High-Efficiency Dual-Site Biomimetic Catalyst for Lignin Depolymerization

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-01-28 DOI:10.1021/acscatal.4c0711310.1021/acscatal.4c07113

Wenzhi Jiang, Qifeng Li, Meifang Cao, Hongming Lou, Zhixian Li* and Xueqing Qiu*,

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引用次数: 0

Abstract

Developing biomimetic catalysts with enhanced catalytic efficiency is a promising strategy to address the challenges of lignin depolymerization under mild conditions. In this study, we designed a dual-site biomimetic catalyst, Pd@Ce-PZDC, engineered to emulate the lignin-degrading functions of natural laccase and peroxidase enzymes, thereby facilitated lignin depolymerization. The laccase-like activity of Pd@Ce-PZDC exhibited a catalytic efficiency (V_max/K_m) of 1.3 × 10^–2 min^–1, which is 3.14 times higher than that of natural laccase and 1.62 times greater than that of the single-site bioinspired laccase MOF catalyst Ce-PZDC. Its peroxidase-like activity, assessed with TMB and H₂O₂, is 5.6 and 11.2 times higher, respectively, than that of Ce-PZDC. Density Functional Theory (DFT) calculations indicated a synergistic dual-site effect where Pd NPs activate Ce(IV) within the MOF, imparting it with laccase-like activity akin to Ce(III), thereby increasing the number of active sites and enhancing overall catalytic efficiency. Under mild conditions (60 °C in aqueous solution), Pd@Ce-PZDC demonstrated high efficiency in the oxidative depolymerization of birch lignin, selectively cleaving β-O-4 and β–β linkages. This resulted in a reduction in molecular weight of lignin and produced aromatic monomers (approximately 13.0%), including vanillin, syringaldehyde, and vanillic acid. This dual-site synergistic strategy offers a promising avenue for valorization of lignin and the development of effective catalytic systems for biomass conversion.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.