Wet-Spun Porous Carbon Microfibers for Enhanced Electrochemical Detection.

We present a novel copolymer-based, uniform porous carbon microfiber (PCMF) formed via wet-spinning for significantly improved electrochemical detection. Carbon fiber (CF), fabricated from a polyacrylonitrile (PAN) precursor, is commonly used in batteries or for electrochemical detection of neurochemicals due to its biplanar geometry and desirable edge plane sites with high surface free energy and defects for enhanced analyte interactions. Recently, the presence of pores within carbon materials has presented interesting electrochemistry leading to detection improvements; however, there is currently no method to uniformly create pores on a carbon microfiber surface impacting a broad range of electrochemical applications. Here, we synthesized controllable porous carbon fibers from a spinning dope of the copolymers PAN and poly(methyl methacrylate) (PMMA) in dimethylformamide via wet spinning for the first time. PMMA serves as a sacrificial block introducing macropores of increased edge-plane character on the fiber. Methods were optimized to produce porous CFs at similar dimensions to traditional CF. We prove that an increase in porosity enhances the degree of disorder on the surface, resulting in significantly improved detection capabilities with fast-scan cyclic voltammetry. Local trapping of analytes at porous geometries enables electrochemical reversibility with improved sensitivity, linear range of detection, and measurement temporal resolution. Overall, we demonstrate the utility of a copolymer synthetic method for PCMF fabrication, providing a stable, controlled macroporous fiber framework with enhanced edge plane character. This work will significantly advance fundamental investigations of how pores and edge plane sites influence electrochemical detection.