Photoreforming of cellulose is a promising route for sustainable H₂ production. Herein, ball-milling (BM, with varied treatment times of 0.5–24 h) was employed to pretreat microcrystalline cellulose (MCC) to improve its activity in photoreforming over a Pt/TiO₂ catalyst. It was found that BM treatment reduced the particle size, crystallinity index (CrI), and degree of polymerization (DP) of MCC significantly, as well as produced amorphous celluloses (with >2 h treatment time). Amorphous cellulose water-induced recrystallization to cellulose II (as evidenced by X-ray diffraction (XRD) and solid-state NMR analysis) was observed in aqueous media. Findings of the work showed that the BM treatment was a simple and effective pretreatment strategy to improve photoreforming of MCC for H₂ production, mainly due to the decreased particle size and, specifically in aqueous media, the formation of the cellulose II phase from the recrystallization of amorphous cellulose, the extent of which correlates well with the activity in photoreforming.

Photocatalytic reforming of biomass has emerged as an area of significant interest within the last decade. The number of papers published in the literature has been steadily increasing with keywords such as ‘hydrogen’ and ‘visible’ becoming prominent research topics. There are likely two primary drivers behind this, the first of which is that biomass represents a more sustainable photocatalytic feedstock for reforming to value-added products and energy. The second is the transition towards achieving net zero emission targets, which has increased focus on the development of technologies that could play a role in future energy systems. Therefore, this review provides a perspective on not only the current state of the research but also a future outlook on the potential roadmap for photocatalytic reforming of biomass. Producing energy via photocatalytic biomass reforming is very desirable due to the ambient operating conditions and potential to utilise renewable energy (e.g., solar) with a wide variety of biomass resources. As both interest and development within this field continues to grow, however, there are challenges being identified that are paramount to further advancement. In reviewing both the literature and trajectory of the field, research priorities can be identified and utilised to facilitate fundamental research alongside whole systems evaluation. Moreover, this would underpin the enhancement of photocatalytic technology with a view towards improving the technology readiness level and promoting engagement between academia and industry.

Glucose is a key intermediate in cellulose photoreforming for H₂ production. This work presents a mechanistic investigation of glucose photoreforming over TiO₂ and Pt/m-TiO₂ catalysts. Analysis of the intermediates formed in the process confirmed the α-scission mechanism of glucose oxidation forming arabinose (C_n-1 sugar) and formic acid in the initial oxidation step. The selectivity to sugar products and formic acid differed over Pt/TiO₂ and TiO₂, with Pt/TiO₂ showing the lower selectivity to formic acid due to enhanced adsorption/conversion of formic acid over Pt/TiO₂. In situ ATR-IR spectroscopy of glucose photoreforming showed the presence of molecular formic acid and formate on the surface of both catalysts at low glucose conversions, suggesting that formic acid oxidation could dominate surface reactions in glucose photoreforming. Further in situ ATR-IR of formic acid photoreforming showed Pt-TiO₂ interfacial sites to be key for formic acid oxidation as TiO₂ was unable to convert adsorbed formic acid/formate. Isotopic studies of the photoreforming of formic acid in D₂O (with different concentrations) showed that the source of the protons (to form H₂ at Pt sites) was determined by the relative surface coverage of adsorbed water and formic acid.