂-PAIHF provides a physical barrier to prevent cooperative Lewis acid/base species and nucleophilic parts movement, aggregation, and detachment from the support into the product stream. The performance of Br/APS/Zr-PAIHFs as heterogeneous catalyst was investigated for the reaction of carbon dioxide (CO₂) with styrene oxide (SO) which leads to the formation of styrene carbonate (SC). The influence of various reaction parameters including reaction temperature, reaction time, solvents, and CO₂ pressure were systematically investigated in detail. Our results indicated that the synergistic cooperative effect of nucleophilic bromide ion (Br-) and Lewis acid/base species on PAIHF supports leads to a maximum SC selectivity of 99.1%. Additionally, SO conversion of 100% and excellent SC selectivity of 98% were obtained over Br/APS/Zr-PAI-HF catalyst.


Chemical and Biochemical Engineering

Keywords and Phrases

Carbon; Carbon Dioxide; Catalysts; Crosslinking; Fibers; Ions; Polymers; Styrene; 3-Aminopropyl Trimethoxysilane; Bi-Functional Catalysts; Co-Operative Effects; Heterogeneous Catalyst; Hollow Fiber; Immobilizing Acid/Base and Nucleophilic Species; Reaction Parameters; Reaction Temperature; Catalyst Selectivity; CO2 Cycloaddition; Cooperative Heterogeneous Catalyst; Porous ZrO2-PAI Hollow Fiber Polymer

International Standard Serial Number (ISSN)


Document Type

Article - Journal

Document Version


File Type





© 2017 Elsevier, All rights reserved.

Publication Date

01 Oct 2017