Surface properties of porous carbons obtained from polystyrene-based polymers within inorganic templates: role of polymer chemistry and inorganic template pore structure

Three inorganic adsorbents were applied as templates to produce porous carbons from polystyrene-based organic polymers. As matrices, amorphous silica gel, mesoporous alumina and microporous zeolite 13X were used. Organic precursors were polystyrene sulfonic acid (co-maleic acid) sodium salt and polystyrene co-maleic acid isobutyl/methyl mixed ester. The impregnated templates were carbonized at 800 °C. After removal of inorganic matrices porous carbons were obtained. Materials were characterized by adsorption of nitrogen, thermal analysis, potentiometric titration and SEM. Owing to the template carbonization, highly mesoporous carbons were obtained (S_BET up to 1500 m²/g, V_t up to 3 cm³/g) with majority of pores with sizes between 20–200 Å. Although the carbons were not replicas of their matrices, the carbonization within the confined space with utilization of self-released pore formers resulted in unique carbonaceous materials with very acidic surface. That acidity is linked to either exothermic effect of sodium reactivity with moist air or susceptibility for air oxidation of small graphene layers formed in the confined pore space.     

Preparation of ordered mesoporous SiCN ceramics with large surface area and high thermal stability

For the first time, highly ordered two-dimensional (2-D) and three-dimensional (3-D) mesoporous SiCN ceramics with high surface area and high thermal stability were prepared by nanocasting a preceramic polymer solution into mesoporous carbon templates, CMK-3 and CMK-8, respectively. As a negative replica of CMK-3 carbon, the obtained mesoporous SiCN ceramic possessed an ordered 2-D hexagonal mesostructure, which is similar to the structure of SBA-15 silica except for the reduced dimensions. An ordered 3-D cubic mesoporous SiCN ceramic was also fabricated using CMK-8 as a template. The wall of the mesoporous SiCN replicas consisted of an amorphous SiCN ceramic phase, which possessed high thermal stability at high temperature up to 1000 °C. N₂-sorption isotherms revealed that these ordered mesoporous SiCN ceramics have high BET surface areas (up to 472 m² g⁻¹) and narrow pore-size distributions, which was preserved even after a re-treatment at 1000 °C in air. The use of carbon template played an important role in the preparation of mesoporous SiCN replicas and enhanced the thermal stability of the SiCN products. It is expected that many other types of ordered mesoporous ceramics can be prepared from nanoporous carbon by nanocasting method.     

Methyltrimethoxysilane based monolithic silica aerogels via ambient pressure drying

We have developed a novel route to monolithic silica aerogels via ambient pressure drying by the acid–base sol–gel polymerization of methyltrimethoxysilane (MTMS) precursor. An extent of silica polymerization in the alcogels plays a crucial role in obtaining the monolithic aerogels which could be optimized by a proper control over the MeOH/MTMS molar ratio (S) during the sol–gel synthesis. The alcogel undergoes the distinct “spring-back effect” at the critical stage of the drying and thereby preserving the highly porous silica network without collapse. The process yields silica aerogels exhibiting very low bulk density and high specific surface area of 0.062 g/cm³ and 520 m²/g, respectively. The average pore diameter and the cumulative pore volume varied from 4.5 to 12.1 nm and 0.58 to 1.58 cc/g, respectively. In addition, the aerogels are superhydrophobic with contact angle as high as 152°. We anticipate that the new route of the monolithic silica aerogel production will greatly expand the commercial exploitation of these materials.     

Sintering characteristics of in situ formed low expansion ceramics from a powder precursor in the form of hydroxy hydrogel

Lithium aluminosilicate powder precursors of compositions Li₂O:Al₂O₃:SiO₂ as 1:1:2; 1:1:2.5 and 1:1:3 were prepared in the hydroxy hydrogel form by wet interaction technique in aqueous medium followed by sintering for ultimate synthesis of low expansion ceramics. Phases formed in the sintered specimens were analyzed by XRD technique. Thermal expansion of the specimens sintered at 1100, 1200 and 1300 °C were also measured. It was found that β-spodumene, lithium aluminum oxide and silica were the predominat phases in all the specimens. Sintering was optimum up to 1200 °C beyond which no further noticeable shrinkage was observed. The sintered specimens remained highly porous even after firing at 1300 °C, whose bulk density and apparent porosity were in the range of 1.25–1.42 g/cm³ and 43–48%, respectively. Thermal expansion characteristics and density of the sintered specimens were found to be primarily related to the composition of the phases formed during sintering. A porous low expansion ceramic monolith could be prepared using the present technique.     

Hydrotreating of heavy vacuum gas oil (HVGO) on molybdenum and tungsten nitrides catalytic phases

A series of supported and unsupported Mo₂N and W₂N phases were synthesized by means of the treatment under ammonia atmosphere at 700°C of Mo and W oxides. The X-ray diffraction and electron microscopy techniques verified the formation of the Mo₂N and W₂N ceramic phases, while the N₂ adsorption (BET) was used to determine the surface areas, between 46–133 m²/g for Mo₂N (unsupported) and 81–101 m²/g for W₂N (unsupported). The supported phases had surface areas between 109–113 and 109–122 m²/g, for Mo₂N/Al₂O₃ and W₂N/Al₂O₃, respectively. The catalytic hydrotreating of a heavy vacuum gas oil (HVGO) derived from Maya crude (i.e. 2.21 wt.% S, 0.184 wt.% N₂) was performed on both, supported and unsupported Mo nitrides and W nitrides, which promoted the HDN reaction preferentially, up to 26.6% on Mo₂N/Al₂O₃ and up to 22.3% on W₂N/Al₂O₃, against 3.26% on the reference catalyst, i.e. CoMo/Al₂O₃ at 350°C and 80 kg/cm². Also, the rates for HDN increased with the crystallite size in the unsupported W₂N series. Also, the pore volume and mean pore diameters of the Mo₂N/Al₂O₃ and W₂N/Al₂O₃ series improve substantially with respect to the pure ceramic phases.     

Porous YSZ ceramics by water-based gelcasting

Gelcasting, as a novel method to form ceramic bodies, has been successfully developed to fabricate porous YSZ ceramics with an open porosity of 33.1–50.3%, mean pore size of 0.66–0.98 μm and the nitrogen permeability of 215–438 m³/m².bar.h. In order to further illustrate the features of this water-based gelcasting process to prepare porous ceramics, the same YSZ powders were blended with the same additives, and then cold pressed and sintered at the same conditions employed for gelcasting process. Compared with the cold pressed samples, the gelcast bodies exhibit higher open porosity, lower closed porosity, relatively larger pore size and thus higher gas permeability. Therefore, the developed gelcasting process is a very effective method to fabricate porous ceramics for filters or supports.     

Production of high porosity nanoparticles of cerium oxide in clay

Cerium oxide nanoparticles modified montmorillonite was obtained by interaction of a clay with (NH₄)₂Ce(NO₃)₆. The mean size of cerium oxide nanoparticles in clay was at 3.5 nm. The product was an amorphous solid and showed high permanent porosity and stability at high temperatures. The amorphous structure of the sample was proven by X-ray diffraction and electronic diffraction. The porous structure was studied by means of chemisorption and it was shown that samples calcined at 550 °C had S_BET = 239 m²/g; micropore volume = 0.1839 cm³/g; average pore diameter = 3.07 nm.     

Mesoporous and nanostructured CeO2 as supports of nano-sized gold catalysts for low-temperature water-gas shift reaction

Mesoporous particles and 1D nanorods of cerium oxides have been prepared by modifying the hydrothermal route of a surfactant-assisted controllable synthesis. Mesoporous cerias were obtained in a sealed glass vessel under continuous stirring, while ceria nanorods were obtained in a Teflon-lined autoclave without stirring. The mesoporous cerias did not show long-range mesoscopic organization, exhibiting a broad mesopore size distribution in the region 8–15 nm. A BET surface area of 100 m²/g with a total pore volume of 0.33 cm³/g is obtained for as-synthesized mesoporous ceria. The ceria nanorods exhibit a cubic crystalline structure after calcination, having the lengths in the range of 150–300 nm and diameters in the range of 10–25 nm. The growth direction of ceria nanorods is along [1 1 0]. A surface area of above 50 m²/g is obtained in the calcined nanorods. These synthesized ceria materials were used as supports of nano-sized gold catalysts, prepared by deposition–precipitation method. Their catalytic activity was evaluated by the low-temperature water-gas shift reaction. The gold/mesoporous ceria catalytic system exhibited higher catalytic activity than gold/ceria nanorods. It is revealed that the mesoporous and nanostructured cerias are of much interest as potential supports for gold-based catalysts that are effective for low-temperature water-gas shift reaction.     

Synthesis of ordered mesoporous carbon containing highly dispersed copper–sulphur compounds in the carbon framework via a nanocasting route

We report a synthesis of ordered mesoporous carbon containing highly dispersed copper–sulphur particles in its carbon framework via the nanocasting route, involving the use of SBA-15 as the template and copper(II) phthalocyanine-tetrasulfonic acid tetrasodium salt (denoted as PcS) as the single precursor. It was found that below a pyrolysis temperature of 600 °C, PcS molecules are stable, allowing the formation of stable nanocast carbon. However, at higher pyrolysis temperature, PcS molecules decompose to carbon and copper–sulphur compounds in the carbon framework, or big copper particles, depending on the conditions. The obtained carbons show tunable specific surface areas in the range of 530–980 m²/g and pore volumes in the range of 0.5–1.2 cm³/g. Using phthalocyanine as carbon precursor, it is possible to directly prepare nanocast carbon containing highly dispersed metallic nanoparticles in its skeleton.     

High-quality, oriented and mesostructured organosilica monolith as a potential UV sensor

We synthesized high-quality and oriented periodic mesoporous organosilica (PMO) monoliths through a solvent evaporation process using a wide range of mole ratios of the components: 0.17–0.56 1,2-bis(triethoxysilyl)ethane (BTSE): 0.2 cetyltrimethylammonium chloride (CTACl): 0–1.8 × 10⁻³ HCl: 0–80 EtOH: 5–400 H₂O. X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM) images indicated that the mesoporous channels within the monolith samples were oriented parallel to the flat external surface of the PMO monolith and possessed a hexagonal symmetry lattice (p6mm). The PMO monolith synthesized from a reactant composition of 0.35 BTSE: 0.2 CTACl: 1.8 × 10⁻⁶ HCl: 10 EtOH: 10 H₂O had a pore diameter, pore volume, and surface area – obtained from an N₂ sorption isotherm – of 25.0 Å, 0.96 cm³ g⁻¹ and 1231 m² g⁻¹, respectively. After calcination at 280 °C for 2 h in N₂ flow, the PMO monolith retained monolith-shape and mesostructure. Pore diameter and surface area of the calcined PMO monolith sample were 19.8 Å, 0.53 cm³ g⁻¹ and 1368 m² g⁻¹, respectively. We performed ²⁹Si and ¹³C CP MAS NMR spectroscopy experiments to confirm the presence of Si–C bonding within the framework of the PMO monoliths. We investigated the thermal stability of the PMO monoliths through thermogravimetric analysis (TGA). In addition, rare-earth ions (Eu³⁺, Tb³⁺ and Tm³⁺) were doped into the monoliths. Optical properties of those Eu³⁺, Tb³⁺ and Tm³⁺-doped PMO monoliths were investigated by photoluminescence (PL) spectra to evaluate their potential applicability as UV sensors.     

Dielectric and ferroelectric properties of lead indium niobate ceramic prepared by wolframite method

The dielectric and ferroelectric properties of lead indium niobate (Pb(In_1/2Nb_1/2)O₃, PIN) ceramic prepared by an oxide-mixing method via wolframite route were investigated. The 98.5% perovskite fine-grained PIN ceramics with average grain sizes of 1–2 μm were obtained by sintering at 1050 °C for 2 h. The dielectric properties of the PIN were of relaxor ferroelectric behavior with temperature of dielectric maximum (T_m) 53 °C and dielectric constant (_r) 4300 (at 1 kHz). The P–E hysteresis loop measurements at various temperatures showed that the ferroelectric properties of the PIN ceramic changed gradually from the paraelectric behavior at temperature above T_m to slim-loop type relaxor behavior at temperature below T_m. Moreover, the P–E loop became more open at temperatures much lower than T_m. At −25 °C, the maximum polarization is found to be 8 μm/cm² at a field of 30 kV/cm, with P_r value of 2.5 μm/cm² and E_c of +7.5 kV/cm.     

Synthesis and oxygen transport characteristics of dense and porous cerium/gadolinium oxide materials: Interest in membrane reactors

Cerium/gadolinium oxide (CGO)-based ceramic ion conductive membranes (CICMs) have potential uses in catalytic membrane reactors (CMRs) and solid oxide fuel cells (SOFCs). A supercritical CO₂ aided sol–gel process allowed the synthesis of CGO materials with the composition Ce_0.9Gd_0.1O_1.95. The produced nanophase powders were non-agglomerated, with a controlled morphology, a high purity and a high specific surface area (>100 m²/g). The CGO cubic crystalline phase has been obtained at temperatures <300 °C, lower than those of conventional solid state chemistry routes. With respect to ionic oxygen transport, a high conductivity at intermediate temperature (2 × 10⁻² S cm⁻¹ at 600 °C), almost equivalent in dense and porous samples, has been obtained on sintered materials prepared from these powders. In relation to their porosity characteristics, a modelling approach successfully explained the high ionic oxygen transport of some specific porous samples. Future directions for preparing porous conductive ceramics well adapted to CMR or SOFC applications can be anticipated from this model.     

The preparation of high-surface area, thermally-stable, metal-oxide catalysts and supports by a cellulose templating approach

A simple and convenient templating approach for the preparation of metal-oxide catalysts and supports has been studied. The method, based on the absorption of an aqueous solution of metal salts by cellulose material, followed by drying and combustion of the organic matrix, leads to the formation of high-surface area mesoporous materials with unusually high thermal stability. Examples include Ce–Zr mixed oxides (BET surface areas of 90–130 m²/g after calcination at 800°C for 2 h; 21–30 m²/g after 12 h at 1050°C) and La-stabilized alumina (BET surface areas of 275–320 m²/g after calcination at 800°C for 2 h, 88–141 m²/g after 12 h at 1050°C). The pore-size distribution, morphology, and the effect of preparation parameters on surface area are discussed.     

A template-free, sonochemical route to porous ZnO nano-disks

A template-free, sonochemical aqueous route was used to synthesize hexagonal-shaped ZnO nanocrystals with a combined micro- and mesoporous structure. The products are much more porous when the sonohydrolysis is carried out under argon than their sonication under air. This has been attributed to the higher average specific heat ratio γ (=C_p/C_v) of argon gas, leading to higher bubble collapse temperatures. Small-angle XRD (SAXRD) studies show that the microporosity is lost at 250 °C, while the mesoporous structure persists till a very high temperature (550 °C). The BET surface area of the products synthesized under argon and air are 35 and 13 m²/g, respectively. The pore size is distributed from 1 nm (micropore) to 3.1–3.4 nm (mesopore), while the ZnO nanoparticles are 6.3 ± 1.2 nm. The possible mechanisms of the self-assembled pore formation are attributed to the organic porous framework of basic zinc acetate. The excitonic absorption of the ZnO occurs at 349 nm. The photoluminescence (PL) spectra of the ZnO nano-disks show the red-shifted band edge exciton transitions and the presence of deep levels due to oxygen vacancies or surface-deep traps, because of the porous structure.     

A new technique for preparing ceramics for catalyst support exhibiting high porosity and high heat resistance

A new technique for preparing magnesia ceramics of high porosity and high temperature resistance has been developed. Spray freeze drying of magnesium sulfate aqueous solution produced fine salt particles having open pores due to sublimation of ice crystals. The particles were calcined to porous magnesium oxide and formed a green body. Highly porous magnesia was produced by firing the green body. The porous magnesia exhibited a bimodal pore size distribution of macro-pores of micron order and meso-pores smaller than 100 nm. Porosity was 87–90%. After addition of an aluminum additive with an amount 3–5 mol%, the magnesia exhibited high heat resistance; surface area was greater than 20 m² g⁻¹ after 20 h exposure in a 1573 K oven. Thus, the porous magnesia is expected to be very suitable for combustion catalyst support used in a high temperature environment.     

Thermal stability and catalytic activity of flame-made silica–vanadia–tungsten oxide–titania

Vanadia (0.9 or 2 wt.%) and silica (0–5 wt.%) doping of flame-made tungsten oxide–titania nanostructured catalyst powders (anatase, 100 m²/g, 10 wt.% WO₃) is investigated. The effect of dopants on structural and chemical properties of these powders were analyzed by nitrogen adsorption, X-ray diffraction (XRD), temperature programmed reduction (TPR), transmission electron microscopy (TEM) and Raman spectroscopy. After calcination for 20 h at 700 °C in air, the thermally most stable composite powder conserved its specific surface area (SSA) to 90 m²/g and its anatase content to 96 wt.%. Tungsten oxide and vanadia form thin polymeric layers (1 nm) on the surface of the titania support. Adding silica improves the thermal and crystal stability of the catalysts even at higher reactor temperatures. As a result both NO conversion and the rate of selective catalytic reduction (SCR) with NH₃ were increased.     

Activated carbons prepared from rice hull by one-step phosphoric acid activation

Activated carbons were prepared from rice hull by one-step phosphoric acid activation in this work. The evolution of pore structure and surface chemistry in the activation temperature range of 170–450 °C was investigated through various characterization techniques. The results showed that the development of porosity (extent of activation) was negligible at activation temperature below 300 °C, and rapid evolution occurred in 300–400 °C. Porous activated carbon with bimodel pore structure (pore < 1 nm and pore > 1 nm) and BET surface area as high as 1295 m²/g was obtained at 450 °C. The ash contents of samples prepared in this study were in the range of 5–21%. The ash contents of carbons prepared in this study initially decreased from 21.03% to 4.89% with the change of temperature from 170 to 300 °C, then increased to 8.72% at 450 °C. Boehm titration results suggested that low activation temperature (300 °C) benefits the formation of acidic surface groups. With the increase of activation temperature from 300 to 350 °C, the concentrations of strong, intermediate and weak acidic surface groups decreased from 2.23, 1.87, and 2.73 to 1.66, 1.32, and 2.16 mmol H⁺/g, respectively. Over 350 °C, the change of these groups were insignificant. FTIR results revealed the existence of carbonyl-containing, phosphorus-containing groups, and groups containing Si–O bond. The relative concentration of carbonyl-containing groups decreases with an increase in activation temperature, while that of phosphorus-containing groups follows the reverse trend. The content of Si–O decreased first, then slowly increased with the increase of activation temperature. Boehm titration and FTIR (Fourier transform infrared spectroscopy) results indicated that the surfaces of these carbons contain both temperature-sensitive and temperature-insensitive groups. The temperature-sensitive part consists mainly of carbonyl-containing groups, such as carboxylic groups, while the temperature-insensitive part is primarily phosphorus-containing groups and groups containing Si–O bond. This study demonstrated that carbon products with relative low ash content and high activation degree can be prepared from rice hull by H₃PO₄ activation at suitable temperature.     

Template synthesis of large pore ordered mesoporous carbon

Nanocast carbon (NCC-1) with large pores and ordered structure was synthesized via a nanocasting process using aluminum-containing SBA-15 as template and furfuryl alcohol (FA) as carbon precursor. This carbon has several interesting features, such as two steps with distinguished hystereses in the nitrogen sorption isotherm, high surface area of 2000 m²/g and large pore volumes of 3.0 cm³/g. It was found that the key factors in the synthesis of such carbons are the aging temperature of the SBA-15 template, the concentration of furfuryl alcohol (dissolved in trimethylbenzene), and the carbonization temperature. The optimal conditions for materials with high surface area and pore volumes are SBA-15 starting materials aged at 140 °C, 25 vol% of FA solution and 850–1100 °C carbonization temperatures. Moreover, it has been demonstrated that such nanocast carbon can be synthesized in a more facile way than previously reported. Purely siliceous SBA-15 without the need of Al³⁺-incorporation can be directly used as template. In this case, the polymerization catalyst—oxalic acid and FA were simultaneously introduced into the pore space of SBA-15.     

Novel alumina ‘KK Leaf Structures’ as catalyst supports

A method has been devised in which alumina can be formed into a layer of thin leaf-like structures that have a thickness of 0.2–0.8 μm. This consists of a process in which aluminium iso-propoxide is transformed into a sol–gel and then: frozen (−195 °C), freeze-dried (−60 °C), and finally calcined (450 °C). These special conditions lead to the formation of a structure that is named: ‘KK Leaves’.

After calcining at 450 °C, the leaves have a specific surface area of 282 m²/g, an average pore size of 2.8 nm, and exhibit a curly shape. The structure has the appearance of a loosely packed (but ordered) collection of thin curly leaves with fine ribs resembling leaf veins on trees and plants. They would readily act as a support, e.g., for a catalyst, or adsorbents, or act as a membrane filter.     

Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO2

A visible-light-active TiO₂ photocatalyst was prepared through carbon doping by using glucose as carbon source. Different from the previous carbon-doped TiO₂ prepared at high temperature, our preparation was performed by a hydrothermal method at temperature as low as 160 °C. The resulting photocatalyst was characterized by XRD, XPS, TEM, nitrogen adsorption, and UV–vis diffuse reflectance spectroscopy. The characterizations found that the photocatalyst possessed a homogeneous pore diameter about 8 nm and a high surface area of 126 m²/g. Comparing to undoped TiO₂, the carbon-doped TiO₂ showed obvious absorption in the 400–450 nm range with a red shift in the band gap transition. It was found that the resulting carbon-doped TiO₂ exhibits significantly higher photocatalytic activity than the undoped counterpart and Degussa P25 on the degradation of rhodamine B (RhB) in water under visible light irradiation (λ > 420 nm). This method can be easily scaled up for industrial production of visible-light driven photocatalyst for pollutants removal because of its convenience and energy-saving.