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...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.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.22273065 and No.21673158)Science&Technology Commission of Shanghai Municipality(14DZ2261100).
基金the National Natural Science Foundation of China(22368014)the Guizhou Provincial S&T Project(ZK[2022]011,GCC[2023]011)+2 种基金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)。
文摘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.
