In this study, rare earth (RE) metal doped ZrO₂ was prepared by a surfactant-assisted coprecipitation/hydrothermal crystallization method and used to load Co as catalyst for the hydrogenation of aromatic carbonyl compounds in water. Furfural was hydrogenated to furfural alcohol in water with up to 95 mol % yield over Co/ZrLa_0.2O_x at 40 °C, 2 MPa H₂ in 10 h. The doping of rare earth metal oxide has three advantages: (I) it promotes the ZrO₂ to reach a small-sized, stable, and high-activity tetragonal phase zirconia and thus lead to a high specific surface area for metal loading; (II) it interacts with Co to reach an ultrasmall average particle size of 1.1 nm; and (III) it modifies the ZrO₂ surface to increase the amount of acidic sites for the adsorption of carbonyl feedstock. The adsorption experiment indicated a tight interaction between not only the carrier and C═O bond but also the Co clusters and C═O bond, which were of benefit for the hydrogenation of carbonyl groups. The surfactant addition during the carrier preparation improves the strong metal–support interactions (SMSI) to promote Co dispersion and stability. Various rare earth metals including La, Pr, Nd, and Ce could modify ZrO₂ with a similar mechanism. The as-prepared Co catalyst could also catalyze the selective hydrogenation of various aromatic aldehydes and ketones (such as 5-hydroxymethyl furfural, benzaldehyde, and acetophenone) in water, and 100% yield to corresponding alcohols was achieved. The catalyst remained stable and showed little deactivation during the recycling tests. This study not only presented a high-efficient, low-cost, and stable catalyst for the selective hydrogenation of various aromatic aldehydes and ketones but also give rise to an understanding of rare earth metal oxide doped ZrO₂ supported nano Co ternary catalysts.

中文翻译：

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ZrRE _n O _x上负载的钴纳米团簇用于水中生物质衍生的芳香醛和酮的选择性加氢

在这项研究中，稀土（RE）金属掺杂的ZrO ₂是通过表面活性剂辅助共沉淀/水热结晶法制备的，并用作负载Co的催化剂，用于在水中氢化芳族羰基化合物。在40°C，2 MPa H _{2的条件下，}于10小时内，将Co / ZrLa _0.2 O _x中的糠醛在水中氢化为糠醛醇，产率高达95 mol％。稀土金属氧化物的掺杂具有三个优点：（I）促进ZrO ₂达到小尺寸，稳定和高活性的四方相氧化锆，从而导致高的金属负载比表面积；（II）它与Co相互作用以达到1.1 nm的超小平均粒径；（III）修饰ZrO ₂表面增加酸性位点的数量，以吸附羰基原料。吸附实验表明，不仅载体与C═O键紧密结合，而且Co簇与C═O键紧密结合，有利于羰基的加氢。在载体制备过程中添加表面活性剂可改善强金属与载体之间的相互作用（SMSI），从而促进Co的分散和稳定性。La，Pr，Nd和Ce等多种稀土金属可以修饰ZrO ₂具有类似的机制。所制备的Co催化剂还可以催化在水中的各种芳族醛和酮（例如5-羟甲基糠醛，苯甲醛和苯乙酮）的选择性加氢，获得了相应醇的100％收率。催化剂在循环测试过程中保持稳定，几乎没有失活。这项研究不仅提出了一种高效，低成本，稳定的催化剂，用于各种芳香醛和酮的选择性加氢反应，而且使人们对稀土金属氧化物掺杂的ZrO ₂负载的纳米Co三元催化剂有了更深入的了解。