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Hexaniobate as a Recyclable Solid Base Catalyst to Activate C–H Bonds in Lignin Linkage Boosting the Production of Aromatic Monomers
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-04-03 , DOI: 10.1021/acscatal.2c06206
Jie Li 1 , Zhen Li 1 , Jing Dong 2 , Renbo Fang 1 , Yingnan Chi 1 , Changwen Hu 1
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-04-03 , DOI: 10.1021/acscatal.2c06206
Jie Li 1 , Zhen Li 1 , Jing Dong 2 , Renbo Fang 1 , Yingnan Chi 1 , Changwen Hu 1
Affiliation
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The targeting cleavage of lignin into value-added aromatic monomers has attracted increasing attention. Although the base-catalyzed depolymerization of lignin has been developed, the use of excess corrosive bases and their poor recyclability limit their industrial implementation. Herein, a catalytic amount of solid base K7HNb6O19 (KNb6) coupled with copper-modified graphitic carbon nitride (Cu/C3N4) shows enhanced catalytic performance for the oxidative cleavage of β-O-4 lignin linkages using molecular oxygen. Due to the synergetic effect between KNb6 and Cu/C3N4, 96% of the β-O-4 ketone model was converted under relatively mild conditions, and phenol (yield: 90%) and other aromatic monomers (yield: 90%) were obtained. Moreover, KNb6–Cu/C3N4 is robust, and its catalytic activity is basically maintained after five cycles. Experimental and theoretical studies (spectroscopic analysis, control experiments, kinetic study, density functional theory calculations, etc.) reveal that the surface basic O atoms of KNb6 can simultaneously activate the Cβ–H bond of β-O-4 ketone to promote the insertion of molecular oxygen, and subsequently, Cu/C3N4 catalyzes the selective cleavage of the Cα–Cβ bond. The catalysts were also active for the oxidative cleavages of other lignin models and oxidized organosolv lignin.
中文翻译：
己铌酸盐作为可回收固体碱催化剂激活木质素连接中的 C-H 键促进芳香单体的生产
将木质素靶向裂解成具有附加值的芳香族单体已引起越来越多的关注。尽管已经开发了碱催化的木质素解聚，但过量腐蚀性碱的使用及其较差的可回收性限制了其工业实施。在此，催化量的固体碱 K 7 HNb 6 O 19 (KNb 6 ) 与铜改性石墨碳氮化物 (Cu/C 3 N 4 ) 结合显示出增强的 β-O-4 木质素键氧化裂解催化性能使用分子氧。由于KNb 6与Cu/C 3 N 4的协同作用，96%的β-O-4酮模型在相对温和的条件下转化，得到苯酚（收率：90%）和其他芳族单体（收率：90%）。此外，KNb 6 –Cu/C 3 N 4具有较强的催化活性，循环5次后基本保持催化活性。实验和理论研究（光谱分析、对照实验、动力学研究、密度泛函理论计算等）表明，KNb 6的表面碱性O原子可以同时激活β-O-4酮的C β -H键，促进分子氧的插入，随后，Cu/C 3 N 4催化 C α –C的选择性裂解β键。该催化剂还对其他木质素模型和氧化有机溶剂木质素的氧化裂解具有活性。
更新日期：2023-04-03
中文翻译：
己铌酸盐作为可回收固体碱催化剂激活木质素连接中的 C-H 键促进芳香单体的生产
将木质素靶向裂解成具有附加值的芳香族单体已引起越来越多的关注。尽管已经开发了碱催化的木质素解聚，但过量腐蚀性碱的使用及其较差的可回收性限制了其工业实施。在此，催化量的固体碱 K 7 HNb 6 O 19 (KNb 6 ) 与铜改性石墨碳氮化物 (Cu/C 3 N 4 ) 结合显示出增强的 β-O-4 木质素键氧化裂解催化性能使用分子氧。由于KNb 6与Cu/C 3 N 4的协同作用，96%的β-O-4酮模型在相对温和的条件下转化，得到苯酚（收率：90%）和其他芳族单体（收率：90%）。此外，KNb 6 –Cu/C 3 N 4具有较强的催化活性，循环5次后基本保持催化活性。实验和理论研究（光谱分析、对照实验、动力学研究、密度泛函理论计算等）表明，KNb 6的表面碱性O原子可以同时激活β-O-4酮的C β -H键，促进分子氧的插入，随后，Cu/C 3 N 4催化 C α –C的选择性裂解β键。该催化剂还对其他木质素模型和氧化有机溶剂木质素的氧化裂解具有活性。
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