Comparative study of the effect of TiO₂ support composition and Pt loading on the performance of Pt/TiO₂ photocatalysts for catalytic photoreforming of cellulose

Herein, catalytic aqueous phase photoreforming of cellulose was carried out over Pt/m-TiO₂ (i.e., mixed phase of anatase and rutile) and Pt/anatase catalysts to investigate the effect of the TiO₂ support structure and Pt loading on the production of H₂. The effect of the TiO₂ support on the properties of the resulting Pt/TiO₂ catalysts (such as actual Pt loading and BET surface area) was not significant. At low Pt loading of 0.16 wt.%, the TiO₂ supports affected the sub-nanometre Pt structures which was confirmed by the diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) characterisation (using CO as the probe). Conversely, the effect of TiO₂ supports on larger Pt particles (on 1 wt.% catalysts) was insignificant possibly due to the reduced effect of restructuration of bigger Pt particles on the TiO₂ supports. With an increase in Pt loading from 0.16 wt% to 1.00 wt.%, the normalised H₂ production rate (with respect to the actual supported Pt amount and specific surface area of the catalysts) showed a decreasing trend over the two types of the catalysts, i.e., from 10.6 to 1.4 μmol h⁻¹ m⁻² mg_Pt⁻¹ for Pt/m-TiO₂, and from 8.5 to 1.2 μmol h⁻¹ m⁻² mg_Pt⁻¹ for Pt/anatase. Specifically, large Pt particle sizes reduced the CO₂/H₂ production from cellulose photoreforming over both Pt/m-TiO₂ and Pt/anatase catalysts, indicting an important role played by Pt particle size in photoreforming. Interestingly, in this study, the m-TiO₂ supported catalysts only showed the benefits of enhanced charge separation across the phase junction in producing H₂ with small Pt particles (at sub-nanometre), whilst, when large Pt particles (at around 1–2 nm) were supported, such a benefit was not significant in cellulose photoreforming. The promoting effect of small, sub-nm particles is attributed to the better capture of photoelectrons from bulk TiO₂ and better activity of H⁺ coupling on small Pt particle. Further fundamental study on such guest-host interactions is devised to optimise Pt/TiO₂ catalysts for improving H₂ production from photoreforming reactions.