Shi Yun
School of Chemistry & Chemical Engineering, Linyi University, Linyi 276000, China.
ACS Omega. 2020 Jul 16;5(29):18040-18049. doi: 10.1021/acsomega.0c01483. eCollection 2020 Jul 28.
In this study, the selectively catalytic hydrodeoxygenation of furfural (F-CHO) to 2-methylfuran (F-CH) on the CuNiCu(111) bimetallic catalyst surface was systematically investigated based on the periodic density functional theory, including dispersion correction. The formation of furfuryl alcohol (F-CHOH) involved two steps: the preferred first step was the hydrogenation of the branched C atom, forming the alkoxyl intermediate (F-CHO + H = F-CHO), and the second step was H addition to the alkoxyl group, resulting in furfuryl alcohol (F-CHO + H = F-CHOH), which was the rate-controlling step. In contrast, in the formation of 2-methylfuran, the first step was the dehydroxylation of furfuryl alcohol, resulting in alkyl (F-CH) and OH (F-CHOH = F-CH + OH) groups, the second step was the hydrogenation of F-CH (F-CH + OH + H = F-CH + OH), and the rate-controlling step was the hydrogenation of OH to HO (OH + H = HO). Based on the comparison results of the NiCuCu(111), Cu(111), and CuNiCu(111) surfaces, it was concluded that the catalytic performance of the catalyst was closely related to the adsorption structure of furfural. These results provide a basis for studying the intrinsic activity of NiCu catalysts during the hydrodeoxygenation of refined oxygenated compounds involving biomass-derived oils.
在本研究中，基于包含色散校正的周期性密度泛函理论，系统研究了糠醛（F-CHO）在CuNiCu(111)双金属催化剂表面选择性催化加氢脱氧生成2-甲基呋喃（F-CH）的过程。糠醇（F-CHOH）的形成涉及两个步骤：优先发生的第一步是支链C原子的加氢，形成烷氧基中间体（F-CHO + H = F-CHO），第二步是H加成到烷氧基上，生成糠醇（F-CHO + H = F-CHOH），这是速率控制步骤。相比之下，在2-甲基呋喃的形成过程中，第一步是糠醇的脱羟基反应，生成烷基（F-CH）和OH（F-CHOH = F-CH + OH）基团，第二步是F-CH的加氢反应（F-CH + OH + H = F-CH + OH），速率控制步骤是OH加氢生成HO（OH + H = HO）。基于NiCuCu(111)、Cu(111)和CuNiCu(111)表面的比较结果，得出催化剂的催化性能与糠醛的吸附结构密切相关的结论。这些结果为研究NiCu催化剂在涉及生物质衍生油的精制含氧化合物加氢脱氧过程中的本征活性提供了依据。
