Metal Nanowire Felt as a Flow-Through Electrode for High-Productivity Electrochemistry

Flow-through electrodes such as carbon paper are used in redox flow batteries, water purification, and electroorganic syntheses. This work examines the extent to which reducing the size of the fibers to the nanoscale in a flow-through electrode can increase the productivity of electrochemical processes. A Cu nanowire felt, made from nanowires 45 times smaller than the 10 mu m wide fibers in carbon paper, can achieve a productivity 278 times higher than carbon paper for mass-transport-limited reduction of Cu ions. Higher increases in productivity were predicted for the Cu nanowire felt based on the mass transport-limited current, but Cu ion reduction became charge transfer-limited on Cu nanowire felt at high concentrations and flow rates when the mass-transport-limited current became comparable to the charge transfer-limited current. In comparison, the reaction rate on carbon paper was mass-transport-limited under all concentrations and flow rates because its mass-transport-limited current was much lower than its charge transfer-limited current. Higher volumetric productivities were obtained for the Cu nanowire felt by switching from Cu ion reduction to Alizarin Red S (ARS) reduction, which has a higher reaction rate constant. An electroorganic intramolecular cyclization reaction with Cu nanowire felt achieved a productivity 4.2 times higher than that of carbon paper, although this reaction was also affected by charge transfer kinetics. This work demonstrates that large gains in productivity can be achieved with nanostructured flow-through electrodes, but the potential gains can be limited by the charge transfer kinetics of a reaction.