Efficient hydrogenolysis of 5-hydroxymethylfurfural over Ni-C3N4 catalysts

Utilization of biomass as the basic feedstock for the production and chemicals and energy storage has been demonstrated to be an important alternative to achieve sustainable society, which has attracted increasing interests in both academic and industrial communities for decades. 5-hydroxymethylfurfural (HMF), one of the most important bio-based platform compounds, could serve as a bridge feedstock between biomass resources and chemicals. It is possible to synthesize a series of high-value added chemicals from HMF through hydrogenation, oxidative dehydrogenation, esterification, hydrolysis, and etc., due to the presence of both aldehyde and hydroxymethyl groups. Among them, the selective hydrogenolysis of HMF to 2,5-dimethylfuran (DMF) as a potential liquid biofuel candidate has attracted extensive attention. As a biomass fuel, DMF can be used in internal combustion engines with higher compression ratios to improve fuel utilization efficiency as a result of its higher RON (Research octane number, 119) compared to those of commercial gasoline (90-100) and ethanol (110). In addition, DMF could be the important reactant for the direct synthesis of bio-based p-xylene (PX) by Diels-Alder reaction with ethylene. Compared to the conventional petroleum-based PX production process, such bio-based process shows high selectivity and avoids the complex separation procedure.

Recently, a research team led by Prof. Weimin Yang from East China University of Science and Technology and Sinopec Shanghai Research Institute of Petrochemical Technology Co., Ltd. reported the Ni-C₃N₄ catalyst supported on H₂ activated carbon (HC) with ultra-low Ni loading for the selective hydrogenolysis of HMF to DMF. The Ni-C₃N₄/HC catalyst achieves DMF yield of 94.2% with high sustainability (longer than 120 h life time in fixed-bed reactor), and exhibits remarkably high productivity (12.8 mmol_DMF⋅mmolNi-1 ⋅h^-1) across the temperatures of 100-200 °C, outperforming the recently reported all state-of-the-art Ni, Co and Cu-based catalysts, and is also comparable to noble metal catalysts (Ru, Pd and Pt). The combination of characterizations and theoretical calculations revealed that Ni₃N is the active component for the hydrogenolysis, and the C₃N₄ shells stabilize the Ni particles and prevent the agglomeration during the reaction. This work would advance the design of single non-noble metal catalysts for hydrogenation and hydrogenolysis reactions. The results were published in Chinese Journal of Catalysis (https://doi.org/10.1016/S1872-2067(24)60017-3).

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About the Journal

Chinese Journal of Catalysis is co-sponsored by Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Chinese Chemical Society, and it is currently published by Elsevier group. This monthly journal publishes in English timely contributions of original and rigorously reviewed manuscripts covering all areas of catalysis. The journal publishes Reviews, Accounts, Communications, Articles, Highlights, Perspectives, and Viewpoints of highly scientific values that help understanding and defining of new concepts in both fundamental issues and practical applications of catalysis. Chinese Journal of Catalysis ranks among the top one journals in Applied Chemistry with a current SCI impact factor of 15.7. The Editors-in-Chief are Profs. Can Li and Tao Zhang.

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