Keto-alcohols, which are traditionally produced from fossil resources with multisteps, are considered as important intermediates for diversified high-value-added fine chemical synthesis due to their involved carbonyl and hydroxyl groups. Herein, direct cellulose hydrogenolysis to C₃-C₄ keto-alcohol products (hydroxyacetone and 1(3)-hydroxy-2-butanone) was achieved over Ni-WO_x/C catalysts with an W/Ni atom ratio of 1.0–5.0. The keto-alcohol yield was proposed to strongly depend on the W/Ni ratio and the catalyst annealing temperature. The highest keto-alcohol yield of 63% was obtained at the optimal balance of basic/acidic WO_x species and metallic Ni. The introduction of Ni facilitated the formation of the basic W⁵⁺ sites, which enhanced the formation of basic sites at the Ni-WO_x interface. The synergistic effect between the basic W⁵⁺ and acidic oxygen vacancy (Vö) could activate the target C–O/C═O bonds, promoting the isomerization of glucose and C₃-C₄ aldehyde intermediates with the assistance of the interfacial Ni. The cooperative adsorption of the −OH and −C═O groups at the Ni-O-W-Vö interface stabilized the adjacent ketone and hydroxyl groups and kept the other hydroxyl groups for hydrogenolysis, obtaining the final C₃-C₄ keto-alcohols. This work expanded the application of cellulosic biomass, enabling the green and sustainable synthesis of the high-value C₃-C₄ keto-alcohol products using lignocellulosic biomass as a raw material.

中文翻译：

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Ni-WO _x / C催化剂上的纤维素氢解选择性生产C ₃ -C ₄酮醇

传统上由化石资源生产的多步合成酮醇由于涉及羰基和羟基，因此被认为是多样化高附加值精细化学合成的重要中间体。在此，在W / Ni原子比为1.0-5.0的Ni-WO _x / C催化剂上，将纤维素直接氢解为C ₃ -C ₄酮醇产物（羟基丙酮和1（3）-羟基-2-丁酮）。提出的酮醇产率强烈地取决于W / Ni比和催化剂退火温度。在碱性/酸性WO _x物种和金属Ni的最佳平衡下，酮醇的最高收率为63％。镍的引入促进了碱性W ⁵⁺的形成部位，这增强了Ni-WO _x界面上基本部位的形成。碱性W ⁵⁺与酸性氧空位（Vö）之间的协同作用可以激活目标C–O /C═O键，并借助界面Ni促进葡萄糖和C ₃ -C ₄醛中间体的异构化。Ni-OW-Vö界面上-OH和-C═O基团的协同吸附可稳定相邻的酮和羟基，并保留其他羟基进行氢解，获得最终的C ₃ -C ₄酮醇。这项工作扩大了纤维素生物质的应用范围，使绿色和可持续的高价值C ₃ -C合成成为可能。₄种以木质纤维素生物质为原料的酮醇产品。