Abstract
The strong interaction of higher transition metal oxides with inorganic non-metals can be promising for generating highly acidic three-dimensional materials by design. A comprehensive controlled acidity of heteropolyacid-like catalyst and interpretation of the microstructure and mechanism of the formation of a versatile heterogeneous solid acid catalyst, HPW4Mo10Ox has been heterogenized by biomass-derived cystine as organic linkers to control the acidity of as-synthesized materials, which have greater acidity and complexity in separation from the reaction mixture. The new and unique results obtained in catalysis done in biphasic reaction. Cystine binds to the surface of HPW4Mo10Ox, and the topotactic transition occurred, change the morphology and lattice parameter. We described here a sustainable transformation of highly acidic (0.84 mmol g−1) heteropoly acid (HPW4Mo10Ox) to cystine anchored on the active surface of the heteropoly acid and controlled the acidity (0.63 mmol g−1) and heterogenized the materials. As synthesized materials have been showing that for the direct formation of alkyl levulinate and furanics intermediate from carbohydrates. HPW4Mo10Ox and HPW4Mo10Ox-Cys, act as acidic catalyst, and catalyse the mono- and disaccharides that are dissolved in primary and secondary alcohols to alkyl levulinate (AL) and alkyl methylfurfural at 170 °C under microwave irradiation with glucose as the substrate, AL yield reaches 62% with 84.95% selectivity. The catalyst can be easily recovered by filtration and minimum five times reused after calcination without any substantial change in the product selectivity. The analytical analysis of as-synthesis materials done by NH3-TPD, BET, XRD, FESEM, TEM, HRTEM, FTIR, ATR, TGA, DTA to stabilized the morphology and acidity controlled mechanism.
Highlights
IntroductionFossil-based petroleum products are currently major, gigantic players in chemicals industry for the synthesis of chemicals, fuels, and materials
Replacement of mineral acids, costly heterogeneous metal oxides and precious acidic ionic liquids by low-cost non-noble solid acid catalysts for the selective dehydration and rehydration of carbohydrates to alkyl levulinates and furanic intermediates holds tremendous promise for the clean and carbon neutral synthesis of biofuels and chemicals.[1]
Our approach to heterogenized and controlling the acidity of heteropoly acid (HPA) affords various advantages compared to conventional heterogeneous catalysis: (i) the catalyst system can show greater reactivity and selectivity like a homogeneous catalyst; (ii) unlike most homogeneous catalysts with comparable performance, the heterogenized HPW4Mo10Ox-Cys can be recycled; (iii) signi cantly enhanced the selectivity of the desired product and stopped the rehydration of furanics
Summary
Fossil-based petroleum products are currently major, gigantic players in chemicals industry for the synthesis of chemicals, fuels, and materials. Direct utilization of lignocellulosic biomass has hurdles of its over-functionality and excess of oxygen In this regards chemist and engineered designed environmentally sound reaction-design, cost-effective, and energy saving and atom efficiency chemical processes.[12] Design of such type of process, catalyst always lined center-point to minimized the hazardous waste, increased the atom-efficiency and selectivity of product in an energy-efficient manner. These should be capable of efficient dehydration and etheri cation of carbohydrate to biofuels which could help us in our future design of biobased fuels and chemicals at moderate cost and environmentally friendly manner
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