Functionalized carbon nanotube and carbon nanodot modified multiblock poly(arylene ether ketone sulfone) copolymer as proton exchange composite membranes for fuel cell applications

Abstract The present study describes the successful synthesis of –COOH functionalized carbon nanodots (f‐CNDs) via pyrolysis of citric acid and 4,4′‐bis(4‐hydroxyphenyl)valeric acid (DPA‐OH, Sigma Aldrich, St. Louis, Missouri, United States) based hydrophilic oligomer at 250 °C. The multiblock copolymers were prepared by a coupling reaction between phenoxide terminated valeric acid based poly(arylene ether ketone) (DPA‐OH) hydrophilic oligomer and decafluorobiphenyl (DFBP, Alfa Aesar, Haverhill, Massachusetts, United States) end‐capped poly(arylene ether sulfone) (BP‐X‐F) hydrophobic oligomers (where X is 6, 9 and 12). Multiblock poly(arylene ether ketone sulfone) copolymer crosslinked membranes were prepared using 6F‐bisphenol‐A based novolac epoxy resin (EFN) and –COOH functionalized multiwalled carbon nanotubes/functionalized carbon nanodots (f‐MWCNTs/f‐CNDs, Nanoshell company, Utah, U. S) were used for the preparation of acid doped composite membranes for fuel cell applications. From high resolution TEM images, the average size of the prepared f‐CNDs found to be ca 10–12 nm. The N 1 multiblock copolymer membrane with loading of 0.9 wt% ratio of CNTs showed better proton exchange membrane related properties such as proton conductivity (0.136 S cm −1 ), ion exchange capacity (1.18 meq g −1 ) and selectivity ratio (0.17) compared to the prepared pristine, crosslinked and CND based composite membranes. The overall results revealed that the composite membranes with loading of 0.9 wt% of CNTs and CNDs exhibited a superior combination of fuel cell related properties such as higher proton conductivity, high dimensional and oxidative stability and low methanol permeability and also showed better fuel cell performance compared to the respective pristine and EFN crosslinked membranes. © 2022 Society of Industrial Chemistry.