Toward biomass-based single-atom catalysts and plastics: Highly active single-atom Co on N-doped carbon for oxidative esterification of primary alcohols

• Published in: Applied catalysis. B, Environmental Vol. 256; p. 117767
• Main Authors: Zhou, Hua, Hong, Song, Zhang, Hao, Chen, Yongting, Xu, Huanghui, Wang, Xueke, Jiang, Zheng, Chen, Shengli, Liu, Yun
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 05.11.2019; Elsevier BV
• Subjects: Alcohol; Alcohols; Aldehydes; Benzoates; Biomass; Biomass conversion; Biorefineries; Carbohydrates; Carbon; Catalysis; Catalysts; Coordination compounds; Copper; Dispersion; Esterification; Furans; Intermediates; Iron; Lignin; Metal-lignin complexes; Methyl benzoate; Nanoparticles; Nickel; Nitrogen; Oxidative esterification; Pesticides; Polymers; Renewable plastics; Single atom catalysts; Renewable plastics; Single-atom catalysts; Metal-lignin complexes; Biomass conversion; Oxidative esterification
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2019.117767

[Display omitted] •Coordination directed assembly of metal-lignin complexes.•Engineering metal-lignin coordination complexes to single-atom catalysts.•Atomically dispersed Co on N-doped carbon are active sites for oxidative esterification of primary alcohols.•Co SAs-N@C catalyst directly transforms HMF to building block of plastics. Supported single-atom catalysts (SACs) have attracted much attention as their advantageous performances in heterogenous catalysis. Here, we report a general synthesis approach to produce SACs on nitrogen-doped carbon (M SAs-N@C, where M = Fe, Co, Ni, Cu) by engineering bioinspired metal-lignin coordination complexes. The Co SAs-N@C catalyst shows extraordinary reactivity for the oxidative esterification of primary alcohols via aldehyde intermediates, achieving a high turnover frequency (TOF, 55.6 mol methyl benzoate mol−1Co h−1) for benzyle alcohol, which is approx. 18 times of Co nanoparticles. Experiments and theoretical calculations reveal that the atomically dispersed Co species in Co SAs-N@C are active sites for this reaction. As a proof-of-concept, we demonstrate an integrated biorefinery that lignin-based catalyst enables the effective transformation of carbohydrate-derived furans into building block of plastics and fragrance. Our technique not only provides a facile, low-cost and scalable method to atomically dispersed catalysts but also opens new avenue toward lignin valorization and biomass economy.