Many
nanofabrication processes require sophisticated equipment,
elevated temperature, vacuum or specific atmospheric conditions, templates,
and exotic chemicals, which severely hamper their implementation in
real-world applications. In this study, we outline a fully wet-chemical
procedure for equipping a 3D carbon felt (CF) substrate with a multifunctional,
titania nanospike-supported Pt-Pd nanoparticle (Pt-Pd-TiO2@CF) layer in a facile and scalable manner. The nanostructure, composition,
chemical speciation, and formation of the material was meticulously
investigated, evidencing the conformal coating of the substrate with
a roughened layer of nanocrystalline rutile spikes by chemical bath
deposition from Ti3+ solutions. The spikes are densely
covered by bimetallic nanoparticles of 4.4 ± 1.1 nm in size,
which were produced by autocatalytic Pt deposition onto Pd seeds introduced
by Sn2+ ionic layer adsorption and reaction. The as-synthesized
nanocomposite was applied to the (photo)electro-oxidation of formic
acid (FA), exhibiting a superior performance compared to Pt-plated,
Pd-seeded CF (Pt-Pd@CF) and commercial Pt-C, indicating the promoting
electrocatalytic role of the TiO2 support. Upon UV–Vis
illumination, the performance of the Pt-Pd-TiO2@CF electrode
is remarkably increased (22-fold), generating a current density of
110 mA cm–2, distinctly outperforming titania-free
Pt-Pd@CF (5 mA cm–2) and commercial Pt-C (6 mA cm–2) reference catalysts. In addition, the Pt-Pd-TiO2@CF showed a much better stability, characterized by a very
high poisoning tolerance for in situ-generated CO intermediates, whose
formation is hindered in the presence of TiO2. This overall
performance boost is attributed to a dual enhancement mechanism (∼30%
electrocatalytic and ∼70% photoelectrocatalytic). The photogenerated
electrons from the TiO2 conduction band enrich the electron
density of the Pt nanoparticles, promoting the generation of active
oxygen species on their surfaces from adsorbed oxygen and water molecules,
which facilitate the direct FA electro-oxidation into CO2.