Ordered mesoporous carbon prepared from triblock copolymer/novolac composites

Ordered mesoporous carbon is synthesized by the organic–organic self-assembly method with novolac as carbon precursor and two kinds of triblock copolymers (Pluronic F127 and P123) as template. The hexagonal structure and a worm-hole structure are observed by TEM. The carbonization temperature is determined by TG and FT-IR. Characterization of physical properties of mesoporous carbon is executed by N₂ absorption–desorption isotherms and XRD. The mass ratios of carbon precursor/template affect the textural properties of mesoporous carbon. The mesoporous carbon with F127/PF of 1/1 has lager surface area (670 m² g^?1), pore size (3.2 nm), pore volume (0.40 cm³ g^?1), smaller microporous surface area (368 m² g^?1) and wall thickness (3.7 nm) compare to that with F127/PF of 0.5/1 (576 m² g^?1, 2.7 nm, 0.29 cm³ g^?1, 409 m² g^?1 and 4.3 nm, respectively). The mesoporous carbon prepared by carbonization at high temperature (700 °C) exhibits lager surface area, lower pore size and pore volume than the corresponding one obtained at 500 °C. The structure and order of the resulting materials are notably affected with types of templates. The mesoporous carbon with P123 as template exhibits worm-hole structure compare to that with F127 as template with hexagonal structure. In general, the pore size of mesoporous carbon with novolac as precursor is smaller than that with resorcinol–formaldehyde as precursor.     

Hydrothermal and soft-templating synthesis of mesoporous NiCo2O4 nanomaterials for high-performance electrochemical capacitors

Mesoporous nickel cobaltite (NiCo₂O₄) nanoparticles were synthesized via a hydrothermal and soft-templating method through quasi-reverse-micelle mechanism. The physicochemical properties of the NiCo₂O₄ materials were characterized via X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectra, and nitrogen sorption isotherms measurements. The electrochemical performances of the NiCo₂O₄ electrode were investigated by cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy tests. The obtained NiCo₂O₄ materials exhibit typical mesoporous structures, with an average particle size of about 200 nm, a specific surface area of 88.63 m² g^?1, and a total pore volume of 0.337 cm³ g^?1. The facile electrolytes penetration for the mesoporous structures favors high-performance of the NiCo₂O₄ electrode. The NiCo₂O₄ electrode shows a high specific capacitance (591 F g^?1 at 1 A g^?1), high-rate capability (248 F g^?1 at 20 A g^?1), and a good cycling behavior for tested 3,000 cycles, indicating a promising application for electrochemical capacitors.     

Activated carbon from cherry stones by chemical activation: Influence of the impregnation method on porous structure

Cherry stones are utilized as a precursor for the preparation of activated carbons by chemical activation with phosphoric acid (H₃PO₄). The activation process typically consists of successive impregnation, carbonization, and washing stages. Here, several impregnation variables are comprehensively studied, including H₃PO₄ concentration, number of soaking steps, H₃PO₄ recycling, washing of the impregnated material, and previous semi-carbonization. The choice of a suitable impregnation methodology opens up additional possibilities for the preparation of a wide variety of activated carbons with high yields and tailored porous structures. Microporous activated carbons with specific surface areas of ～800 m² g^?1 are produced, in which > 60% of the total pore volume is due to micropores. High surface areas of ～1500 m² g^?1 can be also developed, with micropore volumes being a 26% of the total pore volume. Interestingly, using the same amount of H₃PO₄, either carbons with surface areas of 791 and 337 m² g^?1 or only one carbon with a surface area of 640 m² g^?1 can be prepared. The pore volumes range very widely between 0.07–0.55, 0.01–0.90, and 0.09–0.79 cm³ g^?1 for micropores, mesopores, and macropores, respectively.     

Dual mesoporous carbon with high nitrogen doping level as an efficient electrode material for supercapacitors

This paper reports a dual mesoporous carbon (NDMC) with high nitrogen doping level derived from the amino production of the sucrose synthesized under hydrothermal condition. The S _BET and total pore volume of the reported materials reaches up to 1101 and 1.67 cm³ g^?1, the small mesopores center at about 3.22–3.31 nm while the larger mesopores locate at 8.98–12.58 nm. The doping content of the nitrogen heteroatoms is found to be more than 11.6 at.%, and depend on the carbonization temperature. The maximum specific capacitance of the reported materials reaches up to 512 F g^?1 due to the additional contribution of pseudo-capacitance induced by the nitrogen heteroatoms doping. The capacitance retention rate is found to be up to 95% after 1000 times cycles. The dual mesoporous structure, high specific area, additional pseudo-capacitance, enhanced wettability and conductivity are found to response for the superior capacitance performance of the reported materials.     

Worm-hole structured mesoporous carbon monoliths synthesized with amphiphilic triblock copolymer

In the present work, mesoporous carbon monoliths with worm-hole structure had been synthesized through hydrothermal reaction by using amphiphilic triblock copolymer F127 and P123 as templates and resole as carbon precursor. Synthesis conditions, carbonization temperature and pore structure were studied by Fourier transform infrared, thermogravimetric analysis, transmission electron microscopy and N₂ adsorption–desorption. The results indicated that the ideal pyrolysis temperature of the template is 450 °C. The organic ingredients were almost removed after further carbonized at 600 °C and the mesoporous carbon monoliths with worm-hole structure were obtained. The mesoporous carbon synthesized with P123 as single template exhibited larger pore size (6.6 nm), higher specific surface area (747 m² g^?1), lower pore ratio (45.9 %) in comparison with the mesoporous carbon synthesized with F127 as single template (with the corresponding value of 4.9 nm, 681 m² g^?1, 49.6 %, respectively), and also exhibited wider pore size distribution and lower structure regularity. Moreover, the higher mass ratio of template P123/resole induced similar pore size, larger specific surface area and lower pore ratio at the same synthesizing condition. It was also found that the textural structure of mesoporous carbon was affect by calcination atmosphere.     

One-pot synthesis of wormhole-like mesostructured silica with a high amine loading for enhanced adsorption of clofibric acid

A series of ordered amine-functionalized hexagonal mesoporous silicas (HMS-NH₂) were synthesized successfully via direct co-condensation using dodecylamine as a structure-directing agent in the presence of 3-aminopropyltrimethoxysilane (APS), [aminoethylamino]propyltrimethoxysilane or [(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEEA) as amine group precursors. Tetrahydrofuran was used as the organic solvent to control the interaction and sol–gel reaction of the silica source and aminosilanes. The effect of the type and concentration of the added aminosilanes on the physicochemical properties of the resulting HMS-NH₂ materials were investigated. Thermogravimetric analysis, Fourier-transform infrared spectroscopy and solid-state ²⁹Si nuclear magnetic resonance spectroscopy confirmed a successful functionalization of the HMS surface with different amine groups. X-ray diffraction and transmission electron microscopy indicated that their wormhole-like mesostructured framework was retained after functionalization at a high APS loading level (15 mol%) or using AEEA as the aminosilane precursor. A high degree (88–98%) of aminosilanes was incorporated into the HMS framework, corresponding to an amine concentration of 0.72–2.16 mmol g^?1. The HMS-NH₂ materials had a high surface area (272–627 m² g^?1), a large total pore volume (0.48–1.92 cm³ g^?1) and exhibited an enhanced adsorption capacity for clofibric acid in aqueous solution.     

Synthesis of magnetical microspheres with tunable large pore mesostructures

The synthesis of core–shell structured magnetic mesoporous silica particles with large pore sizes through a recently developed oil–water biphase stratification coating strategy was reported. The obtained nanoparticles exhibited spherical morphology, high surface area (347–430 m² g^?1) and easily accessible large pore size. Significantly, the pore size of the silica shells can be finely controlled to range from 5.1 to 8.4 nm through tuning the coating conditions, including reaction temperature and the concentration of silica source in the upper oil phase. Such material might have great promising applications in drug delivery, catalysis and purification of water, etc.     

Application of attapulgite/maltose system on mesoporous carbon material preparation for electrochemical capacitors

Mesoporous carbon materials were prepared through atmospheric pressure impregnation at room temperature using attapulgite as hard template and maltose as carbon source. N₂ absorption–desorption, X-ray diffraction, and transmission electron microscopy were used to determine the construction and morphology of the materials. The results showed that the prepared carbon materials possessed chain-layered structures whose surfaces were filled with ample nanoscale apertures. The materials also exhibited partial fasciculus with specific surface area and total pore volume of 628.6 m² g^?1 and 1.31 cm³ g^?1, respectively. Constant current charge/discharge, cyclic voltammetry, and AC impedance tests were performed to evaluate the electrochemical performance of the materials. The constant current charge/discharge tests showed that the materials have excellent energy storage capacity. When the current density was 600 mA g^?1, the specific capacitance value reached 171 F g^?1. The materials showed quasi-rectangular features of typical cyclic voltammetry curve even at high scan rate (200 mV s^?1), indicating that they possess excellent rate capacity. The AC impedance tests showed that the materials were typical porous electrode materials with combination resistance of 0.82 Ω. The specific capacitance of the materials reached 79 % after 1,000 constant current charge/discharge cycles, indicating that they have superior cyclic stability.     

Synthesis of High Surface Area MgAl2O4 Nanopowder as Adsorbent for Leather Dye Removal

Abstract

MgAl₂O₄ nanopowder has been prepared by alkoxides hydrolysis with further calcination at temperature of 700°C. The adsorption of a leather dye, Direct Black 38, onto this material was investigated. The sample was characterized by X-ray-diffraction (XRD), N₂ adsorption–desorption isotherm and Fourier transform infrared spectroscopy. The results showed that sample present a pure phase, and the average nanocrystal size of 8 nm, the BET surface area is about 206.5 m² · g^?1 and total pore volume is about 1.44 cm³ · g^?1. Adsorption kinetics data were modeled by film and pore diffusion model. The experimental isotherm was described by the Langmuir model. MgAl₂O₄ nanopowder presented a great removal efficiency of leather dye by adsorption process, with a maximum adsorption capacity of 833 mg of dye per gram of adsorbent.     

Mesoporous TiO<Subscript>2</Subscript> microspheres synthesized via a facile hydrothermal method for dye sensitized solar cell applications

Mesoporous TiO₂ microspheres were successfully synthesized by a facile hydrothermal process and the obtained product was sintered at 450 °C. The sintered TiO₂ powder was characterised by powder X-ray diffraction pattern and the result shows pure anatase phase with good crystalline nature. The morphological image of field emission scanning electron microscopy and high resolution transmission electron microscopy shows spherical shape and size of the particles is around 100 to 300 nm. The Brunauer–Emmett–Teller surface area of synthesized TiO₂ material was 56.32 m² g^?1 and average pore width of synthesized materials was 7.1 and 9.3 nm. Bimodal pore structure of TiO₂ microspheres has been very effective for electrolyte diffusion into photoanode in dye sensitized solar cells. The synthesized anatase TiO₂ microsphere based dye sensitized solar cells have high surface area with light scattering effect to enhance the photocurrent and conversion efficiency than the commercial P25 photoanode material. The power conversion efficiency of synthesized mesoporous TiO₂ microspheres and commercial P25 material is 4.2 and 2.7 % respectively. Therefore bimodal mesoporous anatase TiO₂ microsphere appears to be a promising and potential candidate for dye sensitized solar cells (DSSC) application.     

One-pot generation of mesoporous carbon supported nanocrystalline H3PW12O40 heteropoly acid with high performance in microwave esterification of acetic acid and isoamyl alcohol

Ordered mesoporous carbon-supported H₃PW₁₂O₄₀ heteropoly acid materials (HPW/OMCs) have been rationally synthesized for the first time. The method is based on the evaporation-induced triconstituent co-assembly effect using the sol–gel process, wherein soluble resol polymer is used as an organic precursor, and triblock copolymer F127 is used as a template. The ordered mesoporous carbon-supported H₃PW₁₂O₄₀ heteropoly acid materials were analyzed and characterized by X-ray diffraction, N₂ adsorption and desorption (BET), and transmission electron microscope. The mesoporous carbon-supported H₃PW₁₂O₄₀ materials possess an ordered mesostructure, narrow pore size distributions (around 2.8–3.6 nm), high pore volumes (up to 0.49 cm³ g^?1), high specific BET surface areas (up to 590 m² g^?1), tailorable HPW content (up to 30 wt%), and well dispersion of HPW particles. Moreover, the resultant mesoporous ordered mesoporous carbon-supported H₃PW₁₂O₄₀ materials exhibit high catalytic activity in microwave esterification of acetic acid and isoamyl alcohol. The obtained 20 % HPW/OMC catalyst exhibits high catalytic performance with 96.7 % of isoamyl acetate yield at temperature of 120 °C, alcohol/acid molar ratio of 2, catalyst amount of 0.2 g, microwave irradiation power of 800 W, and reaction time of 18 min. It was believed that the concentration of H₃PW₁₂O₄₀ have a crucial effect on the HPW/OMCs’ porosity, mesostructure and catalytic performance.     

Hypercrosslinked porous polyporphyrin by metal-free protocol: characterization,uptake performance,and heterogeneous catalysis

Through metal-free protocol, hypercrosslinked porous polyporphyrin with permanent porosity was obatined via the Friedel–Crafts alkylation of tetracarbazolylporphyrin using formaldehyde dimethyl acetal as an external cross-linker. Its chemical structure and porosity was well characterized and confirmed. The BET specific surface area value of HCP-TCPP is 1050 m² g^?1 and related dominant pore size is centered at 0.63 nm. The adsorption amount of methanol by HCP-TCPP is high up to 800 mg g^?1 (about 25.0 mmol g^?1) at its saturated vapor pressure, which is higher than that of toluene (600 mg g^?1, 6.5 mmol g^?1). Further study indicates that polymer HCP-TCPP, possessing the high BET specific surface area and total pore volume, exhibits good hydrogen uptake of 3.44 wt % (77 K) and high carbon dioxide uptake of 41.1 wt % (298 K) at 18.0 bar. Besides, the obtained porous polymer can also be used as an effective heterogeneous catalyst for the Knoevenagel condensation between various aldehydes and malononitrile.     

Preparation and Characterization of Activated Carbon from Eucalyptus Sawdust I. Activated by NaOH

Eucalyptus sawdust was used as a precursor to prepare activated carbon using NaOH as a chemical activation agent. The effect of preparation conditions on the characteristics of the produced activated carbon used as an adsorbent was investigated. The performance of the activated carbon was characterized by N₂ adsorption–desorption isotherms, Brunauer–Emmett–Teller equation, Barett–Joyner–Halenda equation, scanning electron microscopy and Fourier transform infrared analysis. When the eucalyptus sawdust mass was 30.00 g, with particle sizes between 0.25 and 0.42 mm, and the sawdust was heated and charred before activation by NaOH, the optimized conditions for the preparation of activated carbon was found to be as follows: mass ratio of NaOH to eucalyptus sawdust, 1:2; activation time, 30 min; and activation temperature, 700 °C. The Iodine number and BET surface area of the produced activated carbon was 899 and 1.12 × 10³ m² g^?1, respectively, with a 13.3 % yield. Activated carbon exhibits adsorption isotherms of type IV. The total pore volume, micropore volume and average pore diameter were recorded as 0.636, 0.160 cm³ g^?1 and 2.27 nm, respectively. The pore structure of the activated carbon is mainly mesoporous. Carbonyl and hydroxyl groups may also exist on the activated carbon surface.     

Ni-doped TiO2 hollow spheres as electrocatalysts in water electrolysis for hydrogen and oxygen production

This work represented the electrocatalytic properties of Ni-doped titania hollow sphere materials in hydrogen and oxygen evolution during water electrolysis from acidic media. Titania hollow sphere particles were synthesized using poly(styrene-methacrylic acid) latex as template material, and various amount of nickel were doped over the sphere using nickel (II) sulfate as the precursor of nickel. The presence of rutile TiO₂ and NiO phases were revealed during XRD analysis, indicating the critical growth of nickel on the surface of the hollow sphere catalysts. BET surface area results also shown the 166.76 m² g^?1 value for 30 wt% Ni/TiO₂ hollow sphere sample. The SEM and TEM images were confirmed the hollow sphere structure of the catalysts with diameter of 0.8–0.9 μm. The cyclic voltammetric studies proved the presence of both hydrogen and oxygen evolution peaks for all the hollow sphere samples. The anodic peak current density value, which usually represents the oxygen evolution phenomenon, was revealed as 13 mA cm^?2 for 25 wt% Ni-loaded sample; whereas, the hydrogen evolution peak was most intense for 30 wt% Ni/TiO₂ material with cathodic peak current density of 32 mA cm^?2. The average value of ?1.42 were determined as the reaction order of the system irrespective of the nickel loading and heating duration in the synthesis of hollow sphere materials. During photocatalytic water splitting, 30 wt% Ni/TiO₂ hollow sphere sample yielded the highest amount of hydrogen in all irradiation time span.     

Synthesis and application of amine functionalized silica mesoporous magnetite nanoparticles for removal of chromium(VI) from aqueous solutions

In this research, novel nanoparticles of Kit-6 mesoporous silica magnetite were synthesized with 9.6 nm pore diameter and 241.68 m² g^?1 surface area. The synthesized mesoporous magnetite nanoparticles (MMNPs) were functionalized with amine groups. Scanning electron microscopy, powder X-ray diffraction, Fourier transform infrared spectroscopy and nitrogen adsorption–desorption method confirmed the morphology and structure of the synthesized nanoparticles. The amine functionalized MMNPs were used for sorption of toxic chromate ions from aqueous samples. The effect of various experimental parameters (four factors at three levels) on the sorption efficiency of Cr(VI) was studied and optimized via Taguchi L₉ (3⁴) orthogonal array experimental design. At optimum conditions, the sorption of the Cr(VI) was best described by a pseudo second-order kinetic model with R² = 0.9999 and q_eq = 129.8 mg g^?1, suggesting chemisorption mechanism. Adsorption data were fitted well to the Langmuir isotherm and the synthesized sorbent showed complete ion removal with 185.2 mg g^?1sorption capacity.     

The efficient removal of dyes over magnetic Ni embedded on mesoporous graphitic carbon material

Magnetically separable Ni embedded on graphitic mesoporous carbon (NMC) material was fabricated through a facile “sol–gel” route using glucose, nickle nitrate, poly(ethylene glycol)–poly(propylene glycol)–poly(ethylene glycol) (P123) and tetraethyl orthosilicate as carbon source, catalyst and magnetic precursor, soft template and porogen. The obtained NMC material exhibited highly graphitic degree with high surface area of 790 m² g^?1, large pore size at 3.9 nm and pore volume of 0.69 cm³ g^?1. The saturation magnetization was enhanced to 6.82 emu g^?1 because of aggregation of magnetic Ni particles to clusters. NMC material showed excellent removal to Rhodamine B and the adsorption capacity reached to 168.1 mg g^?1 within 120 min. NMC material could be easily separated by an external magnet and reused after ethanol extraction.     

Unexpected Photocatalytic Activity of Simple and Platinum Modified Tubular SiO2 for the Oxidation of Oxalic Acid to CO2

The photocatalytic mineralization of oxalic acid over SiO₂-based materials was investigated in the 200–800 nm range. The photocatalytic activity was found to be strongly related to the morphology of SiO₂ materials. The simple as well as the Pt-modified SiO₂ particles having a predominant spherical shape exhibited null photocatalytic activity. In contrast, the tubular shaped SiO₂ particles revealed an interesting photocatalytic activity, the rate of CO₂ evolvement being 45 µmol g _cat ^?1  h^?1. The initial activity was significantly enhanced (428 µmol CO₂ g _cat ^?1  h^?1) by platinum photodeposition on the outer and inner surface of tubular SiO₂. The catalytic materials were characterized by TEM, UV–VIS and XPS to obtain rational explanations for the phocatalytic activity that was noticed. The experiments revealed that SiO₂ tubes behave as efficient photooxidation microreactors. The morphology-dependent photocatalysis can be an efficient tool in future for the abatement of pollutants in liquid phase.     

Synthesis of bimodal mesoporous carbon nanospheres for methyl orange adsorption

Mesoporous materials with bimodal mesopores show advantages in adsorption, energy storage, and catalysis because such unique structures are beneficial to the mass transfer. Here, we describe the synthesis of bimodal mesoporous carbon nanospheres (BMCSs) by using phenolic resin as carbon precursor, triblock copolymer Pluronic F127 as the soft template, and mesoporous silica spheres as hard templates. The BMCSs with uniform spherical morphology, high specific surface area (1489 m² g^??1), large pore volume (0.92 cm³ g^??1), and bimodal mesoporous structure (3.8 and 6.8 nm) exhibit promising properties for adsorption of methyl orange (MO). The maximum adsorption capacity of the BMCSs is 5.5?×?10² ± 0.2?×?10² mg g^??1, which is higher than that of many adsorbents reported. The kinetics studies show a better fit of pseudo-second-order model. Meanwhile, fitting equilibrium data show that the Langmuir model is more suitable to describe the MO adsorption than Freundlich model.     

Preparation of Mesoporous V–Ce–Ti–O for the Selective Oxidation of Methanol to Dimethoxymethane

Mesoporous V–Ce–Ti–O oxides were synthesized through the combination of sol–gel and hydrothermal methods and were characterized by different techniques. N₂ adsorption showed that the mesoporous oxides with 0–20 wt.% V₂O₅ possessed the surface areas of about 160 m² g^?1 with narrow pore size distribution centered around 4–5 nm. Vanadium species were highly dispersed in the samples, as confirmed by the wide angle XRD and Raman spectroscopy. The surface acidity of the materials was determined by the microcalorimetric adsorption of NH₃. Temperature programmed reduction and O₂ chemisorption were used to probe the redox property of the materials. It was found that the mesoporous V–Ce–Ti–O possessed bifunctional characters of acidic and redox properties that catalyzed the oxidation of methanol to dimethoxymethane (DMM). These bifunctional characters were further enhanced by the addition of V₂O₅ and SO₄ ^2? onto V–Ce–Ti–O simultaneously. Such supported catalysts exhibited excellent performance for the selective oxidation of methanol to DMM. Specifically, 72% conversion of methanol with 85% selectivity to DMM was achieved at 423 K over a SO₄ ^2?–V₂O₅/V–Ce–Ti–O catalyst.     

Hydrogen Production from Aqueous Solutions of Glycerol on TiO<Subscript>2</Subscript>/Ru-MCM-41 Photocatalysts Using Solar Light

Ru-MCM-41 molecular sieves were prepared (Si/Ru atomic ratio?=?50 or 100) by a hydrothermal method and impregnated with TiO₂. The materials were characterized by XRD, N₂ physisorption, DRS, SEM and TEM. Their potential application to hydrogen production by photolysis of water using solar light was tested in a batch reactor using mixtures of water and glycerol (0–6.85 mol L^?1) at pH varying from 1 to 11. The photocatalytic efficiency under simultaneous UV (0.05 μW cm^?2) and visible light (90.07 W m^?2) irradiation was compared to the activity of TiO₂/MCM-41 (i.e., no Ru incorporated) and commercial Degussa TiO₂ P25. The most active material was 20%TiO₂/Ru-MCM-41(100) whose performance (220.6 µmol g_Ti ^?1 H₂) was approximately 47 times higher than TiO₂ P25. Characterization results showed the deposition of TiO₂ and revealed the formation of RuO₂ on the surface. Hydrogen generation was improved due to higher charge separation at the TiO₂/RuO₂ heterojunction and to the enhancement of visible light absorption caused by surface plasmon resonance (SPR). Hydrogen production increased with glycerol concentration, tending to stabilize around 40.3 µmol h^?1 g_Ti ^?1 above 4 mol L^?1 of glycerol. Hydrogen generation reached its maximum at extreme values of pH (1 and 11).