Photocatalytic cellulose reformation is regarded as a potential and affordable route for sustainable H₂ evolution. However, direct photoreformation still suffers from challenges such as the limited solubility of cellulose and the dependence on the catalytic activity of noble metals. Herein, we report a new photoreformation of cellulose into H₂ over TiO₂ that is modified with nickel sulfide (Ni_xS_y) and chemisorbed sulfate species (SO₄²⁻) by a one‐pot approach. A significant elevation in the photocatalytic hydrogen evolution rate is achieved with a maximal value of 3.02 mmol g⁻¹ h⁻¹ during the first 3 h, which is almost 76‐fold higher than that of P25 and comparable to that of Pt‐P25. Aided by systematic investigation, it is proposed that nickel sulfide and sulfate modification contribute synergistically to the remarkably increased efficiency of biomass transformation. Specifically, Ni_xS_y acts as a cocatalyst for photocatalytic H₂ production, and we infer that SO₄²⁻ ions promote cellulose hydrolysis and the consequent accessibility of the biomass to catalysts. Further, the accumulated formate intermediates have a poisoning effect on the catalysts, the desorption of which can be controlled by tuning the aqueous alkalinity. Overall, our strategy for the modification of TiO₂ with SO₄²⁻ and Ni_xS_y provides a new perspective for the concurrent acceleration of cellulose hydrolysis and increase of the number of hydrogen evolution sites for the efficient photocatalytic reformation of cellulose into H₂.

中文翻译：

---

硫化镍和硫酸盐物种对二氧化钛的轻松改性，以将纤维素光转化为氢

光催化纤维素重整被认为是可持续发展H ₂的潜在且负担得起的途径。然而，直接光重整仍然遭受挑战，例如纤维素的溶解度有限以及对贵金属催化活性的依赖性。在本文中，我们报道了通过单锅法用硫化镍（Ni _x S _y）和化学吸附的硫酸盐类（SO ₄ ^2-）改性的TiO ₂上纤维素向H _2的光转化。以3.02 mmol g ^-1  h ^-1的最大值实现了光催化氢释放速率的显着提高。在最初的3小时内，比P25高出近76倍，与Pt-P25相当。在系统研究的辅助下，提出硫化镍和硫酸盐的修饰协同作用显着提高了生物质转化的效率。具体而言，Ni _x S _y充当光催化H ₂产生的助催化剂，并且我们推断SO ₄ ^2-离子促进纤维素水解以及随之而来的生物量对催化剂的可及性。此外，积累的甲酸酯中间体对催化剂具有中毒作用，其解吸可通过调节含水碱度来控制。总体而言，我们的TiO ₂改性策略SO ₄ ^2-和Ni _x S _y的存在为纤维素的同时加速水解和氢释放位点数量的增加提供了新的视角，从而使纤维素有效地光催化重整为H ₂。