Synergy of heterogeneous Co/Ni dual atoms enabling selective C-O bond scission of lignin coupling with in-situ N-functionalization  

作　　者：Baoyu Wang Jinshu Huang Hongguo Wu Ximing Yan Yuhe Liao Hu Li 

机构地区：[1]National Key Laboratory of Green Pesticide,Key Laboratory of Green Pesticide&Agricultural Bioengineering,Ministry of Education,State-Local Joint Laboratory for Comprehensive Utilization of Biomass,College of Pharmacy&Center for R&D of Fine Chemicals,Guizhou University,Guiyang 550025,Guizhou,China [2]Guangxi Key Laboratory of Green Chemical Materials and Safety Technology,Beibu Gulf University,Qinzhou 535011,Guangxi,China [3]Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences,Guangzhou 510640,Guangdong,China

出　　处：《Journal of Energy Chemistry》2024年第5期16-25,共10页能源化学（英文版）

基　　金：the National Natural Science Foundation of China(22368014);the Guizhou Provincial S&T Project(ZK[2022]011,GCC[2023]011);the Natural Science Foundation of Guangxi Zhuang Autonomous Region(2023JJA120098);the Guangxi Key Laboratory of Green Chemical Materials and Safety Technology,the Beibu Gulf University(2022SYSZZ02,2022ZZKT04);the Guizhou Provincial Higher Education Institution Program(Qianjiaoji[2023]082)。

摘　　要：Selective cleavage of Csp^(2)-OCH_(3)bond in lignin without breaking other types of C-O bonds followed by N-functionalization is fascinating for on-purpose valorization of biomass.Here,a Co/Ni-based dual-atom catalyst CoNiDA@NC prepared by in-situ evaporation and acid-etching of metal species from tailor-made metal–organic frameworks was efficient for reductive upgrading of various lignin-derived phenols to cyclohexanols(88.5%–99.9%yields),which had ca.4 times higher reaction rate than the single-atom catalyst and was superior to state-of-the-art heterogeneous catalysts.The synergistic catalysis of Co/Ni dual atoms facilitated both hydrogen dissociation and hydrogenolysis steps,and could optimize adsorption configuration of lignin-derived methoxylated phenols to further favor the Csp^(2)-OCH_(3)cleavage,as elaborated by theoretical calculations.Notably,the CoNi_(DA)@NC catalyst was highly recyclable,and exhibited excellent demethoxylation performance(77.1%yield)in real lignin monomer mixtures.Via in-situ cascade conversion processes assisted by dual-atom catalysis,various high-value N-containing chemicals,including caprolactams and cyclohexylamines,could be produced from lignin.

关 键 词：Biomass conversion Heterogeneous catalysis LIGNIN Dual-atom catalyst Selective C-ocleavage 

分 类 号：O641.1[理学—物理化学]