Yuan Man, Long Yu, Yang Jin, Hu Xiwei, Xu Dan, Zhu Yangyang, Dong Zhengping
College of Chemistry and Chemical Engineering, Gansu Provincial Engineering Laboratory for Chemical Catalysis, Laboratory of Special Function Materials and Structure Design of the Ministry of Education, Lanzhou University, Lanzhou, 730000, P. R. China.
ChemSusChem. 2018 Dec 11;11(23):4156-4165. doi: 10.1002/cssc.201802163. Epub 2018 Oct 26.
Fabrication of non-noble metal-based heterogeneous catalysts by a facile and cost-effective strategy for ecofriendly catalytic transfer hydrogenation (CTH) is of great significance for organic transformations. A cobalt@nitrogen-doped carbon (Co@NC) catalyst was prepared from renewable biomass-derived sucrose, harmless melamine, and earth-abundant Co(AcO) as the precursor materials by hydrothermal treatment and carbonization. Co nanoparticles (NPs) were coated with NC shells and uniformly embedded in the NC framework. The as-obtained Co@NC-600 (carbonized at 600 °C) catalyst exhibited excellent catalytic efficiency for CTH of various functionalized nitroarenes with formic acid (FA) as hydrogen donor in aqueous solution. The uniformly incorporated N atoms in the C matrix and the encapsulated Co NPs showed synergistic effects in the CTH reactions. A mechanistic analysis indicated that the protons from FA were activated by Co sites after being captured by N atoms, and then reacted with nitroarenes adsorbed on the surface of the catalysts to generate the corresponding aromatic amines. Moreover, the catalyst showed excellent durability and reusability without obvious decrease in activity even after five reaction cycles. Thus, the study reported herein provides a cost-effective, sustainable strategy for fabrication of biomass-derived non-noble metal-based catalysts for green and efficient catalytic transformations.
通过简便且经济高效的策略制备非贵金属基多相催化剂用于环境友好型催化转移氢化(CTH)对有机转化具有重要意义。以可再生生物质衍生的蔗糖、无害的三聚氰胺和储量丰富的Co(AcO)为前驱体材料,通过水热处理和碳化制备了钴@氮掺杂碳(Co@NC)催化剂。钴纳米颗粒(NPs)被NC壳包覆并均匀嵌入NC骨架中。所制备的Co@NC-600(在600℃碳化)催化剂在水溶液中以甲酸(FA)为氢供体对各种功能化硝基芳烃的CTH表现出优异的催化效率。C基质中均匀掺入的N原子和封装的Co NPs在CTH反应中表现出协同效应。机理分析表明,FA中的质子在被N原子捕获后被Co位点活化,然后与吸附在催化剂表面的硝基芳烃反应生成相应的芳香胺。此外,该催化剂表现出优异的耐久性和可重复使用性,即使经过五个反应循环后活性也没有明显降低。因此,本文报道的研究为制备用于绿色高效催化转化的生物质衍生非贵金属基催化剂提供了一种经济高效、可持续的策略。