Self-catalyzed synthesis of mesoporous carbons with tunable pore size and structure by soft-templating method

A series of mesoporous carbons (MCs) have been obtained through organic–organic self-assembly method by using phloroglucinol–formaldehyde as carbon precursor and a reverse amphiphilic triblock copolymer as a template. Because of its acidity, the phloroglucinol was used as a catalyst itself. Results show that the pore size and structure of MCs were tailored by simply tuning the weight content of formaldehyde while keeping other reactants constant. A cylindrical mesostructure was obtained when the weight content was 1.0, 1.2 and 1.4. Further increasing the weight content to 1.6 or 2.0, a three-dimensional cage-like mesostructure was obtained. Specific surface area and pore volume up to 485 m²/g and 0.78 cm³/g can be reached, respectively. In addition, the pore size can be tuned in the range of 4.9–14.8 nm by changing the content of formaldehyde.     

Biodiesel Production from Waste Cooking Oil over Mesoporous SO42-/Zr-SBA-15

Biodiesel production from waste cooking oils over SO₄^2-/Zr-SBA-15 catalyst was successfully carried out and investigated. SO₄^2-/Zr-SBA-15 catalyst was prepared by one-step process using anhydrous zirconium nitrate as zirconium resource, and endowed with the strong Lewis acid sites formed by supporting the zirconium species onto the SBA-15 surface. The asprepared SO₄^2-/Zr-SBA-15 showed excellent triglyceride conversion efficiency of 92.3% and fatty acid methyl esters (FAME) yield of 91.7% for the transesteriffication of waste cooking oil with methanol under the optimized reaction conditions: the methanol/oil molar ratio of 30, the reaction temperature of 160 oC, the reaction time of 12 h and 10wt% of catalyst. It was noticed that the as-prepared SO₄^2-/Zr-SBA-15 materials with the higher area surface of mesoporous framework and the surface acidity displayed excellent stability and reusability, maintaining high FAME yield of (74±1)% after seven runs of reaction.     

Clean synthesis of biodiesel over solid acid catalysts of sulfonated mesopolymers

FDU-15-SO₃H, a solid acid material prepared from the sulfonation of FDU-15 mesoporous polymer, has been demonstrated to serve as an efficient catalyst in the esterification of palmitic acid with methanol as well as in the transesterification of fatty acid-edible oil mixture. FDU-15-SO₃H achieved an acid conversion of 99.0% when the esterification was carried out at 343 K with a methanol/palmitic acid molar ratio of 6:1 and 5 wt% catalyst loading. It was capable of giving 99.0% yield of fatty acid methyl esters (FAME) when the transesterification of soybean oil was performed at 413 K and the methanol/oil weight ratio of 1:1. FDU-15-SO₃H was further applied to the transesterification/esterification of the oil mixtures with a varying ratio of soybean oil to palmitic acid, which simulated the feedstock with a high content of free fatty acids. The yield of FAME reached 95% for the oil mixtures containing 30 wt% palmitic acid. This indicated the sulfonated mesopolymer was a potential catalyst for clean synthesis of fuel alternative of biodiesel from the waste oil without further purification.     

Kinetics of thiophene hydrodesulfurization over a supported Mo–Co–Ni catalyst

In this study, the kinetics of thiophene (TH) hydrodesulfurization (HDS) over the Mo–Co–Ni-supported catalyst was investigated. Trimetallic catalyst was synthesized by pore volume impregnation and the metal loadings were 11.5 wt % Mo, 2 wt % Co, and 2 wt % Ni. A large surface area of 243 m²/g and a relatively large pore volume of 0.34 cm³/g for the fresh Mo–Co–Ni-supported catalyst indicate a good accessibility to the catalytic centers for the HDS reaction. The acid strength distribution of the fresh and spent catalysts, as well as for the support, was determined by thermal desorption of diethylamine (DEA) with increase in temperature from 20 to 600 °C. The weak acid centers are obtained within a temperature range between 160 and 300 °C, followed by medium acid sites up to 440 °C. The strong acid centers are revealed above 440 °C. We found a higher content of weak acid centers for fresh and spent catalysts as well as alumina as compared to medium and strong acid sites. The catalyst stability in terms of conversion as a function of time on stream in a fixed bed flow reactor was examined and almost no loss in the catalyst activity was observed. Consequently, this fact demonstrated superior activity of the Mo–Co–Ni-based catalyst for TH HDS. The activity tests by varying the temperature from 200 to 275 °C and pressure from 30 to 60 bar with various space velocities of 1–4 h^?1 were investigated. A Langmuir–Hinshelwood model was used to analyze the kinetic data and to derive activation energy and adsorption parameters for TH HDS. The effect of temperature, pressure, and liquid hourly space velocity on the TH HDS activity was studied.     

Fabrication and characterization of dodecylamine derived monodispersed mesoporous bioactive glass sub-micron spheres

This paper reports a facile method for fabricating monodispersed mesoporous bioactive glass sub-micron spheres (MBGS) using dodecylamine (DDA) as a catalyst and template agent in sol–gel process. The effects of synthesis conditions including the amount of DDA, temperature of hydrolysis and the volume ratio of alcohol to water (AW ratio) on the resulting particle size, morphology, monodispersity and pore size distribution of MBGS are investigated and discussed. The results indicate that the particle size, morphology, monodispersity and pore size distribution of MBGS depend on the amount of DDA, the temperature of hydrolysis and the AW ratio. Meanwhile, using DDA as the structure directing agent and hydrolysis catalyst under optimal synthesis conditions (e.g. 4 g DDA, hydrolysis temperature at 40 °C and AW ratio at 4) is in favor of obtaining MBGS with mesoporous surface structure, large specific surface area (362.073 m² g^?1), relatively homogeneous particle size (~560 nm) as well as good apatite-forming activity. The unique structure and properties may turn MBGS into a good candidate as a drug delivery carrier or an injectable biomaterial for bone tissue regeneration.     

Synthesis of SBA-15 from low cost silica precursor obtained from sugarcane leaf ash and its application as a support matrix for lipase in biodiesel production

Ordered mesoporous silica material was synthesized from a low-cost precursor, sugarcane leaf ash, was used as a support matrix for lipase for the production of biodiesel. The mesoporous samples were characterized using Fourier transform infra red spectroscopy. The surface topography and morphology of the mesoporous materials were studied using scanning electron microscope. The pore diameter, pore volume, Brunauer Emmett and Teller surface area of the mesoporous material were determined by N₂ gas adsorption technique. Different pore size Santa Barbara Acid-15 (SBA-15) samples were synthesized and their lipase immobilization capacity and specific enzyme activity of immobilization lipase were determined and compared. Lipase from Candida Antarctica immobilized on SBA-15 (C) had shown maximum percentage immobilization and specific enzyme activity. The immobilized lipase mesoporous matrix was used for biodiesel production from crude non-edible Calophyllum inophyllum oil. The percentage yield of fatty acid methyl ester, 97.6 % was obtained under optimized conditions: 100 mg of lipase immobilized on SBA-15, 6:1 methanol to oil molar ratio, the reaction of 2 g C. inophyllum oil with methanol.     

Biodiesel Production via the Transesterification of Soybean Oil Using Waste Starfish (Asterina pectinifera)

Calcined waste starfish was used as a base catalyst for the production of biodiesel from soybean oil for the first time. A batch reactor was used for the transesterification reaction. The thermal characteristics and crystal structures of the waste starfish were investigated by thermo-gravimetric analysis and X-ray diffraction. The biodiesel yield was determined by measuring the content of fatty acid methyl esters (FAME). The calcination temperature appeared to be a very important parameter affecting the catalytic activity. The starfish-derived catalyst calcined at 750 °C or higher exhibited high activity for the transesterification reaction. The FAME content increased with increasing catalyst dose and methanol-over-oil ratio.     

Nitric acid oxidation of ordered mesoporous carbons for use in electrochemical supercapacitors

Ordered mesoporous carbon materials with high microporosity were synthesized by a low temperature autoclaving of citric acid-catalyzed polymerized resorcinol/formaldehyde in the presence of the triblock copolymer F127 and were activated by nitric acid oxidation. The materials were used as electrode materials in electrochemical supercapacitors. A bimodal pore size distribution of 2.1–2.3 and 5.3 nm with a surface area of 465–578 m² g^?1 and pore volume of 0.44–0.54 cm³ g^?1 was obtained with the retention of an ordered mesoporous structure after nitric acid (2 M) treatment. The introduced functional groups produced a pseudocapacitance, which resulted in an increase in the specific capacitance. The electrochemical capacitance of the resulting mesoporous carbons showed a marked increase after 3 h of nitric acid activation, exhibiting a high value of 295 F g^?1 at the scan rate of 10 mV s^?1 in 6 M KOH aqueous solution and good cycling stability with specific capacitance retention over 500 cycles.     

Fast Biodiesel Production with One-Phase Reaction

The feasibility of fatty acid methyl ester (FAME) as a co-solvent used to increase the mass transfer between oil and methanol was investigated. FAME, as the co-solvent, does not require additional separation after the reaction because it is the end product of the reaction. To examine intermediate phenomena during the transesterification of soybean oil, the agitation speed was controlled at a slow rate. When the molar ratio of oil to methanol was 1:6 at 0.8wt.% of KOH to oil, oil was at the bottom layer, and methanol and the catalyst were at the top layer. Under the slow agitation process, the contact surface became initially darkened with the production of FAME and glycerol. After a few minutes, the entire top layer became dark. The top layer, containing methanol, KOH, FAME, and glycerol, fell to the bottom layer and then formed the one-phase system. When 0, 5, and 10 wt.% of FAME to oil was initially introduced to the reaction mixture, the FAME content rapidly increased with the FAME concentration level. After forming the one-phase system, the rate of increase of the FAME content was very slow. The time required for the formation of the one-phase system decreased with the amount of FAME and KOH and with temperature.     

Hierarchical mesoporous carbon materials: preparation by direct tri-constituent co-assembly and the electrochemical performance

Hierarchical mesoporous carbon materials with large microporosity were prepared by direct tri-constituent co-assembly with the use of resols as the carbon precursor, tetraethyl orthosilicate as the inorganic precursor, and triblock copolymer F127 as the soft template. Bimodal pore size distributions in the range of 1.5–4 and 7.5–12 nm were obtained in the synthesized hierarchical mesoporous carbon materials after etching of silica by HF acid, showing a high surface area of 1,675 m²?g^?1 with a large pore volume of 2.06 cm³?g^?1. The electrochemical performance of the hierarchical mesoporous carbons was evaluated as an electrode material for electrochemical supercapacitor, showing a specific capacitance as high as 152 F?g^?1 at a scan rate of 5 mV?s^?1 in 6 M KOH aqueous solution and a good cycling stability with capacitance retention of 99 % over 500 cycles.     

Mesoporous carbon nitride loaded with Pt nanoparticles as a bifunctional air electrode for rechargeable lithium-air battery

A composite comprised of oxygen reduction reaction (ORR) catalyst and oxygen evolution reaction (OER) catalyst was designed and applied as a bifunctional electrocatalyst for the air electrode of the lithium-air battery. The ordered mesoporous carbon nitride (MCN) prepared by a nano hard-templating approach displayed a surface area as high as 648 m² g^?1 and a large pore volume of 0.7 cm³ g^?1 and acted as both the ORR catalyst and the support for the in situ-formed OER catalyst of Pt particles with a diameter of 3–4 nm. The electrochemical performances of the electrode were examined in a solid-state lithium-air cell structured as Li/LATP-based electrolyte/cathode, which demonstrated a higher round-trip efficiency and lower overpotential compared with the Pt@AB and MCN electrodes. The combination of the OER and ORR catalysts is proved as an effective way to improve the performance of lithium-air batteries.     

Highly efficient mesoporous WO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/KIT-6 catalysts for oxidative desulfurization of dibenzothiophene with hydrogen peroxide

Oxidative desulfurization (ODS) of organic compounds containing sulfur element from a model oil was performed using tungsten oxide catalysts supported on mesoporous silica with cubic Ia3d mesostructure, well-defined mesopores (7.2 nm), high surface area (719 m²/g), and three-dimensional pore network (WO _x /KIT-6). The prepared WO _x /KIT-6 catalysts (5–20 wt% WO _x ) were characterized by X-ray diffraction analysis, N₂ sorption measurements, electron microscopy, H₂-temperature programmed reduction, Raman spectroscopy, and thermogravimetric analysis. Among the mesoporous catalysts, 10 wt% WO _x /KIT-6 exhibited the best catalytic performance. Sulfur-containing organic compounds, such as dibenzothiophene, 4,6-dimethyldibenzothiophene, and benzothiophene, were completely (100 %) removed from the model oil over 10 wt% WO _x /KIT-6 catalyst in 2 h. In addition, the catalyst could be reused several times with only slight decrease in catalytic activity.     

Structural and surface heterogeneity of phosphorus-containing polyimide-derived carbons: effect of heat treatment temperature

Phosphorus-containing carbons have been obtained by carbonization of porous copolymer of 4,4′-bis(maleimidodiphenyl)methane (50 mol%) and divinylbenzene (50 mol%) in presence of phosphoric acid at temperatures 400–1000 °C. Porous structure was analyzed by nitrogen adsorption isotherms while surface chemistry was investigated by potentiometric titration method. It has been shown that carbons obtained at 500–1000 °C are micro-mesoporous with pore sizes of 1–1.1, 2–3 and 5.4 nm. The most developed porosity was achieved at 600 °C reaching BET surface area 890 m²/g and total pore volume 0.45 cm³/g. Carbons obtained by carbonization of polyimide precursor in presence of phosphoric acid showed acidic character with 30–40 % of phosphate surface groups. Maximum total amount of acidic surface groups was achieved at 800 °C reaching 3.2 mmol/g. Assignment of strongly acidic surface groups to phosphates was corroborated by pK value, phosphorus content and thermal gravimetric analysis.     

High Catalytic Performance of Mesoporous Dual Brønsted Acidic Ternary Poly (Ionic Liquids) for Friedel‐Crafts Alkylation

A newfangled cross‐linked dual Brønsted acidic ternary mesoporous poly (ionic liquids)(MPILs) with mesoporous structure was successfully synthesized with divinylbenzene as cross linker, 1‐vinyl‐3‐butyl imidazole bromide and sodium p‐styrene sulfonate as functional group through an ordinary post‐modification method and anion exchange process. A sponge‐like mesoporous tunnel structure was observed and the obtained P (BVS‐SO₃H)‐SO₃CF₃ sample appeared a relatively high thermal stability, a large surface area (up to 286.8 m²/g) and great pore volume (0.73 cm³/g). The abundant dual acidic group of sulfonic acid and trifluoromethanesulfonic acid of the composite in the polymer framework impart Brønsted acidity. For the sake of demonstrating our claims, the sample has been used as a novel solid acid catalyst for the reaction of alkylation of o‐xylene with styrene to 1‐diphenylethane (PXE). Under optimal reaction conditions (reaction under 120 °C for 3 hr, catalyst amount was 0.5 wt% of the reaction system, and the mass ratio of o‐xylene/styrene was 7.5:1, a 100% conversion of styrene and 93.7% PXE yield was acquired. After four times recycle, the yield remains 53.3%. Comparing with the commercial liquid acid catalyst, it processing a higher catalytic property and recyclability. Moreover, this fresh dual acidic heterogeneous catalyst owning a promising future applied in other acidic catalytic reactions and provide a new method to modify catalyst.     

Alkali Hydrothermal Synthesis of Na0.1Ca0.9TiO3 Nanorods as Heterogeneous Catalyst for Transesterification of Camelina Sativa Oil to Biodiesel

Orthorhombic perovskite Na_0.1Ca_0.9TiO₃ nanorods were synthesized at low calcination temperature via alkali hydrothermal synthesis. The synthesized nanorods exhibits a square based prism morphology, with a width and length of 200–500 nm and 2–3 μm respectively. The structural, textural and basic characteristics of the catalyst were examined by SEM, TEM, XRD and BET. The growth direction of the nanorods was confirmed to be along the long symmetry [110] zone axis and the exterior surfaces are found to be polar (110) and (002) with either Ti or Ca exposed in those facets. The catalytic activity of the nanorods was investigated for the transesterification of the low-input Camelina Sativa oil and methanol to give the fatty acid methyl ester (FAME). Effects of important reaction parameters such as methanol to oil molar ratio, catalyst dosage, reaction temperature and reaction time on oil conversion were examined. Optimized biodiesel yield of 93 % was achieved with catalyst dosage of 6 % w/w, methanol to oil molar ratio of 36:1 at reaction temperature of 60 °C for 8 h.     

Improved Performance of Lipase Immobilized on Tannic Acid-Templated Mesoporous Silica Nanoparticles

Mesoporous silica nanoparticles were synthesized by using tannic acid as a pore-forming agent, which is an environmentally friendly, cheap, and non-surfactant template. SEM and TEM images indicated that the tannic acid-templated mesoporous silica nanoparticles (TA-MSNs) are monodisperse spherical-like particles with an average diameter of 195?±?16 nm. The Brunauer–Emmett–Teller (BET) results showed that the TA-MSNs had a relatively high surface area (447 m²/g) and large pore volume (0.91 cm³/g), and the mean pore size was ca. 10.1 nm. Burkholderia cepacia lipase was immobilized on the TA-MSNs by physical adsorption for the first time, and the properties of immobilized lipase (BCL@TA-MSNs) were investigated. The BCL@TA-MSNs exhibited satisfactory thermal stability; strong tolerance to organic solvents such as methanol, ethanol, isooctane, n-hexane, and tetrahydrofuran; and high operational reusability when BCL@TA-MSNs were applied in esterification and transesterification reactions. After recycling 15 times in the transesterification reaction for biodiesel production, over 85 % of biodiesel yield can be maintained. With these desired characteristics, the TA-MSNs may provide excellent candidates for enzyme immobilization.     

Mesoporous activated carbon from <Emphasis Type="Italic">Pentace</Emphasis> species sawdust via microwave-induced KOH activation: optimization and methylene blue adsorption

This work studied the optimization of preparation conditions of Pentace species sawdust activated carbon (PSAC) via microwave-induced KOH activation for the adsorption of methylene blue (MB) dye from aqueous solutions. The produced activated carbon was characterised through Brunauer–Emmett–Teller (BET) surface area and pore structural analysis, proximate and ultimate, scanning electron microscopy, and Fourier transform infrared spectroscopy. Response surface methodology technique was used to optimize the radiation power, radiation time and impregnation ratio for MB removal and PSAC yield through central composite design. The optimum preparation conditions for PSAC were obtained at a radiation power of 418 W, radiation time of 6.4 min, and an impregnation ratio of 0.5, which resulted in 27% PSAC yield and 93.74% MB removal. A mesoporous structure of PSAC was formed, with a BET surface area, total pore volume and average pore diameter of 914.15 m²/g, 0.52 cm³/g, and 3.19 nm, respectively. The experimental kinetic data were well described by a pseudo-second-order model and intraparticle diffusion. Adsorption data fitted the Redlich–Peterson equation better than the Langmuir, Freundlich, Temkin, Dubinin–Radushkevich and Sips equations. However, the exponential value of Redlich–Peterson approached unity, hence, resulting in the original Langmuir equation, with adsorption capacity of 357.14 mg/g. The adsorption performance was effectively preserved even after four consecutive cycles, demonstrating good regeneration ability.     

Optimization of process conditions for biodiesel production over CaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript> catalyst using response surface methodology

CaO–Al₂O₃/ZrO₂ mixed oxide catalyst was prepared using free-solvent method. The catalyst was characterized using X-ray diffraction, BET surface area, acidity index (obtained by titration method), and scanning electron microscopy (SEM). With calcium aluminate and calcium zirconate been successfully formed, the mix exhibited small crystal size, high acidity, and large surface area, pore size, and pore volume, making it a catalyst of choice for biodiesel production. The activity of catalyst was evaluated in the course of esterification of oleic acid as well as transesterification of waste cooking oil (WCO) into biodiesel. Based on a four-variable central composite design (CCD), response surface methodology (RSM) was used to optimize effective variables on oleic acid conversion. The optimum yield of 94.68% was obtained at the following set of optimum conditions: reaction temperature of 120 °C, methanol/oleic acid molar ratio of 15.64, catalyst concentration of 2.94 wt%, and reaction time of 4 h; the result was in excellent agreement with the predicted values. Furthermore, under the optimum conditions, the catalyst succeeded to convert 93.48% of WCO into biodiesel.     

Partially graphitized ordered mesoporous carbons for high-rate supercapacitors

Partially graphitized ordered mesoporous carbons have been prepared with a soft template method using low-molecular-weight phenolic resol as a carbon source, triblock copolymer F127 as a template, and ferric citrate as a graphitization catalyst. N₂ sorption and transmission electron microscopy analysis show that the ordered mesoporous carbons have been partially graphitized when the carbonization temperature is above 700 °C. The graphitic ordered mesoporous carbons exhibit better rate performance than amorphous ordered mesoporous carbons. The specific capacitance of the graphitic ordered mesoporous carbons (GOMCs) prepared at 700 °C reaches to 112 F g^?1 at a scan rate of up to 1,000 mV s^?1. Its capacitance retention ratio is 64 %, which is much higher than that of the amorphous ordered mesoporous carbons prepared at 600 °C (33 %). High electronic conductivity and ordered mesoporous structure lead to the high electrochemical performance of the partially graphitized ordered mesoporous carbons.     

Sol–gel synthesis of mesoporous silicas containing albumin and guanidine polymers and its application to the bilirubin adsorption

The organic–inorganic composite materials based on mesoporous silica were synthesized using sol–gel method. The surface area of silicas was modified by bovine serum albumin (BSA) and guanidine polymers: polyacrylate guanidine (PAG) and polymethacrylate guanidine. The mesoporous silicas were characterized by nitrogen adsorption–desorption analysis, Fourier transform infrared spectroscopy, transmission electron microscopy. The obtained materials were used as adsorbents for selective bilirubin removal. It was shown that the structural properties and surface area of modified materials depend on the nature of polymers. Incorporation of polymers in silica gel matrix during sol–gel process leads to the formation of mesoporous structure with high pore diameter and a BET surface area equals to 346 m²/g for SiO₂/BSA and 160 m²/g for SiO₂/PAG. Analysis of adsorption isotherms showed that modification of silica by BSA and guanidine polymers increases its adsorption ability to bilirubin molecules. According to Langmuir model, the maximum bilirubin adsorption capacity was 1.18 mg/g.