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In the future, hydrogen will be an important energy carrier and industrial raw material. Catalytic steam reforming of bio‐oils is a promising and economically viable technology for hydrogen production. However, during the reforming process, the catalysts are rapidly deactivated due to coke formation and sintering. Thus, maintaining the activity and stability of catalysts is the key issue in this process. Optimized operation conditions could extend the catalyst lifetime by affecting the coke morphology or promoting coke gasification. This article summarizes the recent developments in the field of catalytic steam reforming of bio‐oils, focusing on the operation conditions, the properties of the catalysts, and the effects of the catalyst supports. The expected insights into the catalytic steam reforming of bio‐oils will provide further guidance for hydrogen production from bio‐oils.

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Dealkaline lignin (DAL) was used as a carbon and sulfur source to prepare MoS2/Mo2C-based catalysts (Mo-DAL) with a facile impregnation-pyrolysis two-step process for the hydrogen production from the formic acid decomposition. Comparison of the catalytic performance of the Mo-DAL catalyst with the carbon black-based one (Mo2C-CB) revealed that the Mo-DAL catalyst exhibited superior activity to the Mo2C-CB catalyst. When 20 wt % of Mo was loaded on DAL, the catalyst produced hydrogen quite selectively (99.2%) with almost complete conversion of formic acid (97.4%) at 220 °C. In addition, the catalyst showed stable activity for at least 50 h in these conditions. This catalytic activity and hydrogen selectivity are superior to the other reported nonprecious metal catalysts. Since DAL contains not only carbon but also sodium and sulfur species, multiple kinds of active sites such as Na-intercalated MoS2, MoS2, and β-Mo2C were formed on the Mo-DAL catalysts. Investigation of additional effects of sulfur and sodium species on the Mo-CB catalyst revealed that both activity and selectivity for H2 production was improved by adding those elements. Thus, this study provides a new viewpoint to utilize waste dealkaline lignin as a precursor of sustainable and selective precious metal-free hydrogen production catalysts for formic acid decomposition.

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