High hexitols selectivity in cellulose hydrolytic hydrogenation over platinum (Pt) vs. ruthenium (Ru) catalysts supported on micro/mesoporous carbon

Abstract

The “one-pot” hydrolyltic hydrogenation of cellulose towards C2-C6 sugar alcohols has been recognized as one of the most promising biomass valorization routes for the production of high added-value chemicals. In this work, we studied the performance of Ru and Pt catalysts supported on micro/mesoporous activated carbon, in the hydrolytic hydrogenation of microcrystalline and ball-milled cellulose, in neat water, at 180°C and at relatively low hydrogen pressure of 2MPa. The impact of metal loading (1–5wt.%), metal reduction method (H2 at 350°C or NaBH4) and acidification (sulfonation) of the AC support on cellulose conversion and selectivity to the various products were systematically addressed. It was shown that Pt is significantly more selective towards hexitols (sorbitol and mannitol) compared to Ru, in glucose-rich reaction media, such as those offered by the easily hydrolyzed ball-milled cellulose. For example, the 5wt%Pt/AC-SO3H catalyst afforded hexitols yield of 69.5wt.% (at 96.1% conversion) compared to 10.9wt.% (at 95.2% wt.% conversion) obtained by the corresponding Ru catalyst, the latter being also selective towards glycerol and propane-1,2-diol (propylene glycol). A relatively moderate metal loading, such as in 3wt.%Ru/AC-SO3H, was more favorable for hexitols production (44.5wt.% yield, at 94.8wt.% conversion) with Ru catalysts. These results were also verified by glucose hydrogenation experiments that were conducted at the same experimental conditions. Both Pt and Ru exhibited relatively high glucose hydrogenation activity towards hexitols, versus retro-aldol reactions that lead directly to smaller C2–C4 compounds, while the difference in the final product yields between the two metals was attributed to the higher hexitols hydrogenolysis (CC cleavage) reactivity of Ru. HRTEM data showed the formation of metallic crystalline Pt and Ru nanoparticles (≤4nm, depending on loading) as well as of amorphous oxygen-rich M(O)xδ+ phases, which were also confirmed by the XPS data. The presence of these phases which may be a source of acidity, as well as the bacisity of the parent AC used in this study, were mainly responsible for inducing isomerization, retro-aldol and dehydration reactions leading eventually to increased glycerol and propylene glycol selectivity, as was observed for both low-metal catalysts, i.e. 1wt.% Pt or Ru/AC.