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Facile Modification of Titania with Nickel Sulfide and Sulfate Species for the Photoreformation of Cellulose into Hydrogen
Author(s) -
Hao Hongchang,
Zhang Ling,
Wang Wenzhong,
Zeng Shuwen
Publication year - 2018
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201800743
Subject(s) - cellulose , chemistry , catalysis , nickel sulfide , sulfate , sulfide , formate , photocatalysis , hydrolysis , inorganic chemistry , aqueous solution , hydrogen production , nickel , cellobiose , organic chemistry , cellulase
Photocatalytic cellulose reformation is regarded as a potential and affordable route for sustainable H 2 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 H 2 over TiO 2 that is modified with nickel sulfide (Ni x S y ) and chemisorbed sulfate species (SO 4 2− ) 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 x S y acts as a cocatalyst for photocatalytic H 2 production, and we infer that SO 4 2− 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 TiO 2 with SO 4 2− and Ni x S 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 H 2 .