Chemistry on the inside: green chemistry in mesoporous materials

An overview of the rapidly expanding area of tailored mesoporous solids is presented. The synthesis of a wide range of the materials is covered, both inorganically and organically modified. Their applications, in particular those relating to green chemistry, are also highlighted. Finally, potential future directions for these materials are discussed

Catalytic performance of carbonaceous materials in the esterification of succinic acid

Mesoporous carbonaceous materials have outstanding potential in many different applications such as adsorption, medicine and catalysis. We have recently reported the synthesis of a new form of mesoporous carbon, named Starbon((R)), obtained after low temperature carbonization of expanded starch. Such starch-derived mesoporous materials have several tunable properties including surface energies (ranging from hydrophilic to hydrophobic surfaces), which can be easily controlled by the degree of carbonization (from 200 to 700 degrees C). Due to the diversity of surface functional groups, Starbons((R)) can be easily chemically modified. Treatment of Starbon((R)) materials with sulfuric acid gave a solid acid that has promising properties as heterogeneous catalyst. Comparative catalytic studies with some other similar commercial carbonaceous materials such as DARCO((R)) and NORIT (R), as well as phosphorous-containing microporous carbons, are reported. (c) 2008 Elsevier B.V. All rights reserved

Effect of spruce-derived phenolics extracted using microwave enhanced pyrolysis on the oxidative stability of biodiesel

An investigation has been carried out to characterize and evaluate phenolic compounds of bio-oils produced by the microwave enhanced pyrolysis of spruce woodchips (picea abies) for their potential application in stabilizing biodiesel from autoxidation. Four extracts were isolated from the bio-oil through multi-fractionation steps using a liquid-liquid extraction method: water-soluble, neutral, phenolic and organic acids extracts. The crude bio-oil and the isolated extracts were characterized by GC-MS, GC-FID, total phenols by Folin-Ciocalteu assay, ATR-IR and 13C NMR. The antioxidative effect of the crude bio-oil, its isolated extracts and two significant phenolic components (eugenol and catechol) of the crude bio-oil were also investigated using methyl linoleate as a biodiesel model by means of a high temperature (120°C) oxidation test. The results show that methyl linoleate induction time increased after blending small amounts (1.4-5.6% w/w) of either the crude bio-oil or the isolated extracts. However, the crude bio-oil showed higher induction times in comparison with its isolated extracts, which was significant because the crude bio-oil contained a lower concentration of phenolic species (23% w/w), especially in comparison to the phenolic concentration in the phenolic extract (49.6% w/w). Furthermore, catechol was found to be very effective and was similar to crude bio-oil in the inhibition of methyl linoleate autoxidation, unlike eugenol, which was less effective at equivalent molar concentrations. Also, the effect of catechol and the crude bio-oil on methyl linoleate induction time was approximately comparable with a commercial antioxidant (butylated hydroxytoluene) when treated at equivalent molar concentration of phenols

P-cymenesulphonyl chloride : A bio-based activating group and protecting group for greener organic synthesis

A bio-derived protecting/activating group has been synthesized by introducing a sulphonyl chloride group to the aromatic ring of p-cymene derived from citrus peel waste. The resulting p-cymenesulphonyl chloride was evaluated as an activating group by reacting with 1-octanol, 2-octanol, phenol and piperidine, and further reactions of the activated alcohols. The comparison to tosyl chloride demonstrates that the bio-based alternative can be effectively utilized as a direct replacement for the current fossil derived equivalent

Torrefied fuel pellets from solid waste of sugar industry

The preparation of fuel pellets from the filter cake waste from the sugar industry was studied. Pelletization by a hydraulic press at a pressure of 20 to 50 bar (2 to 5 MPa) was used to produce fuel pellets with a diameter of 1 cm and height of 1. 25 cm. Energy efficiency of the resulting pellets was improved by thermal treatment called “torrefaction”. During this process, the samples were heated to between 200 and 300°C for 0.5 to 2 h under a nitrogen atmosphere. The properties of fuel pellets including calorific value, bulk density, pellet density, proximate analysis, and compressive strength were characterized. The results demonstrated that the minimum pressure needed to produce the pellets without binder was 30 bar. The calorific value was between 13,954–14,468 kJ/ kg for the resulting fuel pellet, which was significantly higher than that of the unpelletized raw material (11,197 kJ/ kg). The fuel pellets had bulk density and pellet density of between 300–440 kg/m3 and 720–890 kg/m3, respectively. Increasing the time and temperature of torrefaction resulted in the lower yields of pellets. Fuel pellets maintain their shape and did not break under the applied torrefaction conditions. Torrefied pellets resulted in higher calorific value of 16,552–22,642 kJ/kg, higher carbon content, lower pellet and bulk densities compared to the fuel pellet without thermal treatment. The compressive strength of torrefied pellets decreased due to the delicate nature of the sample. The suggested conditions for optimal torrefied pellet in thermal and physical properties are 300°C and 1 h. The prepared fuel pellets showed comparable heating values to other fuels, and had properties in agreement with Thailand standards. Therefore, filter cake as a solid waste from production process of sugar has potential as raw material for the production of solid fuel pellets

Novel mesoporous carbon-silica composites from vinasse for the removal of dyes from aqueous silk dyeing wastes

Novel mesoporous carbon-silica composites were prepared from vinasse, a by-product from ethanol production, as the carbon source, and sodium silicate (Na2SiO3) and potassium silicate (K2SiO3) as low-cost silica source alternatives to tetraethyl orthosilicate (TEOS). The composites were characterized for their surface area and porous properties using nitrogen adsorption-desorption porosimetry. The composites possessed a high mesopore volume (45-77%) with moderate specific surface areas (343-656 m2/g) and pore size of 3.12-5.58 nm. The adsorption behaviour of carbon-silica composites for the removal of four silk dyes (Green 41, Blue 32, Dark red 34 and Dark gold brown 35) from aqueous solution was investigated and compared with a commercial activated carbon. The effects of adsorption time, dye concentration, pH and temperature were analyzed. The dye adsorption kinetics of all four dyes followed the pseudo-second order kinetic model, suggesting chemisorption as the dominant mechanism. Moreover, the intraparticle diffusion model showed that both internal diffusion and external diffusion were rate-limiting. The maximum adsorption capacities for all dyes were found at pH ~ 2. The equilibrium data for silk dyes adsorption were best described by the Langmuir equation, thus indicating monolayer adsorption. Thermodynamic parameters indicated that the dye adsorption was an endothermic process (ΔH > 0). The negative values of free energy (ΔG) confirmed that dye adsorption was spontaneous at the investigated temperatures (303-323 K). For all dyes, the maximum adsorption capacities of carbon-silica composites were comparable to the commercial activated carbon. The combination of vinasse with low-cost silica sources is a promising approach to produce inexpensive carbon-silica composites for application as adsorbents for dye removal from aqueous waste solutions generated during silk manufacture and dyeing

Work-hardening Photopolymer from Renewable Photoactive 3,3’-(2,5-Furandiyl)bisacrylic Acid

The design of a photopolymer around a renewable furan-derived chromophore is presented herein. An optimised semi-continuous oxidation method using MnO2 affords 2,5-diformylfuran from 5-(hydroxymethyl)furfural in gram quantities, allowing the subsequent synthesis of 3,3’-(2,5-furandiyl)bisacrylic acid in good yield and excellent stereoselectivity. The photoactivity of the diester of this monomer is confirmed by reaction under UV irradiation, and the proposed [2+2] cycloaddition mechanism supported further by TD-DFT calculations. Oligoesters of the photoreactive furan diacid with various aliphatic diols are prepared via chemo- and enzyme-catalysed polycondensation. The latter enzyme-catalysed (Candida antarctica lipase B) method results in the highest Mn (3.6 kDa), suggesting milder conditions employed with this protocol minimised unwanted side reactions, including untimely [2+2] cycloadditions, whilst preserving the monomer's photoactivity and stereoisomerism. The photoreactive polyester is solvent cast into a film where subsequent initiator-free UV curing leads to an impressive increase in the material stiffness, with work-hardening characteristics observed during tensile strength testing

Synthesis and application of tuneable carbon-silica composites from the microwave pyrolysis of waste paper for selective recovery of gold from acidic solutions

Microwave pyrolysis bio-oil from waste paper and K60 silica gel has successfully been utilised to synthesise mesoporous carbon-silica composites with uniquely tuneable surface properties, where functionality and structural characteristics can be altered and even enhanced by curing at different temperatures. This temperature-dependence resulted in composites ranging from highly oxygenated polymerised bio-oil composites at 300 °C to aromatic carbonaceous materials covering the silica surface at 800 °C, making them attractive materials for gold recovery from mining wastewater. The composite materials exhibit exceptional ability and selectivity to recover gold from dilute solutions. Metal adsorption on the surface of these composites proceeded via both chemisorption and physisorption leading to the reduction of Au(iii) to Au(0), resulting in high recovery capacities for gold. Composite material prepared at 500 °C demonstrated the optimum combination of surface functionality and porosity, allowing for an adsorption capacity of 320 mg g-1 of gold and with 99.5% removal being achieved at concentrations mimicking those of real-life mine tailing wastes. All materials pioneered in this research display great potential as selective adsorbents for the recovery of gold from acidic media. This journal i

Subtle Microwave-Induced Overheating Effects in an Industrial Demethylation Reaction and Their Direct Use in the Development of an Innovative Microwave Reactor

A systematic study of the conventional and microwave (MW) kinetics of an industrially relevant demethylation reaction is presented. In using industrially relevant reaction conditions the dominant influence of the solvent on the MW energy dissipation is avoided. Below the boiling point, the effect of MWs on the activation energy Ea and k0 is found nonexistent. Interestingly, under reflux conditions, the microwave-heated (MWH) reaction displays very pronounced zero-order kinetics, displaying a much higher reaction rate than observed for the conventionally thermal-heated (CTH) reaction. This is related to a different gas product (methyl bromide, MeBr) removal mechanism, changing from classic nucleation into gaseous bubbles to a facilitated removal through escaping gases/vapors. Additionally, the use of MWs compensates better for the strong heat losses in this reaction, associated with the boiling of HBr/water and the loss of MeBr, than under CTH. Through modeling, MWH was shown to occur inhomogeneously around gas/liquid interfaces, resulting in localized overheating in the very near vicinity of the bubbles, overall increasing the average heating rate in the bubble vicinity vis-à-vis the bulk of the liquid. Based on these observations and findings, a novel continuous reactor concept is proposed in which the escaping MeBr and the generated HBr/water vapors are the main driving forces for circulation. This reactor concept is generic in that it offers a viable and low cost option for the use of very strong acids and the managed removal/quenching of gaseous byproducts

Dehydration of Alginic Acid Cryogel by TiCl4 vapor : Direct Access to Mesoporous TiO2@C Nanocomposites and Their Performance in Lithium-Ion Batteries

A new strategy for the synthesis of mesoporous TiO2@C nanocomposites through the direct mineralization of seaweed-derived alginic acid cryogel by TiCl4 through a solid/vapor reaction pathway is presented. In this synthesis, alginic acid cryogel can have multiple roles; i) mesoporous template, ii) carbon source, and iii) oxygen source for the TiO2 precursor, TiCl4. The resulting TiO2@alginic acid composite was transformed either into pure mesoporous TiO2 by calcination or into mesoporous TiO2@C nanocomposites by pyrolysis. By comparing with a nonporous TiO2@C composite, the importance of the mesopores on the performance of electrodes for lithium-ion batteries based on mesoporous TiO2@C composite was clearly evidenced. In addition, the carbon matrix in the mesoporous TiO2@C nanocomposite also showed electrochemical activity versus lithium ions, providing twice the capacity of pure mesoporous TiO2 or alginic acid-derived mesoporous carbon (A600). Given the simplicity and environmental friendliness of the process, the mesoporous TiO2@C nanocomposite could satisfy the main prerequisites of green and sustainable chemistry while showing improved electrochemical performance as a negative electrode for lithium-ion batteries