Tuning the Acid/Metal Balance of Carbon Nanofiber-Supported Nickel Catalysts for Hydrolytic Hydrogenation of Cellulose

Carbon nanofibers (CNFs) are a class of graphitic support materials with considerable potential for catalytic conversion of biomass. Earlier, we demonstrated the hydrolytic hydrogenation of cellulose over reshaped nickel particles attached at the tip of CNFs. The aim of this follow‐up study was to find a relationship between the acid/metal balance of the Ni/CNFs and their performance in the catalytic conversion of cellulose. After oxidation and incipient wetness impregnation with Ni, the Ni/CNFs were characterized by various analytical methods. To prepare a selective Ni/CNF catalyst, the influences of the nature of oxidation agent, Ni activation, and Ni loading were investigated. Under the applied reaction conditions, the best result, that is, 76 % yield in hexitols with 69 % sorbitol selectivity at 93 % conversion of cellulose, was obtained on a 7.5 wt % Ni/CNF catalyst prepared by chemical vapor deposition of CH4 on a Ni/γ‐Al2O3 catalyst, followed by oxidation in HNO3 (twice for 1 h at 383 K), incipient wetness impregnation, and reduction at 773 K under H2. This preparation method leads to a properly balanced Ni/CNF catalyst in terms of Ni dispersion and hydrogenation capacity on the one hand, and the number of acidic surface‐oxygen groups responsible for the acid‐catalyzed hydrolysis on the other. Hanging in the balance: With the potential of cellulose as an alternative resource in the production of sugar alcohols, developing inexpensive non‐precious catalysts is an essential requirement to reduce the overall system cost. This study evaluates the impact of preparation conditions on the acid/metal balance (see picture) and catalytic performance of a series of well‐characterized carbon nanofiber supported nickel catalysts.