Hydrogen-transfer strategy in lignin refinery: Towards sustainable and versatile value-added biochemicals.

Lignin, the most prevalent natural source of polyphenols on Earth, offers substantial possibilities for the conversion into aromatic compounds, which is critical for attaining sustainability and carbon neutrality. The hydrogen-transfer method has garnered significant interest owing to its environmental compatibility and economic viability. The efficacy of this approach is contingent upon the careful selection of catalytic and hydrogen-donating systems that decisively affect the yield and selectivity of the monomeric products resulting from lignin degradation. This paper highlights the hydrogen-transfer technique in lignin refinery, with a specific focus on the influence of hydrogen donors on the depolymerization pathways of lignin. It delineates the correlation between the structure and activity of catalytic hydrogen-transfer arrangements and the gamut of lignin-derived biochemicals, utilizing data from lignin model compounds, separated lignin, and lignocellulosic biomass. Additionally, the paper delves into the advantages and future directions of employing the hydrogen-transfer approach for lignin conversion. In essence, this concept investigation illuminates the efficacy of the hydrogen-transfer paradigm in lignin valorization, offering key insights and strategic directives to maximize lignin's value sustainably.

Hydrogen-Transfer Reductive Catalytic Fractionation of Lignocellulose: High Monomeric Yield with Switchable Selectivity.

Lignin solubilization and in situ hydrogenolysis are crucial for reductive catalytic fractionation (RCF) of lignocellulose to aromatic monomers. In this study, we reported a typical hydrogen bond acceptor of choline chloride (ChCl) to tailor the hydrogen-donating environment of the Ru/C-catalyzed hydrogen-transfer RCF of lignocellulose. The ChCl-tailored hydrogen-transfer RCF of lignocellulose was conducted under mild temperature and low-pressure (<1 bar) conditions, which was applicable to other lignocellulosic biomass sources. We obtained an approximate theoretical yield of propylphenol monomer of 59.2 wt % and selectivity of 97.3 % using an optimal content of ChCl (10 wt %) in ethylene glycol at 190 °C for 8 h. When the content of ChCl in ethylene glycol was increased to 110 wt %, the selectivity of propylphenol switched toward propylenephenol (yield of 36.2 wt % and selectivity of 87.6 %). The findings in this work provide valuable information for transforming lignin from lignocellulose into value-added products.

Deep eutectic solvents boosting solubilization and Se-functionalization of heteropolysaccharide: Multiple hydrogen bonds modulation.

In this study, the favorable feasibility of deep eutectic solvents (DESs) in solubilization and functionalization of natural heteropolysaccharide was validated by experiments and density functional theory calculations. This revealed that choline chloride-based DES/DMSO (dimethyl sulfoxide) binary mixed solvents possessed more and stronger hydrogen bonding sites, facilitating the balance between disruption and reconstruction of hydrogen bonds within branched heteropolysaccharide from Artemisia sphaerocephala (PAS) and achieving efficient solubilization. Further, due to the full exposure and activation of polysaccharide hydroxyls, the efficiency of DES/DMSO-mediated novel Se-functionalization was substantially enhanced compared to the conventional selenylation methods. The derivative exhibited conversion to lower molecular mass with rigid solution conformation based on co-solvent effect and predominant acidic environment influence. This study offered a framework for exploring the potential of individualized polysaccharide functionalization by modulating DES constituents to achieve multiple controllabilities in terms of conversion efficiency and derivative structure.

Acid site-regulated solid acids for polysaccharide Se-functionalization: Structural explanations for high reactivity.

In this work, the application of acid site-regulated solid acids in Se-functionalization of polysaccharide is evaluated for the first time, which aimed to further improve reaction efficiency and realize environmentally friendly chemistry. A series prepared MxOy/HZSM-5 catalysts possesses standard crystal structure, large specific surface area, pore volume, aperture as well as strong acidity. An efficient substitution of seleno-group on polysaccharide backbone is promoted by regulating the acid site of solid acids (Se content up to 15,170.49 µg/g) compared with the conventional Se-functionalization method (1703 µg/g). Strong Lewis and Brønsted acid sites lead to the driving forces toward low molecular mass polysaccharide fragments, but the deletion of main monosaccharide components is not observed. In summary, it is proved that solid acid can be employed in acid-dependent polysaccharide Se-functionalization which will promote useful in expanding our understanding of how to further develop polysaccharide resources.