Functionalised Porous Materials for CO₂ Capture and Conversion

Abstract

Conjugated Microporous Polymers (CMPs) are a versatile class of porous organic polymers that offer high thermal and chemical stability, tuneable functionality, and extended π-conjugation. In this thesis, a series of CMPs based on poly(triphenylamine) (PTPA) frameworks were synthesised via Buchwald–Hartwig amination and systematically investigated for their performance across a range of CO₂-related and broader functional applications. Optimised and functionalised PTPAs were employed as metal-free heterogeneous catalysts in the cycloaddition of CO₂ with epoxides. Under mild, solvent- and co-catalyst-free conditions, PTPA-COOH achieved near-quantitative conversions and demonstrated excellent reusability across diverse epoxide substrates, making these systems attractive for the sustainable synthesis of cyclic carbonates. Beyond chemical CO₂ conversion, the functionalised PTPAs were further evaluated as metal-free electrocatalysts for electrochemical CO₂ reduction. These materials exhibited promising Faradaic efficiencies for the formation of value-added products such as formate and methanol, supported by mechanistic insights from in situ spectroscopic studies. Finally, the scope of these CMPs was extended beyond CO₂ applications, positioning them as multifunctional platforms for emerging smart material technologies. By integrating synthetic optimisation, solvent selection, and performance testing, this thesis contributes to the rational design of next-generation functional materials that address critical challenges in sustainable chemistry and materials science.

Date of Award	30 Sept 2025
Original language	English
Awarding Institution	University of Bristol
Sponsors	Bolashak International Scholarship
Supervisor	Charl F J Faul (Supervisor) & Sean A Davis (Supervisor)