Polyhydroxykanoate-Assisted Photocatalytic TiO₂ Films for Hydrogen Production

The photocatalytic production of hydrogen using biopolymer-immobilized titanium dioxide (TiO₂) is an innovative and sustainable approach to renewable energy generation. TiO₂, a well-known photocatalyst, benefits from immobilization on biopolymers due to its environmental friendliness, abundance, and biodegradability. In another way, to boost the efficiency of TiO₂, its surface properties can be modified by incorporating co-catalysts like platinum (Pt) to improve charge separation. In this work, the surface of commercial TiO₂ PC500 was modified with Pt nanoparticles (Pt1%@PC500) and then immobilized on glass surfaces using polyhydroxyalkanoate biopolymer poly(hydroxybutyrate-co-hydroxyhexanoate) (PHBH). The as-prepared immobilized Pt-modified TiO₂ photocatalysts were fully characterized using various physicochemical techniques. The photocatalytic activity of the photocatalyst film was investigated for photocatalytic hydrogen production through water reduction using ethanol as a sacrificial donor. The impact of the film preparation conditions, e.g., PHBH concentration, PHBH:catalyst ratio, and temperature, on activity and stability was studied in detail. The application of biopolymer PHBH as a binder provides a green alternative to conventional immobilization methods, and with the application of PHBH, a stable and active photocatalyst film that showed lower activity compared to that of the suspended photocatalyst but good recyclability in six runs was prepared. A long-term photocatalytic hydrogen production experiment was carried out. In 98 h of operation, 12 mmol of hydrogen was produced in three consecutive runs with a PHBH/Pt1%@PC500 film having an area of ∼5.3 cm². A significantly lower hydrogen productivity was observed after the first run, possibly due to a change in film structure, but thereafter, the productivity remained almost constant for the second and third runs. Hydrogen was the main product in the gas phase (90%), but carbon dioxide (4-5%) and methane (4-5%) were obtained as important byproducts. The byproducts are a consequence of the use of the sacrificial reagent ethanol. The results of the film performance are very promising, with regard to large-scale continuous hydrogen production.