Natural attapulgite supported nano-Ni catalysts for the efficient reductive amination of biomass-derived aldehydes and ketones  

作　　者：Jia Zhang Jian Yang Xuemei Li Bin Mu Hailong Liu Chungu Xia Aiqin Wang Zhiwei Huang 

机构地区：[1]State Key Laboratory for Oxo Synthesis and Selective Oxidation,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China [2]Key Laboratory of Clay Mineral Applied Research of Gansu Province,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China [3]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Green Synthesis and Catalysis》2024年第1期42-50,共9页绿色合成与催化（英文）

基　　金：This work was financially supported by the National Natural Science Foundation of China(Nos.21872155 and 22102198);the Strategic Pilot Science and Technology Project of the Chinese Academy of Sciences(No.XDA21010700);the Western Young Scholar Program of the Chinese Academy of Sciences and the Open Project of Key Laboratory of Clay Mineral Applied Research of Gansu Province.

摘　　要：The efficient synthesis of useful primary amines via reductive amination of biomass-based aldehydes and ketones over earth-abundant base metal catalysts is an attractive biomass value-adding technology yet facing lots of challenges.Herein,natural attapulgite(ATP)was applied as support for the fabrication of active Ni catalysts with different Ni loadings(5–30 wt%)by the deposition-precipitation method.The Ni/ATP-550 catalyst with 10–15 wt%Ni loadings was found to present the highest catalytic performance for the synthesis of valuable 5-amino-1-pentanol(5-AP)via reductive amination of biofurfural-derived 2-hydroxytetrahydropyran among a variety of commonly used oxide supports loaded Ni catalysts,as well as ATP supported nickel catalysts with other loadings,achieving 5-AP yield up to 94%.The intrinsic activity of the Ni/ATP catalysts was found to depend strongly on the Ni^(0) crystallite size and Ni^(0) fraction of the catalysts,which generally increased with increasing Ni^(0) crystallite size and fraction,owing probably to the hydrogenation of imine intermediate is a structure-sensitive reaction.The efficient 10Ni/ATP-550 catalyst also exhibited good activity and stability in the reductive amination of several other biomass-derived aldehydes and ketones to their corresponding primary amines with good to excellent yields(81%–99%).This work provided a clean and efficient natural ATP-supported non-noble metal nickel-based catalytic system for the reductive amination of aldehydes and ketones to synthesize high-value-added primary amines,which could be a promising candidate for the industrial production of amines.

关 键 词：ATTAPULGITE Nano-Ni catalyst Reductive amination 5-Amino-1-pentanol Structure-activity relationship 

分 类 号：O62[理学—有机化学]