The distinct role of the flexible polymer matrix in catalytic conversions over immobilised nanoparticles

Martinuzzi, Stefano; Cozzula, Daniela; Centomo, Paolo; Zecca, Marco; Müller, Tobias

doi:10.1039/c5ra05061h

Cited by 6 publications

(2 citation statements)

References 60 publications

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“…Thus, cellulose is converted to polyols over ruthenium supported on crosslinked polystyrene [149,151]. Swelling of the polymer [152] thereby facilitates access of the substrate to the catalytic sites.…”

Section: Ruthenium Catalysts In Cellulose Conversionmentioning

confidence: 99%

Hydrogenation and Hydrogenolysis with Ruthenium Catalysts and Application to Biomass Conversion

Müller¹

2022

Ruthenium - An Element Loved by Researchers

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With the rising emphasis on efficient and highly selective chemical transformations, the field of ruthenium-catalysed hydrogenation and hydrogenolysis reactions has grown tremendously over recent years. The advances are triggered by the detailed understanding of the catalytic pathways that have enabled researchers to improve known transformations and realise new transformations in biomass conversion. Starting with the properties of ruthenium, this chapter introduces the concept of the catalytic function as a basis for rational design of ruthenium catalysts. Emphasis is placed on discussing the principles of dissociative adsorption of hydrogen. The principles are then applied to the conversion of typical biomolecules such as cellulose, hemicellulose and lignin. Characteristic features make ruthenium catalysis one of the most outstanding tools for implementing sustainable chemical transformations.

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Section: Ruthenium Catalysts In Cellulose Conversionmentioning

confidence: 99%

Hydrogenation and Hydrogenolysis with Ruthenium Catalysts and Application to Biomass Conversion

Müller¹

2022

Ruthenium - An Element Loved by Researchers

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“…Moreover, it has already been reported that in resin catalysts, additional functional groups can favor the adsorption of the reagents with no appreciable increase of their swelling degree ("assisted adsorption"), provided they have some kind of affinity towards the molecules of the reagents. In that case, the "assisted adsorption" was based on hydrophobic interaction [50][51][52]. It can be therefore argued that also in AME 40-40 and AME 45-40 there is an "assisted adsorption" of the β-(1,4)-glucans sustained by the interactions of their molecules with hydroxyl and carboxylic groups.…”

Section: Catalytic Hydrolysismentioning

confidence: 99%

Gel-Type and Macroporous Cross-Linked Copolymers Functionalized with Acid Groups for the Hydrolysis of Wheat Straw Pretreated with an Ionic Liquid

et al. 2019

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Several sulfonated cross-linked copolymers functionalized with hydroxyl and carboxylic groups have been synthesized. The amount of the cross-linking monomer was tailored (from 4% up to 40%) to tune the resulting micro-and nano-morphologies, and two types of catalysts, namely, gel-type and macroreticular catalysts, were obtained. These copolymers were employed in the catalytic hydrolysis of wheat straw pretreated in 1-ethyl-3-methylimidazolium acetate to obtain sugars. Remarkably, the presence of additional oxygenated groups enhances the catalytic performances of the polymers by favoring the adsorption of β-(1,4)-glucans and makes these materials significantly more active than an acidic resin bearing only sulfonic groups (i.e., Amberlyst 70). In addition, the structure of the catalyst (gel-type or macroreticular) appears to be a determining factor in the catalytic process. The gel-type structure provides higher glucose concentrations because the morphology in the swollen state is more favorable in terms of the accessibility of the catalytic centers. The observed catalytic behavior suggests that the substrate diffuses within the swollen polymer matrix and indirectly confirms that the pretreatment based on dissolution/precipitation in ionic liquids yields a substantial enhancement of the conversion of lignocellulosic biomass to glucose in the presence of heterogeneous catalysts.Catalysts 2019, 9, 675 2 of 18 substrate [5]. In this way, the particle size can be reduced, the porosity can be improved, and the crystallinity of the cellulose can be altered. After fractioning its main components, e.g., cellulose, hemicellulose and lignin, biomass can be converted into a wide variety of industrial products, such as biofuels, biomaterials, cellulose pulps, cellulose nanofibers, oligosaccharides and a large number of by-products, in addition to lignin derivatives.Numerous studies have shown ionic liquids (ILs) to be effective at solubilizing lignocellulosic biomass, allowing for subsequent regeneration by precipitation with anti-solvents. Depending on the anti-solvent used, it is possible to achieve selective precipitation and separate the lignocellulosic biomass into its main components [6][7][8][9][10][11][12][13][14]. Among the most commonly employed ILs, 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) holds a privileged position due to its physico-chemical properties.The acid hydrolysis of the polysaccharide fractions of lignocellulosic biomass, which leads to monosaccharides that can be converted into fine chemicals or platform molecules used for industrial applications, can be performed in the presence of enzymes, homogeneous catalysts or heterogeneous catalysts [15][16][17][18][19][20][21]. During the last few years, increasing attention has been focused on the heterogeneous approach, which leads to several advantages in terms of the process design and plant costs [22][23][24][25]. Some of us have investigated using resins as catalysts or scaffolds in material chemistry [26][27][28][29][30]. These resins could be more...

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Conjugated Thermolysis of Metal-Containing Monomers: Toward Core–Shell Nanostructured Advanced Materials

Джардималиева

Uflyand

2019

J Inorg Organomet Polym

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The distinct role of the flexible polymer matrix in catalytic conversions over immobilised nanoparticles

Cited by 6 publications

References 60 publications

Hydrogenation and Hydrogenolysis with Ruthenium Catalysts and Application to Biomass Conversion

Hydrogenation and Hydrogenolysis with Ruthenium Catalysts and Application to Biomass Conversion

Gel-Type and Macroporous Cross-Linked Copolymers Functionalized with Acid Groups for the Hydrolysis of Wheat Straw Pretreated with an Ionic Liquid

Conjugated Thermolysis of Metal-Containing Monomers: Toward Core–Shell Nanostructured Advanced Materials

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