Origin of the electrocatalytic activity in carbon nanotube fiber counter-electrodes for solar-energy conversion

Carbon nanotubes are a versatile platform to develop sustainable and stable electrodes for energy-related applications. However, their electrocatalytic activity is still poorly understood. This work deciphers the origin of the catalytic activity of counter-electrodes (CEs)/current collectors made of self-standing carbon nanotube fibers (CNTfs) using Co²⁺/Co³⁺redox couple electrolytes. This is based on comprehensive electrochemical and spectroscopic characterization of fresh and used electrodes applied to symmetric electrochemical cells using platinum-based CEs as a reference. As the most relevant findings, two straight relationships were established: (i) the limiting current and stability increase rapidly with the surface concentration of oxygen-containing functional groups, and (ii) the catalytic potential is inversely related to the amount of residual metallic Fe catalyst nanoparticles interspersed in the CNTf network. Finally, the fine tuning of the metal nanoparticle content and the degree of functionalization enabled fabrication of efficient and stable dye-sensitized solar cells with cobalt electrolytes and CNTf-CEs outperforming those with reference Pt-CEs.