Electrochemical Reduction of Carbon Dioxide in an MFC–MEC System with a Layer-by-Layer Self-Assembly Carbon Nanotube/Cobalt Phthalocyanine Modified Electrode

Abstract

Electrochemical reduction of carbon dioxide (CO(2)) to useful chemical materials is of great significance to the virtuous cycle of CO(2). However, some problems such as high overpotential, high applied voltage, and high energy consumption exist in the course of the conventional electrochemical reduction process. This study presents a new CO(2) reduction technique for targeted production of formic acid in a microbial electrolysis cell (MEC) driven by a microbial fuel cell (MFC). The multiwalled carbon nanotubes (MWCNT) and cobalt tetra-amino phthalocyanine (CoTAPc) composite modified electrode was fabricated by the layer-by-layer (LBL) self-assembly technique. The new electrodes significantly decreased the overpotential of CO(2) reduction, and as cathode successfully reduced CO(2) to formic acid (production rate of up to 21.0 ± 0.2 mg·L(-1)·h(-1)) in an MEC driven by a single MFC. Compared with the electrode modified by CoTAPc alone, the MWCNT/CoTAPc composite modified electrode could increase the current and formic acid production rate by approximately 20% and 100%, respectively. The Faraday efficiency for formic acid production depended on the cathode potential. The MWCNT/CoTAPc composite electrode reached the maximum Faraday efficiency at the cathode potential of ca. -0.5 V vs Ag/AgCl. Increasing the number of electrode modification layers favored the current and formic acid production rate. The production of formic acid was stable in the MFC-MEC system after multiple batches of CO(2) electrolysis, and no significant change was observed on the performances of the modified electrode. The coupling of the catalytic electrode and the bioelectrochemical system realized the targeted reduction of CO(2) in the absence of external energy input, providing a new way for CO(2) capture and conversion.