In coordination chemistry, catalytically active metal complexes in a zero- or low-valent state often adopt four-coordinate square-planar or tetrahedral geometry. By applying this principle, we have developed a stable Pt1 single-atom catalyst with a high Pt loading (close to 1 wt %) on phosphomolybdic acid(PMA)-modified active carbon. This was achieved by anchoring Pt on the four-fold hollow sites on PMA. Each Pt atom is stabilized by four oxygen atoms in a distorted square-planar geometry, with Pt slightly protruding from the oxygen planar surface. Pt is positively charged, absorbs hydrogen easily, and exhibits excellent performance in the hydrogenation of nitrobenzene and cyclohexanone. It is likely that the system described here can be extended to a number of stable SACs with superior catalytic activities.
Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed.
Mechanochemical synthesis emerged as the most advantageous, environmentally sound alternative to traditional routes for nanomaterials preparation with outstanding properties for advanced applications. Featuring simplicity, high reproducibility, mild/short reaction conditions and often solvent-free condition (dry milling), mechanochemistry can offer remarkable possibilities in the development of advanced catalytically active materials. The proposed contribution has been aimed to provide a brief account of remarkable recent findings and advances in the mechanochemical synthesis of solid phase advanced catalysts as opposed to conventional systems. The role of mechanical energy in the synthesis of solid catalysts and their application is critically discussed as well as the influence of the synthesis procedure on the physicochemical properties and the efficiency of synthesized catalysts is studied. The main purpose of this feature article is to highlight the possibilities of mechanochemical protocols in (nano)materials engineering for catalytic applications.
Novel biomass‐derived porous carbons are attractive candidates for the preparation of carbon‐supported catalysts with a wide range of catalytic applications. Such carbonaceous catalysts are environmentally benign and could provide a cost‐competitive advantage as compared to existing heterogeneous catalysts. Tunable surface properties of carbon materials and excellent physical properties (e.g., hydrophobicity, chemically inert nature, etc.) are compatible with diverse catalysis reactions including organic transformations, as well as electro‐ and photochemical processes in aqueous solutions. This contribution provides an overview on the utilization of different biomass feedstocks and/or biomass‐derived precursors for the synthesis of carbonaceous materials to design advanced catalytic systems and their emerging applications in catalysis.
Utilization of CO2 as feedstock to produce fine chemicals and renewable fuels is a highly promising field, which presents unique challenges in its implementation at scale. Heterogeneous catalysis with its simple operation and industrial compatibility can be an effective means of achieving this challenging task. This review summarizes the current developments in heterogeneous thermal catalysis for the production of carbon monoxide, alcohols and hydrocarbons from CO2. A detailed discussion is provided regarding structure-activity correlations between catalyst surface and intermediate species which can aid in rational design of future generation catalysts. Effects of active metal components, catalyst supports, and promoters are discussed in each section, which will guide researchers to synthesize new catalysts with improved selectivity and stability. Additionally, a brief overview regarding process design considerations has been provided. Future research directions are proposed with special emphasis on the application scope of new catalytic materials and possible approaches of increasing catalyst performance.
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