Catalytic Hydrogenolysis of Lignin into Serviceable Products.

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Accounts of Chemical Research Pub Date : 2025-02-18 Epub Date: 2025-02-05 DOI:10.1021/acs.accounts.4c00644
Shuizhong Wang, Xiancheng Li, Rumin Ma, Guoyong Song
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Abstract

ConspectusLignin, a major component of lignocellulosic biomass, accounts for nearly 30% of organic carbon on Earth, making it the most abundant renewable source of aromatic carbon. The valorization of lignin beyond low-value heat and power has been one of the foremost challenges for a long time. On the other hand, aromatic compounds, constituting a substantial segment of the chemical industry and projected to reach a market value of $382 billion by 2030, are predominantly derived from fossil resources, contributing to increased CO2 emissions. Integrating lignin into the aromatic chemical supply chain will offer a promising strategy to reduce the carbon footprint and boost the economic viability of biorefineries. Thus, depolymerizing lignin biopolymers into aromatic chemicals suitable for downstream processing is an important starting point for its valorization. However, owing to lignin's complexity and heterogeneity, achieving efficient and selective depolymerization that yields desirable, isolable aromatic monomers remains a significant scientific challenge.The structure of lignins varies significantly in terms of subunits and linkages across plant species, leading to considerable differences in their reactivity, in the distribution of resulting monomers, and in their subsequent utilization. In this context, this Account highlights our recent studies on the catalytic hydrogenolysis of lignin into serviceable products for preparing valuable materials, fuels, and chemicals. First, we designed a series of catalytic systems for lignin hydrogenolysis specifically tailored to the structural features of lignin from wood, grass, and certain seed coats. To reduce reliance on expensive commercial catalysts like Pd/C, Ru/C, and Pt/C, we advanced heterogeneous metal catalysts by shifting from high-loaded nanostructured metals to low-loaded, atomically dispersed metals and replacing precious metals with nonprecious alternatives. This approach significantly reduces the cost of catalysts, enhances their atomic economy, and improves their catalytic activity and/or selectivity. Then, using the developed catalysts, phenolic monomers tethering a distinct side chain were selectively generated from the hydrogenolysis of lignin (from various plants), achieving yields close to the theoretical maximum. The high selectivity allowed the separation and purification of monomeric phenols from lignin reaction mixtures readily. To gain deeper insights into the cleavage of lignin C-O bonds, we designed deuterium-incorporated β-O-4 mimics (dimers and one polymer) for a mechanistic study, which excluded the pathways involving the loss of linkage protons and led to the proposal of a concerted hydrogenolysis process for β-O-4 cleavage. Finally, to enable the utilization of depolymerized lignin phenolic monomers, unconventional feedstocks in the current chemical industry, we developed a series of methods to transform them into valuable bioactive molecules, functional materials, and high-energy fuels. Overall, these contributions opened new avenues for converting lignin into serviceable products, encompassing upstream processing and downstream applications.

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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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