p-n heterojunction of nickel oxide on titanium dioxide nanosheets for hydrogen and value-added chemicals coproduction from glycerol photoreforming

Selective photocatalysis to simultaneously produce sustainable hydrogen and value-added chemicals from biomass or biomass derivates is attracting extensive investigations. However, the lack of bifunctional photocatalyst greatly limits the possibility to realize the "one stone kills two birds" scenario. Herein, anatase titanium dioxide (TiO2) nanosheets are rationally designed as the n-type semiconductor, combining with nickel oxide (NiO) nanoparticles, the p-type semiconductor, resulting in the formation of a p-n heterojunction structure. The shorten charge transfer path and the spontaneous formation of p-n heterojunction endow the photocatalyst with efficient spatial separation of photogenerated electrons and holes. As a result, TiO2 accumulates electrons for efficient hydrogen generation while NiO collects holes to selectively oxidize glycerol into value-added chemicals. The results showed that by loading 5% nickel into the heterojunction caused a remarkable rise in the generation of hydrogen (H2). The combination of NiO-TiO2 created 4000 µmolh-1g-1 of H2, which is 50% greater than the H2 production from pure nanosheet TiO2 and 63 times more than the H2 production from commercial nanopowder TiO2. Then, by changing loading amount of Ni, it is found that when 7.5 % of Ni is loaded the highest amount of hydrogen production achieved, 8000 µmolh-1g-1. By employing best sample (S3), 20 % of glycerol converted to value added products, glyceraldehyde and dihydroxyacetone. The feasibility study revealed that glyceraldehyde generates the largest portion of yearly earnings at 89%, while dihydroxyacetone and H2 account for 11% and 0.03% of the annual revenue, respectively. This work provides a good example to simultaneously produce green hydrogen and valuable chemicals with the rational design of dually functional photocatalyst.