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      Photocatalytic transformations of lignocellulosic biomass into chemicals

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          Abstract

          This review highlights recent advances in photocatalytic transformations of lignocellulosic biomass (polysaccharides and lignin) into chemicals (in particular organic oxygenates).

          Abstract

          As the largest renewable carbon resource, lignocellulosic biomass has great potential to replace fossil resources for the production of high-value chemicals, in particular organic oxygenates. Catalytic transformations of lignocellulosic biomass using solar energy have attracted much recent attention, because of unique reactive species and reaction patterns induced by photo-excited charge carriers or photo-generated reactive species as well as the mild reaction conditions, which may enable the precise cleavage of target chemical bonds or selective functionalisation of specific functional groups with other functional groups kept intact. Here, we present a critical review on recent advances in the photocatalytic transformation of lignocellulosic biomass with an emphasis on photocatalytic cleavage of C–O and C–C bonds in major components of lignocellulosic biomass, including polysaccharides and lignin, and the photocatalytic valorisation of some key platform molecules. The key issues that control the reaction paths and the reaction mechanism will be discussed to offer insights to guide the design of active and selective photocatalytic systems for biomass valorisation under mild conditions. The challenges and future opportunities in photocatalytic transformations of lignocellulosic biomass are also analysed.

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          Cellulose: fascinating biopolymer and sustainable raw material.

          As the most important skeletal component in plants, the polysaccharide cellulose is an almost inexhaustible polymeric raw material with fascinating structure and properties. Formed by the repeated connection of D-glucose building blocks, the highly functionalized, linear stiff-chain homopolymer is characterized by its hydrophilicity, chirality, biodegradability, broad chemical modifying capacity, and its formation of versatile semicrystalline fiber morphologies. In view of the considerable increase in interdisciplinary cellulose research and product development over the past decade worldwide, this paper assembles the current knowledge in the structure and chemistry of cellulose, and in the development of innovative cellulose esters and ethers for coatings, films, membranes, building materials, drilling techniques, pharmaceuticals, and foodstuffs. New frontiers, including environmentally friendly cellulose fiber technologies, bacterial cellulose biomaterials, and in-vitro syntheses of cellulose are highlighted together with future aims, strategies, and perspectives of cellulose research and its applications.
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            Visible light photocatalysis as a greener approach to photochemical synthesis.

            Light can be considered an ideal reagent for environmentally friendly, 'green' chemical synthesis; unlike many conventional reagents, light is non-toxic, generates no waste, and can be obtained from renewable sources. Nevertheless, the need for high-energy ultraviolet radiation in most organic photochemical processes has limited both the practicality and environmental benefits of photochemical synthesis on industrially relevant scales. This perspective describes recent approaches to the use of metal polypyridyl photocatalysts in synthetic organic transformations. Given the remarkable photophysical properties of these complexes, these new transformations, which use Ru(bpy)(3)(2+) and related photocatalysts, can be conducted using almost any source of visible light, including both store-bought fluorescent light bulbs and ambient sunlight. Transition metal photocatalysis thus represents a promising strategy towards the development of practical, scalable industrial processes with great environmental benefits.
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              Lignin valorization: improving lignin processing in the biorefinery.

              Research and development activities directed toward commercial production of cellulosic ethanol have created the opportunity to dramatically increase the transformation of lignin to value-added products. Here, we highlight recent advances in this lignin valorization effort. Discovery of genetic variants in native populations of bioenergy crops and direct manipulation of biosynthesis pathways have produced lignin feedstocks with favorable properties for recovery and downstream conversion. Advances in analytical chemistry and computational modeling detail the structure of the modified lignin and direct bioengineering strategies for future targeted properties. Refinement of biomass pretreatment technologies has further facilitated lignin recovery, and this coupled with genetic engineering will enable new uses for this biopolymer, including low-cost carbon fibers, engineered plastics and thermoplastic elastomers, polymeric foams, fungible fuels, and commodity chemicals.
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                Author and article information

                Contributors
                Journal
                CSRVBR
                Chemical Society Reviews
                Chem. Soc. Rev.
                Royal Society of Chemistry (RSC)
                0306-0012
                1460-4744
                September 1 2020
                2020
                : 49
                : 17
                : 6198-6223
                Affiliations
                [1 ]State Key Laboratory of Physical Chemistry of Solid Surfaces
                [2 ]Collaborative Innovation Center of Chemistry for Energy Materials
                [3 ]National Engineering Laboratory for Green Chemical Productions of Alcohols
                [4 ]Ethers and Esters
                [5 ]College of Chemistry and Chemical Engineering
                [6 ]State Key Laboratory of Catalysis
                [7 ]Dalian National Laboratory for Clean Energy
                [8 ]Dalian Institute of Chemical Physics
                [9 ]Chinese Academy of Sciences
                [10 ]Dalian 116023
                Article
                10.1039/D0CS00314J
                32756629
                37f9b984-1fb3-47c2-b121-7533a76f006b
                © 2020

                http://rsc.li/journals-terms-of-use

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