Steam reforming of glycerol to produce hydrogen is considered to be the very promising strategy to generate clean and renewable energy. The incipient-wetness impregnation method was used to load Ni on the reducible carrier TiO₂ (P25). In the process of catalyst preparation, the interaction and electronic effect between metal Ni and support TiO₂ were adjusted by changing the calcination temperature, and then the activity and hydrogen production of glycerol steam reforming reaction (GSR) was explored. A series of modern characterizations including XRD, UV-vis DRS, BET, XPS, NH₃-TPD, H₂-TPR, TG, and Raman have been applied to systematically characterize the catalysts. The characterization results showed that the calcination temperature can contribute to varying degrees of influences on the acidity and basicity of the Ni/TiO₂ catalyst, the specific surface area, together with the interaction force between Ni and the support. When the Ni/TiO₂ catalyst was calcined at 600 °C, the Ni species can be produced in the form of granular NiTiO₃ spinel. Consequently, due to the moderate metal–support interaction and electronic activity formed between the Ni species and the reducible support TiO₂ in the NiO/Ti-600C catalyst, the granular NiTiO₃ spinel can be reduced to a smaller Ni⁰ at a lower temperature, and thus to exhibit the best catalytic performance.

CeO₂ nanosphere-supported nickel catalysts were prepared by the wetness impregnation method and employed for hydrogen production from glycerol steam reforming. The dried catalyst precursors were either reduced by H₂ after thermal calcination or reduced by H₂ directly without calcination. The catalysts that were reduced by H₂ without calcination achieved a 95% glycerol conversion at a reaction temperature of only 475 °C, and the catalytic stability was up to 35 h. However, the reaction temperature required of catalysts reduced by H₂ with calcination was 500 °C, and the catalysts was rapidly inactivated after 25 h of reaction. A series of physicochemical characterization revealed that direct H₂ reduction without calcination enhanced the concentration of oxygen vacancies. Thus, the nickel dispersion was improved, the nickel nanoparticle size was reduced, and the reduction of nickel was increased. Moreover, the high concentration of oxygen vacancy not only contributed to the increase of H₂ yield, but also effectively reduced the amount of carbon deposition. The increased active nickel surface area and oxygen vacancies synergistically resulted in the superior catalytic performance for the catalyst that was directly reduced by H₂ without calcination. The simple, direct hydrogen reduction method remarkably boosts catalytic performance. This strategy can be extended to other supports with redox properties and applied to heterogeneous catalytic reactions involving resistance to sintering and carbon deposition.