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α,ß-Unsaturated aldehydes are important building blocks for the synthesis of a wide range of chemicals, including polymers. The synthesis of these molecules from cheap feedstocks such as alkenes remains a scientific challenge, mainly due to the low reactivity of alkenes. Here we report a selective and metal-free access to α,ß-unsaturated aldehydes from alkenes with formaldehyde. This reaction is catalyzed by dimethylamine and affords α,ß-unsaturated aldehydes in yields of up to 80 %. By combining Density Functional Theory (DFT) calculations and experiments, we elucidate the reaction mechanism which is based on a cascade of hydride transfer, hydrolysis and aldolization reactions. The reaction can be performed under very mild conditions (30-50 °C), in a theoretically 100 % carbon-economical fashion, with water as the only by-product. The reaction was successfully applied to non-activated linear 1-alkenes, thus opening an access to industrially relevant α,ß-unsaturated aldehydes from cheap and widely abundant chemicals at large scale.
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Oil foams stabilized by surface-active catalytic particles bearing fluorinated chains and Pd nanoparticles allowed fast and efficient aerobic oxidation of a variety of aromatic and aliphatic alcohols compared to bulk catalytic systems at ambient O2 pressure. High foam stability was achieved at low particle concentration (<1 wt %) provided that the contact angle locates in the range 41°-73°. The catalytic performance was strongly affected by the foaming properties, with 7-10 times activity increase in pure O2 compared to nonfoam systems. Intermediate foam stability was required to achieve good catalytic activity, combining large interfacial area and high gas exchange rate. Particles were conveniently recycled with high foamability and catalytic efficiency maintained for at least seven consecutive runs.
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A designed N-heterocyclic carbene (NHC) catalyst was covalently anchored on a range of mesoporous and hierarchical supports, to study the influence of pore size in the benzoin condensation of furfural. The structural and spectroscopic characteristics of the anchored catalysts were investigated, also with the help of molecular dynamics simulations, in order to rationalize the degree of stability and recyclability of the heterogenized organocatalysts. Quantitative yields (99 %) and complete recyclability were maintained after several cycles, vindicating the design rationale.
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Benzoína , Furaldeído , Benzoína/química , Benzimidazóis , Simulação de Dinâmica Molecular , CatáliseRESUMO
Pickering emulsions, foams, bubbles, and marbles are dispersions of two immiscible liquids or of a liquid and a gas stabilized by surface-active colloidal particles. These systems can be used for engineering liquid-liquid-solid and gas-liquid-solid microreactors for multiphase reactions. They constitute original platforms for reengineering multiphase reactors towards a higher degree of sustainability. This Review provides a systematic overview on the recent progress of liquid-liquid and gas-liquid dispersions stabilized by solid particles as microreactors for engineering eco-efficient reactions, with emphasis on biobased reagents. Physicochemical driving parameters, challenges, and strategies to (de)stabilize dispersions for product recovery/catalyst recycling are discussed. Advanced concepts such as cascade and continuous flow reactions, compartmentalization of incompatible reagents, and multiscale computational methods for accelerating particle discovery are also addressed.
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The catalytic hydroarylation of nonactivated alkenes with aniline is a reaction of high interest, aiming at providing C-functionalized aniline derivatives that are important precursors for the fabrication of polyurethanes. However, this reaction remains a longstanding goal of catalysis, as it requires one to simultaneously address two important goals: (1) the very low reactivity of nonactivated alkenes and (2) control of the hydroarylation/hydroamination selectivity. As a result, the hydroarylation of aniline is mostly restricted to activated alkenes (i.e., featuring ring strain, conjugation, or activation with electron-donating or -withdrawing groups). Here we show that the combination of bismuth triflate and hexafluoroisopropanol (HFIP) leads to the formation of highly active catalytic species capable of promoting the hydroarylation of various nonactivated alkenes, such as 1-octene, 1-heptene, and 1-undecene, among others, with aniline with high selectivity (71-92%). Through a combined experimental and computational investigation, we propose a reaction pathway where HFIP stabilizes the rate-determining transition state through a H-bond interaction with the triflate anion, thus assisting the acid catalyst in the hydroarylation of nonactivated alkenes. From a practical point of view, this work opens a catalytic access to C-functionalized aniline derivatives from two cheap and abundant feedstocks in a 100% atom-economical fashion.
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Among the best-performing homogeneous catalysts for the direct amination of activated secondary alcohols with electron-poor amine derivatives, metal triflates, such as aluminum triflate, Al(OTf)3 , stand out. Herein we report the extension of this reaction to electron-rich amines and activated primary alcohols. We provide detailed insight into the structure and reactivity of the catalyst under working conditions in both nitromethane and toluene solvent, through experiment (cyclic voltammetry, conductimetry, NMR spectroscopy), and density functional theory (DFT) simulations. Competition between aniline and benzyl alcohol for Al in the two solvents explains the different reactivities. The catalyst structures predicted from the DFT calculations were validated by the experiments. Whereas a SN 1-type mechanism was found to be active in nitromethane, we propose a SN 2 mechanism in toluene to rationalize the much higher selectivity observed when using this solvent. Also, unlike what is commonly assumed in homogeneous catalysis, we show that different active species may be active instead of only one.
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Pickering emulsions offer a promising platform for conducting interfacial reactions between immiscible reagents. Despite the significant progress in the engineering of amphiphilic catalysts for such reactions, the mechanism behind their enhanced activity is still poorly understood. Herein, using the glycerol/dodecanol system as a case study, we conducted a combined meso- and microscale study of Pickering emulsions stabilized by amphiphilic silica nanoparticles bearing acid centers by marrying dissipative particle dynamics simulations with emulsification experiments. The optimal surface properties of the silica particles in terms of length and density of alkyl chains were identified, matching the experimental results. The local distribution of glycerol and dodecanol near the acid centers was ascertained, unraveling potential reactivity zones near the catalytic acid centers due to an enhanced nanomixing between glycerol and dodecanol.
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Pickering emulsions combining surface-active and catalytic properties offer a promising platform for conducting interfacial reactions between immiscible reagents. Despite the significant progress in the design of Pickering interfacial catalysts for a broad panel of reactions, the dynamics of Pickering emulsions under reaction conditions is still poorly understood. Herein, using benzene hydroxylation with aqueous H2O2 as a model system, we explored the dynamics of benzene/water Pickering emulsions during reaction by dissipative particle dynamics. Our study points out that the surface wettability of the silica nanoparticles is affected to a higher extent by the degree of polymer grafting rather than an increase of the chain length of hydrophobic polymer moieties. A remarkable decline of the oil-in-water (O/W) interfacial tension was observed when increasing the yield of the reaction product (phenol), affecting the emulsion stability. However, phenol did not alter to an important extent the distribution of immiscible reagents around the nanoparticles sitting at the benzene/water interface. A synergistic effect between phenol and silica nanoparticles on the O/W interfacial tension of the biphasic system could be ascertained.
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Pickering emulsions are surfactant-free dispersions of two immiscible fluids that are kinetically stabilized by colloidal particles. For ecological reasons, these systems have undergone a resurgence of interest to mitigate the use of synthetic surfactants and solvents. Moreover, the use of colloidal particles as stabilizers provides emulsions with original properties compared to surfactant-stabilized emulsions, microemulsions, and micellar systems. Despite these specific advantages, the application of Pickering emulsions to catalysis has been rarely explored. This Minireview describes very recent examples of hybrid and composite amphiphilic materials for the design of interfacial catalysts in Pickering emulsions with special emphasis on their assets and challenges for industrially relevant biphasic reactions in fine chemistry, biofuel upgrading, and depollution.
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Stabilization of oil/oil Pickering emulsions using robust and recyclable catalytic amphiphilic silica nanoparticles bearing alkyl and propylsulfonic acid groups allows fast and efficient solvent-free acetalization of immiscible long-chain fatty aldehydes with ethylene glycol.
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Emulsões/química , Nanopartículas/química , Óleos/química , Dióxido de Silício/química , Tensoativos/química , Aldeídos/química , Alquilação , Catálise , Etilenoglicol/química , Ácidos Sulfônicos/químicaRESUMO
ZIF-7, built as an assembly of Zn(II) centers and benzimidazolate ligands, shows prominent S-shaped isotherms upon CO2 adsorption that can be attributed to sorbate-induced gate-opening phenomena involving a narrow-to-large pore phase transition. This peculiar sorption pattern can be captured via the formulation of thermodynamic isotherms, providing a direct enthalpic and entropic view of the gate-opening process. Relying on such an approach, an energy barrier with preferential enthalpic nature for CO2 adsorption/desorption in the gate-opening region could be unveiled. Moreover, the elastic energy involved during the gate-opening process was revisited to 1.4-2.8 kJ mol(-1) of solid in the temperature range 273-323 K, matching the value measured by isostatic compression of a ZIF-7_lp sample filled with DMF and showing a dominant entropic contribution.
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Gas-liquid-solid catalytic reactions are widespread in nature and man-made technologies. Recently, the exceptional reactivity observed on (electro)sprayed microdroplets, in comparison to bulk gas-liquid systems, has attracted the attention of researchers. In this perspective, we compile possible strategies to engineer catalytically active gas-liquid-(solid) interfaces based on membrane contactors, microdroplets, micromarbles, microbubbles, and microfoams to produce commodity chemicals such as hydrogen peroxide, ammonia, and formic acid. In particular, particle-stabilized microfoams, with superior upscaling capacity, emerge as a promising and versatile platform to conceive high-performing (catalytic) gas-liquid-(solid) nanoreactors. Gas-liquid-(solid) nanoreactors could circumvent current limitations of state-of-the-art multiphase reactors (e.g., stirred tanks, trickle beds, and bubble columns) suffering from poor gas solubility and mass transfer resistances and access gas-liquid-(solid) reactors with lower cost and carbon footprint.
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Nonaqueous foams in low-surface tension solvents (<25 mN·m-1) are highly desired for applications in fire extinguishers and detoxification gels. However, their formation is a Holy Grail of the chemical industry due to the need for stabilizers with low surface energy and high recyclability. Herein, we disclose a new strategy to generate abundant foams in ethanol and a variety of low-surface tension solvents relying on the interfacial coadsorption of two different particles. The particles consist of surface-active fluorinated silica particles, used as a stabilizer, and a novel amphiphilic polyhedral oligomeric silsesquioxane (POSS) decorated with isobutyl cage substituents, used as a frother. The interaction between POSS and fluorinated particles at the ethanol-air interface was thoroughly investigated by combining physicochemical methods (contact angle, dynamic surface tension, and dynamic light scattering methods) and catalytic tests using the model aerobic oxidation reaction of benzyl alcohol. Both particles could be conveniently recycled for at least 5 consecutive runs with high foamability and catalytic activity.
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Amphiphilic Janus silica particles, tunable with oleophobic-oleophilic properties and low fluorine content (8 wt % F), exhibited prominent foamability for a variety of aromatic alcohols at low particle concentrations (<1 wt %) compared to randomly functionalized silica particles. When selectively loaded with Pd nanoparticles on the oleophilic hemisphere, the particles displayed more than a 2-fold increase in catalytic activity for the aerobic oxidation of benzyl alcohol compared to nonfoam bulk catalysis under ambient O2 pressure. The particles were conveniently recycled with high foamability and catalytic activity maintained for at least five consecutive runs.
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In this study, we investigated the effect of the pore volume and mesopore size of surface-active catalytic organosilicas on the genesis of particle-stabilized (Pickering) emulsions for the dodecanal/ethylene glycol system and their reactivity for the acid-catalyzed biphasic acetalization reaction. To this aim, we functionalized a series of fumed silica superparticles (size 100-300 nm) displaying an average mesopore size in the range of 11-14 nm and variable mesopore volume, with a similar surface density of octyl and propylsulfonic acid groups. The modified silica superparticles were characterized in detail using different techniques, including acid-base titration, thermogravimetric analysis, TEM, and dynamic light scattering. The pore volume of the particles impacts their self-assembly and coverage at the dodecanal/ethylene glycol (DA/EG) interface. This affects the stability and the average droplet size of emulsions and conditions of the available interfacial surface area for reaction. The maximum DA-EG productivity is observed for A200 super-SiNPs with a pore volume of 0.39 cm3·g-1 with an interfacial coverage by particles lower than 1 (i.e., submonolayer). Using dissipative particle dynamics and all-atom grand canonical Monte Carlo simulations, we unveil a stabilizing role of the pore volume of porous silica superparticles for generating emulsions and local micromixing of immiscible dodecanal and ethylene glycol, allowing fast and efficient solvent-free acetalization in the presence of Pickering emulsions. The micromixing level is interrelated to the adsorption energy of self-assembled particles at the DA/EG interface.
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Hydrogen uptake at 298 K and 30 bar in hybrid sorbents consisting of n-hexane confined in MIL-101 is found to be 22 times larger than in sole n-hexane. The enhanced solubility in MIL-101, found to be 3 times larger than in mesoporous silica of similar pore size, highlights the key roles played by surface chemistry and accessible surface area.
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Hexanos/química , Hidrogênio/química , Compostos Organometálicos/química , Tamanho da Partícula , Porosidade , Dióxido de Silício/química , Solubilidade , Solventes/química , Propriedades de SuperfícieRESUMO
Debate continues over which active species plays the role of oxidative agent during the Fenton reaction-the HOË radical or oxo iron [Fe(IV)O](2+). In this context, the present study investigates the oxidation of p-chlorophenol by [Fe(IV)O(H(2)O)(5)](2+) using DFT calculations, within gas-phase and micro-solvated models, in order to explore the possible role of oxo iron as a reactant. The results show that the chlorine atom substitution of p-chlorophenol by oxo iron is a highly stabilising step (ΔH = -83 kcal mol(-1)) with a free energy barrier of 5.8 kcal mol(-1) in the micro-solvated model. This illustrates the high oxidising power of the [Fe(IV)O(H(2)O)(5)](2+) complex. On the other hand, the breaking of the Fe-O bond, leading to the formation of hydroquinone, is observed to be the rate-determining step of the reaction. The rather large free energy barrier corresponding to this bond cleavage amounts to 10.2 and 9.3 kcal mol(-1) in the gas-phase and micro-solvated models, respectively. Elsewhere, the lifetime of the HOË radical has previously been shown to be extremely small. These facts, combined with observations of oxo iron under certain experimental conditions, suggest that oxo iron is a highly plausible oxidative species of the reaction. In addition, a trigonal bipyramidal iron complex, coordinated either by hydroxyl groups and/or by water molecules, has been found in all described mechanisms. This structure appears to be a stable intermediate; and to our knowledge, it has not been characterised by previous studies.
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A novel amphiphilic polyhedral oligomeric silsesquioxane (POSS) with surfactant-like behavior was synthesized. By combining this new POSS, used as a frother, with surface-active catalytic organosilica particles, used as a stabilizer, we designed a dual particle system able to generate foams in pure organic solvents. Tunable foamability and foam stability were achieved in a variety of organic solvents by simply adjusting the POSS concentration. As a result, the catalytic activity was drastically boosted in the aerobic oxidation of pure aromatic alcohols under 1 bar O2 pressure. Particles were conveniently recycled with high foamability and the catalytic efficiency was maintained for at least 7 consecutive runs.
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HYPOTHESIS: Can surface-active particles be designed à la carte just by incorporating functional groups mimicking the structure of the solvent and gas? This is based on the idea that, to achieve good foamability, the particle wettability needs to be finely tuned to adjust the liquid-particle and gas-particle surface tensions. In practice, could particles containing phenyl rings and alkyl chains assemble at the air-liquid interface and stabilize foams based on aromatic solvents? EXPERIMENTS: A library of organosilica particles was prepared by sol-gel synthesis using aromatic organosilane precursors. The particles were characterized by TGA, FTIR and 13C/29Si MAS NMR. The foaming properties were studied after hand shaking and high-speed homogenization. The influence of particle wettability and solvent properties on foam formation was systematically investigated. A comparison was carried out between biphenyl-bridged particles and various stabilizers on foamability in benzyl alcohol. FINDINGS: Biphenyl-bridged particles could stabilize foams in aromatic solvents with a high foam volume fraction up to 96% using Ultra-Turrax. The presence of biphenyl rings and short alkyl chains was crucial for foamability. Organic foams were prepared for aromatic solvents with intermediate surface tension (35-44 mN m-1) and contact angle in the range 32-53°. Biphenyl-bridged particles outperformed polytetrafluoroethylene and fluorinated surfactants in benzyl alcohol.