Catalytic Hydrogenolysis of Lignin into Propenyl-monophenol over Ru Single Atoms Supported on CeO2 with Rich Oxygen Vacancies

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-10-17 DOI:10.1021/acscatal.4c0318410.1021/acscatal.4c03184

Kaili Zhang*, Jianchun Jiang*, Zhe Liu, Jun Ye, Ran Tao, Hao Xu, Jingcong Xie, Jing Yang, Jian Zhao, Ning Zhang and Kui Wang*,

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Abstract

Lignin is the most abundant aromatic source of natural products, but developing efficient catalysts to depolymerize it into valuable monophenol with high yield and unique selectivity remains a challenge. Herein, we report a Ru single-atom catalyst (SAC) supported on rod CeO₂ with oxygen vacancies (Ov) for the depolymerization of birch dioxane acidolysis lignin (DAL). A near-theoretical maximum monophenol yield (14.8 wt %) with good selectivity to 4-n-propenyl guaiacol (51.4%), as well as high catalyst stability, was achieved. The calculated turnover (TON) was 387 mol_aromatics/mol_Ru, which is 55× higher than that of the Ru/C catalyst. The possible reaction for this catalyst was proposed by studying a series of lignin model compounds and in situ DRIFT measurements. The mechanism involves the cleavage of C_α–OH and C_β–O bonds to produce coniferyl alcohol, followed by the removal of γ-OH to generate 4-n-propenyl guaiacol. The effects of some key parameters like solvent, Ru content, temperature, reaction time, and H₂ pressure were also investigated in terms of monophenol yields and average molecular weight. This work provides an economically feasible method for the depolymerization of lignin into highly valuable monophenols.

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具有富氧空位的 CeO2 上支持的 Ru 单原子催化水解木质素生成丙烯基单苯酚

木质素是天然产品中最丰富的芳香族来源，但开发高效催化剂将其高产率、高选择性地解聚成有价值的单酚仍是一项挑战。在此，我们报告了一种以具有氧空位（Ov）的棒状 CeO2 为载体的 Ru 单原子催化剂（SAC），用于桦木二恶烷酸解木质素（DAL）的解聚。该催化剂的单苯酚产率接近理论最高产率（14.8 wt %），对 4-正丙烯基愈创木酚具有良好的选择性（51.4%），并且具有很高的稳定性。计算的转化率（TON）为 387 摩尔芳烃/摩尔 Ru，比 Ru/C 催化剂高 55 倍。通过研究一系列木质素模型化合物和原位 DRIFT 测量，提出了该催化剂的可能反应。反应机理包括 Cα-OH 和 Cβ-O 键裂解生成松柏醇，然后去除 γ-OH 生成 4-正丙烯基愈创木酚。该研究还考察了溶剂、Ru 含量、温度、反应时间和 H2 压力等关键参数对单苯酚产率和平均分子量的影响。这项研究为将木质素解聚成高价值的单酚提供了一种经济可行的方法。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.