Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal–support interaction, and metal–reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results o...

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

Conversion of Biomass into Chemicals over Metal Catalysts

The coupling of aryl or vinyl halides with terminal acetylenes catalysed by palladium and other transition metals, commonly termed as Sonogashira cross-coupling reaction, is one of the most important and widely used sp2–sp carbon–carbon bond formation reactions in organic synthesis, frequently employed in the synthesis of natural products, biologically active molecules, heterocycles, molecular electronics, dendrimers and conjugated polymers or nanostructures. This critical review focuses on developments in the Sonogashira reaction achieved in recent years concerning catalysts, reaction conditions and substrates (352 references).

Recent advances in Sonogashira reactions

The production of future transportation fuels and chemicals requires the deployment of new catalytic processes that transform biomass into valuable products under competitive conditions. Furfural has been identified as one of the most promising chemical platforms directly derived from biomass. With an annual production close to 300 kTon, furfural is currently a commodity chemical, and the technology for its production is largely established. The aim of this review is to discuss the most relevant chemical routes for converting furfural to chemicals, biofuels, and additives. This review focuses not only on industrially produced chemicals derived from furfural, but also on other not yet commercialised products that have a high potential for commercialisation as commodities. Other chemicals that are currently produced from oil but can also be derived from furfural are also reviewed. The chemical and engineering aspects such as the reaction conditions and mechanisms, as well as the main achievements and the challenges still to come in the pursuit of advancing the furfural-based industry, are highlighted.

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Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels

Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass

A sustainable process for the production of γ-valerolactone by hydrogenation of biomass-derived levulinic acid

Levulinic acid (LA) is one of the top bio-based platform molecules that can be converted into many valuable chemicals. It can be produced by acid catalysis from renewable resources, such as sugars, lignocellulosic biomass and waste materials, attractive candidates due to their abundance and environmentally benign nature. The LA transition from niche product to mass-produced chemical, however, requires its production from sustainable biomass feedstocks at low costs, adopting environment-friendly techniques. This review is an up-to-date discussion of the literature on the several catalytic systems that have been developed to produce LA from the different substrates. Special attention has been paid to the recent advancements on starting materials, moving from simple sugars to raw and waste biomasses. This aspect is of paramount importance from a sustainability point of view, transforming wastes needing to be disposed into starting materials for value-added products. This review also discusses the strategies to exploit the solid residues always obtained in the LA production processes, in order to attain a circular economy approach.

https://www.mdpi.com/2073-4344/6/12/196/pdf

New Frontiers in the Catalytic Synthesis of Levulinic Acid: From Sugars to Raw and Waste Biomass as Starting Feedstock

The hydrothermal conversion of waste biomass to levulinic acid was investigated in the presence of homogeneous acid catalysts. Different cheap raw materials (poplar sawdust, paper mill sludge, tobacco chops, wheat straw, olive tree pruning) were employed as substrates. The yields of levulinic acid were improved by optimization of the main reaction parameters, such as type and amount of acid catalyst, temperature, duration, biomass concentration, and electrolyte addition. The catalytic performances were also improved by the adoption of microwave irradiation as an efficient heating method, allowing significant energy and time savings. The hydrothermal conversions of inulin and wheat straw were carried out in the presence of niobium phosphate, which up to now have never been employed in these reactions. The preliminary results appeared to be in need of further optimization.

https://ojs.cnr.ncsu.edu/index.php/BioRes/article/download/BioRes_07_2_1824_RaspolliGalletti_ADLLN_Levulinic_Acid_Prodn_Waste_Biomass/1462

Claudia Antonetti

Papers

A sustainable process for the production of γ-valerolactone by hydrogenation of biomass-derived levulinic acid

New Frontiers in the Catalytic Synthesis of Levulinic Acid: From Sugars to Raw and Waste Biomass as Starting Feedstock

Levulinic acid production from waste biomass

From giant reed to levulinic acid and gamma-valerolactone: A high yield catalytic route to valeric biofuels

From giant reed to levulinic acid and gamma-valerolactone: a high yield catalytic route to valeric biofuels