Photocatalytic fuel cells (PFCs) are considered the next generation of energy converter devices, since they can harvest solar energy through relatively low-cost semiconductor material to convert the chemical energy of renewable fuels and oxidants directly into electricity. Here, we report black TiO2 nanoparticle (NP) photoanodes for simple single-compartment PFCs and microfluidic photo fuel cells (μPFCs) fed by methanol. We show that Ti3+ and oxygen vacancy (OV) defects at the TiO2 NPs are easily controlled by annealing in a NaBH4-containing atmosphere. This optimized noble-metal-free black TiO2 photoanode shows superior PFC performance for methanol oxidation and O2 reduction with a maximum power density (Pmax) ∼2000% higher compared to the undoped TiO2. At flow conditions, the black TiO2 photoanode showed a Pmax ∼90 times higher than the μFC equipped with regular TiO2 in the dark. The PFC and μPFC operate spontaneously with little activation polarization, and black TiO2 photoanodes are stable under light irradiation. The improved photoactivity of the black TiO2 photoanode is a consequence of the self-doping with Ti3+/OV defects, which significantly red-shifted the bandgap energy, induced intragap electronic states, and widened both the valence band and conduction band, enhancing the overall absorption of visible light and decreasing the interfacial charge transfer resistance.
Keywords: Ti3+ defect; optofluidics; oxygen vacancy; photo fuel cell; self-doping TiO2.