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This work explores the generation of ethyl diazoacetate (EDA) and its cyclopropanation with isobutene under continuous flow conditions. In the first part, glycine ethyl ester hydrochloride, when subjected to a diazotization reaction, afforded EDA in good yields (70%) in flow. The formation of EDA was quantified by in-line infrared (IR) spectroscopy, which enabled fast and convenient optimization of the reaction conditions. In the second part, a screening of inexpensive and benign catalysts for the cyclopropanation of EDA with isobutene was carried out in batch. The latter can be obtained from bio-based sources, making this reaction especially appealing from a sustainability point of view. Subsequently, a preliminary investigation of flow conditions was conducted, showing great potential in a flow process involving the cyclopropanation of EDA in the future. Our investigations clear the path toward an environmentally-friendly preparation of cyclopropanes, which are in turn important building blocks for molecules such as Cilastatin, a key pharmaceutical deemed essential by the World Health Organization (WHO).

Continuous flow --- diazoesters --- isobutene --- safety --- Physique, chimie, mathématiques & sciences de la terre > Chimie

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Although the compression ignition (C.I.) engine, invented by Rudolf Diesel, was originally intended to work with pure vegetable oils as fuel, more than a century ago, it was adapted to be used with a fuel of fossil origin, obtained from oil. Therefore, there would be no technical difficulties in returning to the primitive design of using biofuels of renewable origin, such as vegetable oils. The main drawback is found in the one billion C.I. engines which are currently in use, which would have to undergo a modification in the injection system in order to adapt them to the higher viscosity of vegetable oils in comparison to that of fossil fuels. Thus, the gradual incorporation of biofuels as substitutes of fossil fuels is mandatory.

Research & information: general --- Technology: general issues --- biodiesel --- Ecodiesel --- selective ethanolysis --- sunflower oil --- Lipozyme RM IM --- Rhizomucor miehei --- ANOVA method --- response surface methodology --- gasoline oil blends --- castor oil --- biofuel --- diesel engine --- electricity generator --- smoke opacity --- Bacharach opacity --- straight vegetable oils (SVO) --- glycerol --- heterogeneous catalysis --- etherification --- isobutene --- tert-Butyl alcohol --- oxygenated fuel additives --- hydrogen production --- photo-reforming --- Ni/TiO2 --- transesterification --- Aspergillus terreus lipase --- polydopamine --- immobilization --- RSM --- fuel properties --- diethyl ether --- Bosch smoke number --- vacuum fractionation --- fuel --- fatty acids composition --- ethyl acetate --- straight vegetable oils --- vegetable oil blends --- biofuels --- soot emissions --- engine power output

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Catalysts are made of nanoparticles of metals, metal oxides, and other compounds that may act as active phases, support the latter, or a combination of both. The initial incentive to reduce as much as possible, up to the nano-scale, the size of the particles of active catalyst components is to maximize the surface area exposed to reactants, thus minimizing the specific cost per function and increasing the rate of conversion of feedstocks to products in relatively simple reactions. Nowadays, the interest in nanocatalyst developments has shifted to an emphasis on improving the selectivity of catalysts, allowing one to obtain desirable reactions in more complex synthetic processes. Thus, new generations of nanocatalysts should be designed at the molecular level to display well-defined structural characteristics, in terms of size, shapes, hierarchical porosity, and morphologies, as well as with controlled chemical composition. The development of efficient nanocatalysts supposes the characterization of their various surface active sites at the nanometer scale, which is focused on establishing synthesis–structure–performance relationships.

Research & information: general --- plasmonic photocatalyst --- metal nanoparticle --- N–TiO2 --- nanocomposites --- photocatalytic selective oxidation --- heterogeneous catalysis --- transition metal nitrides --- hydrogen production --- formic acid decomposition --- nickel catalyst --- calcium oxide promoter --- silica support --- Iron-based perovskites --- copper --- NO oxidation to NO2 --- NO2-assisted diesel soot oxidation --- soot oxidation under GDI exhaust conditions --- aqueous-phase reforming --- nickel --- ceria --- zirconia --- calcium --- yttrium --- methanol --- graphite --- reduced graphene oxide --- nitrogen-doped reduced graphene oxide --- exfoliation --- oxygen reduction reaction --- electrocatalysis --- UiO-66 --- iron --- cobalt --- nanocatalyst --- CO oxidation --- COProx --- methane --- oxidation catalysis --- formaldehyde --- magnetite iron oxide --- Fe3O4 --- palladium --- Pd --- silver --- Ag --- low-temperature activity --- nanocomposite --- Raman --- TG in air --- TG in hydrogen --- XRD --- electron microscopy --- EDS --- coordination polymers --- methane storage --- XRD crystallinity measurements --- mechanical shaping --- compaction --- VAM --- gas separation --- MOF pelletization --- catalysts --- dimerization --- isobutene --- olefins --- plasmonic photocatalyst --- metal nanoparticle --- N–TiO2 --- nanocomposites --- photocatalytic selective oxidation --- heterogeneous catalysis --- transition metal nitrides --- hydrogen production --- formic acid decomposition --- nickel catalyst --- calcium oxide promoter --- silica support --- Iron-based perovskites --- copper --- NO oxidation to NO2 --- NO2-assisted diesel soot oxidation --- soot oxidation under GDI exhaust conditions --- aqueous-phase reforming --- nickel --- ceria --- zirconia --- calcium --- yttrium --- methanol --- graphite --- reduced graphene oxide --- nitrogen-doped reduced graphene oxide --- exfoliation --- oxygen reduction reaction --- electrocatalysis --- UiO-66 --- iron --- cobalt --- nanocatalyst --- CO oxidation --- COProx --- methane --- oxidation catalysis --- formaldehyde --- magnetite iron oxide --- Fe3O4 --- palladium --- Pd --- silver --- Ag --- low-temperature activity --- nanocomposite --- Raman --- TG in air --- TG in hydrogen --- XRD --- electron microscopy --- EDS --- coordination polymers --- methane storage --- XRD crystallinity measurements --- mechanical shaping --- compaction --- VAM --- gas separation --- MOF pelletization --- catalysts --- dimerization --- isobutene --- olefins

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Catalysts are made of nanoparticles of metals, metal oxides, and other compounds that may act as active phases, support the latter, or a combination of both. The initial incentive to reduce as much as possible, up to the nano-scale, the size of the particles of active catalyst components is to maximize the surface area exposed to reactants, thus minimizing the specific cost per function and increasing the rate of conversion of feedstocks to products in relatively simple reactions. Nowadays, the interest in nanocatalyst developments has shifted to an emphasis on improving the selectivity of catalysts, allowing one to obtain desirable reactions in more complex synthetic processes. Thus, new generations of nanocatalysts should be designed at the molecular level to display well-defined structural characteristics, in terms of size, shapes, hierarchical porosity, and morphologies, as well as with controlled chemical composition. The development of efficient nanocatalysts supposes the characterization of their various surface active sites at the nanometer scale, which is focused on establishing synthesis–structure–performance relationships.

plasmonic photocatalyst --- metal nanoparticle --- N–TiO2 --- nanocomposites --- photocatalytic selective oxidation --- heterogeneous catalysis --- transition metal nitrides --- hydrogen production --- formic acid decomposition --- nickel catalyst --- calcium oxide promoter --- silica support --- Iron-based perovskites --- copper --- NO oxidation to NO2 --- NO2-assisted diesel soot oxidation --- soot oxidation under GDI exhaust conditions --- aqueous-phase reforming --- nickel --- ceria --- zirconia --- calcium --- yttrium --- methanol --- graphite --- reduced graphene oxide --- nitrogen-doped reduced graphene oxide --- exfoliation --- oxygen reduction reaction --- electrocatalysis --- UiO-66 --- iron --- cobalt --- nanocatalyst --- CO oxidation --- COProx --- methane --- oxidation catalysis --- formaldehyde --- magnetite iron oxide --- Fe3O4 --- palladium --- Pd --- silver --- Ag --- low-temperature activity --- nanocomposite --- Raman --- TG in air --- TG in hydrogen --- XRD --- electron microscopy --- EDS --- coordination polymers --- methane storage --- XRD crystallinity measurements --- mechanical shaping --- compaction --- VAM --- gas separation --- MOF pelletization --- catalysts --- dimerization --- isobutene --- olefins --- n/a