Inhibition of hydrogen and oxygen recombination using oxygen transfer reagent hemin chloride in Pt/TiO2 dispersion for photocatalytic hydrogen generation

- The recombination of H2 and O2 can be inhibited by addition of O2 transfer reagent HC.
- The photocatalytic hydrogen evolution amount was significantly enhanced by HC addition.
- The HC could be multi-recycled by releasing the O2 with Ar gas bubbling.
- The HC lost O2 transfer property after CO poison leading to low hydrogen generation activity.
- The H2 and O2 recombination activation energy (16.5 kJ/mol) over Pt/P25 calculated by Arrhenius equation.

Recently, photocatalytic hydrogen generation from water-semiconductor catalyst dispersion attracted world-wide attention because the solar energy could be converted directly into hydrogen only in very simple set-up in scale-up scale. Although many photocatalysts were reported to be active for this reaction, the efficiency is still quite low. In this work, we found that hydrogen and oxygen recombination took place rapidly in the Pt/TiO2 dispersion and resulted in very low hydrogen generation rate in pure water. The activation energy of H2 and O2 recombination reaction is 16.5 kJ/mol regardless of light irradiation or not. In this case, the photocatalytic evolved H2 could react rapidly with the evolved O2 to form H2O again, eventually leading to no net H2 and O2 evolution during irradiation. The recombination of hydrogen and oxygen can be inhibited by addition of oxygen transfer reagent hemin chloride (HC). With help of HC, photocatalytic generated oxygen was captured by HC and transferred away from photocatalyst surface, then the backward reaction of hydrogen-oxygen recombination was successfully restrained. The photocatalytic hydrogen evolution amount in Pt/TiO2 dispersion was significantly enhanced under this condition. The isotopes analysis results confirmed that both the H2 and O2 were from water. The HC could be recycled by releasing the O2 with Ar gas bubbling. The HC could be poisoned by carbon monoxide and lost its oxygen transfer property, therefore no hydrogen could be formed under irradiation. This study clarified the main impediment reason of low efficient photocatalytic hydrogen generation in semiconductor-water dispersion and present available method to avoid this negative reaction. This finding will help to design high active catalytic system for solar energy to hydrogen conversion and open a new window for overall water splitting research.

289Hydrogen and oxygen recombination took place rapidly in the Pt/TiO2 dispersion and resulted in very low hydrogen generation rate in pure water. The hemin chloride (HC), an oxygen transfer reagent in the blood of animals, can capture and transfer the photocatalytic generated O2 away from photocatalyst surface and inhibit the recombination of hydrogen and oxygen on the surface of Pt NPS, which provide the reaction active site for H2 evolution. Under this condition, the photocatalytic hydrogen evolution amount in Pt/TiO2 dispersion was enhanced significantly. The isotopes analysis results confirmed that both the H2 and O2 were from water. The HC could be recycled by releasing the O2 with Ar gas bubbling. The HC could be poisoned by carbon monoxide and lost its oxygen transfer property, in this case, no hydrogen could be formed under irradiation.