Desulfurization of fuels by means of a nanoporous carbon adsorbent

Mesoporous carbon, CMK-3, was prepared using hexagonal Al-SBA-15 mesoporous silica, instead of SBA-15, as a template. The synthesized materials were examined via X-ray diffraction and N₂-adsorption. The mesoporous carbon was studied for its adsorption of dibenzothiophene (DBT) from petroleum fuels. The performance of this adsorbent was compared with SBA-15 and Al-SBA-15, through which CMK-3 showed higher sulfur adsorption capabilities due to a larger mesopore volume and a higher specific surface area. The uptake capacity for DBT followed the order CMK-3 > Al-SBA-15 > SBA-15. The results confirmed the importance of the adsorbent pore size and its surface chemistry for the adsorption of DBT from liquid phase.Langmuir and Freundlich isotherm models were used to fit equilibrium data for CMK-3. The equilibrium data were best represented by the Langmuir isotherm. Kinetic studies were carried out and showed the sorption kinetics of dibenzothiophene was best described by a pseudo-second-order kinetic model.     

A simple method to synthesize graphitic mesoporous carbon materials with different structures

Graphitic mesoporous carbon materials with different structure were synthesized by reversed replication method. SBA-15 was used as hard template and the synthesized aromatic polymers with different polymerization degree as the carbon sources. Adopting the impregnation method, the carbon source was assembled into the pore of the SBA-15. The silica/aromatic polymers system was carbonized under N₂ atmosphere (high polymerization degree aromatic polymers) and vacuum (low polymerization degree aromatic polymers) to produce the graphitic mesoporous carbon materials with structure of CMK-3 and CMK-5, respectively. It is a easy way to synthesize the graphitic mesoporous carbon materials, especial for the CMK-5 structure. The porous structure and composition of these carbon materials were characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectrometry, and N₂ adsorption–desorption measurements.     

Adsorption of l-histidine over mesoporous carbon molecular sieves

Mesoporous carbon, CMK-3, was prepared by large pore hexagonal mesoporous silica SBA-15. The structural order and textural properties of all the materials were studied by XRD, HRTEM, and nitrogen adsorption. Adsorption of l-histidine (His) over various porous adsorbents such as CMK-3, SBA-15, and activated carbon was studied from solutions with different pH. His adsorption was observed to be pH dependent with maximum adsorption near the isoelectric point of the amino acid. CMK-3 showed a larger amount of His adsorption as compared to SBA-15 and the conventional adsorbent, namely activated carbon. CMK-3 registers the total adsorption capacity of ca. 1350 μmol g⁻¹ which is ca. 12 times higher than the adsorption capacity of SBA-15. This large difference could be mainly due to the stronger hydrophobic interaction between the non-polar side chains of amino acids and the hydrophobic surface of the mesoporous carbon as compared to mesoporous silica. The influence of ionic strengths on the adsorption of His was also studied and the results are discussed. Nitrogen adsorption of CMK-3 after His adsorption confirmed that His molecules are tightly packed inside the mesopores.     

Easy synthesis of an ordered mesoporous carbon with a hexagonally packed tubular structure

Ordered mesoporous carbon with hexagonal arrays of tubes (CMK-5) was successfully synthesized via a nanocasting process by directly using SBA-15, instead of AlSBA-15, as a template, furfuryl alcohol as a carbon source and oxalic acid as the catalyst. The time consuming impregnation of SBA-15 with aluminum could be saved. The as-synthesized CMK-5 exhibits a tubular structure with double pore system. The loading amount of carbon precursor on the pore walls of SBA-15 is the key factor for the formation of the CMK-5 structure with two-dimensional hexagonal arrays of tubes, and the pore diameter can be adjusted by varying the loading amount of the carbon precursor. The CMK-5 carbon exhibits high apparent surface area up to ∼2500 m²/g and high pore volume reaching ∼2 cm³/g, which is due to the unique structure of CMK-5. The characterization results confirmed that carbonization under argon atmosphere instead of vacuum is sufficient for the structural formation of CMK-5 carbons, and can be used as an alternative pathway to prepare tubular-type carbons.     

Synthesis of mesoporous materials SBA-15 and CMK-3 from fly ash and their application for CO2 adsorption

A supernatant solution of silicate species extracted from coal fly ash in a power plant by alkali fusion was used in acidic condition to prepare a mesoporous silica SBA-15. The SBA-15 was used as a template for the synthesis of a mesoporous carbon CMK-3 using sucrose as a carbon source. Characterization of the produced mesoporous materials by XRD, N₂ adsorption-desorption, SEM, and TEM confirmed the formation of well-ordered hexagonal mesostructures. Textural properties were found close to those prepared by pure chemicals. SBA-15 after polyethyleneimine impregnation and CMK-3 were tested for carbon dioxide adsorption, successfully demonstrating the possibility of recycling the industrial waste product in a power plant into a useful adsorbent.     

Preparation and application of chelating polymer-mesoporous carbon composite for copper-ion adsorption

A mesoporous carbon material, CMK-1 was successfully functionalized with carboxymethylated polyethyleneimine (CMPEI) by a simple adsorption method. The physicochemical properties of the polymer-carbon composite (denoted as CMPEI/CMK-1) were investigated by X-ray diffraction, N₂ adsorption-desorption and X-ray photoelectron spectroscopy (XPS). The adsorption behaviors of Cu(II) ion on the CMK-1 and CMPEI/CMK-1 materials were examined under the batch-type experimental conditions. The CMPEI/CMK-1 material showed a typical Langmuir isotherm with a 10-fold increase in adsorption capacity, compared to that of CMK-1. In the case of 0.02 mM Cu(II) solution, the copper ions were completely removed by utilizing the CMPEI/CMK-1 material both at pH values of 3 and 5. The CMPEI/CMK-1 material also exhibited a remarkably high distribution coefficient value (K_d = 2.75 × 10⁵). The results from XPS depth profiles before and after the copper-ion adsorption indicated that the CMPEI and the adsorbed Cu(II) ions were uniformly distributed within the CMK-1 particles.     

Preparation of nitrogen-doped mesoporous carbon nanopipes for the electrochemical double layer capacitor

The direct functionalization of ordered mesoporous carbon nanopipes was achieved by using nitrogen-containing carbon precursor and SBA-15 as a removable template. The prepared carbon material has uniform pore structure as CMK-5 type and retained a relatively large amount of nitrogen species after pyrolysis and removal of the silica template. The results of cyclic voltammetric measurement showed the prepared nitrogen-functionalized carbon materials was more stable and desirable than CMK-5 for the electrochemical capacitor.     

Simple synthesis of mesoporous carbon with magnetic nanoparticles embedded in carbon rods

Magnetically separable ordered mesoporous carbon containing magnetic nanoparticles embedded in the carbon walls was synthesized using a simple synthetic procedure. The resulting magnetically separable mesoporous carbon was denoted as M-OMC (magnetically separable ordered mesoporous carbon) poly(pyrrole) with residual Fe²⁺ ions in the mesoporous channel was converted to carbon material containing superparamagnetic nanoparticles. The size of the magnetic nanoparticles obtained was restricted by the channel size of the SBA-15 silica template, which resulted in the generation of superparamagnetic nanoparticles embedded in the carbon rods. The blocking temperature of M-OMC is 110 K. Pore size and textural property of M-OMC is similar to that of hexagonally ordered mesoporous carbon fabricated using SBA-15 silica as a template. The saturation magnetization of M-OMC is ca. 30.0 emu/g at 300 K, high enough for magnetic separation.     

Adsorption of vitamin B12 on ordered mesoporous carbons coated with PMMA

Ordered mesoporous carbons CMK-3 and CMK-1 were prepared from SBA-15 and MCM-48 materials with pore diameters 3.9 nm and 2.7 nm, respectively. When both mesoporous carbons were coated with about 10 wt.% poly(methyl methacrylate) (PMMA), the pore diameters decreased from 3.9 nm to 3.4 nm for CMK-3 and from 2.7 nm to 2.5 nm for CMK-1. These mesoporous carbons containing about 10 wt.% PMMA were studied as adsorbents of Vitamin B 12 (VB12) from water solutions, and their performances were compared with that of pristine CMK-3, CMK-1. Compared with CMK-1, CMK-3 showed higher vitamin B12 adsorption due to a larger mesopore volume, a higher BET surface and a larger pore diameter. After coated with PMMA, both mesoporous carbons showed higher adsorption capacity than pristine materials. The adsorption properties were influenced by the pore structure and surface properties of mesoporous carbons.     

New mesoporous carbon materials synthesized by a templating procedure

The new porous carbon materials were obtained by templating procedure using mesoporous silica (SBA-15) as template. The ordered mesoporous silica materials were synthesized by using Pluronic P123 (non-ionic triblock copolymer, EO₂₀PO₇₀O₂₀). SBA-15/cryogel carbon composites were obtained by sol–gel polycondenzation of resorcinol and formaldehyde in the presence of different amount of SBA-15. The polycondenzation was followed by freeze drying and subsequent pyrolysis. One set of SBA-15/sucrose carbon composites was prepared by using sucrose as carbon source. The silica template was eliminated by dissolving in hydrofluoric acid (HF) to recover the carbon material. The obtained carbon replicas were characterized by nitrogen adsorption–desorption measurements, X-ray diffraction and scanning electron microscopy (SEM). It was revealed that the samples have high specific surface (533–771 m² g^?1), developed meso- and micro-porosity and amorphous structure. Porous structure of carbon replicas was found to be a function of the carbon source, properties of SBA-15 and silica/carbon ratio. Room temperature adsorption of nitrogen and adsorption of phenol from aqueous solutions were investigated.     

Synthesis of recyclable catalyst-sorbent Fe/CMK-3 for dry oxidation of phenol

The magnetic mesoporous material Fe/CMK-3 acting as a catalyst-sorbent was synthesized by using ordered mesoporous carbon CMK-3 as the supporter, Fe(NO₃)₃ as the iron source, and glycol as the reducing agent. The samples synthesized were characterized by powder X-ray diffraction (XRD), N₂ adsorption-desorption, scanning electron microscope (SEM) and transmission electron microscopy (TEM). The results show that the prepared Fe/CMK-3 preserved the ordered mesoporous structure of CMK-3, and magnetic species was mainly Fe₃O₄, which was dispersed inside channels of CMK-3 as nanoparticles with the diameter of around 10 nm. The adsorption and catalytic dry oxidation efficiency of the prepared Fe/CMK-3 were determined. The results also show that Fe/CMK-3 had good adsorption performance of phenol in aqueous solution and could be easily separated from water and recycled due to its ferromagnetic nature. Iron oxides supported on CMK-3 were excellent catalysts for dry oxidation of phenol. After 15 adsorption-catalytic oxidation cycles, the phenol adsorption capacity of Fe/CMK-3 only decreased a little, suggesting the good practicality. Combined thermogravimetry and mass spectrum (TG-MS) instrument was used to investigate the catalytic oxidation of phenol on Fe/CMK-3 and the ignition characteristics of the catalyst-sorbent. The supported Fe₃O₄ was found to be not only the magnetic component but also the active catalyst for the oxidation of phenol. The adsorbed phenol could be oxidized into CO₂ and H₂O at 220 °C at which no obvious phenol desorption or CMK-3 ignition occurred.     

Indoor formaldehyde removal over CMK-3

The removal of formaldehyde at low concentrations is important in indoor air pollution research. In this study, mesoporous carbon with a large specific surface area was used for the adsorption of low-concentration indoor formaldehyde. A mesoporous carbon material, CMK-3, was synthesized using the nano-replication method. SBA-15 was used as a mesoporous template. The surface of CMK-3 was activated using a 2N H₂SO₄ solution and NH₃ gas to prepare CMK-3-H₂SO₄ and CMK-3-NH₃, respectively. The activated samples were characterized by N₂ adsorption-desorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The formaldehyde adsorption performance of the mesoporous carbons was in the order of CMK-3-NH₃ > CMK-3-H₂SO₄ > CMK-3. The difference in the adsorption performance was explained by oxygen and nitrogen functional groups formed during the activation process and by the specific surface area and pore structure of mesoporous carbon.     

Pd/CMK-3的合成及其在Suzuki-Miyaura碳-碳偶联反应中的应用

利用介孔二氧化硅（SBA-15）为模板、蔗糖为碳源,制备了有序介孔碳材料CMK-3,然后以CMK-3为载体,利用浸渍还原法得到介孔碳负载Pd纳米粒子的复合催化剂（Pd/CMK-3）,通过XRD、TEM以及氮气吸附-脱附等手段对催化剂的微结构和组分进行分析,结果表明CMK-3为有序介孔结构,孔径约为5nm,Pd/CMK-3保留了介孔结构,且孔道中负载有不同尺寸的Pd粒子。应用于无配体催化的Suzuki-Miyaura相似文献   

Bridging mesoporous carbon particles with carbon nanotubes

The enhancement of the electrical conductivity (EC) of a porous carbon is highly desirable in many applications, especially in those associated with storage and conversion of electrochemical energy. In this work, we demonstrated an approach to largely increasing the EC of ordered mesoporous carbon (OMC) by bridging the OMC particles with carbon nanotubes (CNTs). Infiltration of the pores of ordered mesoporous SBA-15 silica with a carbon precursor yielded a carbon/mesoporous silica composite, which was further used as a support for Ni catalyst. Subsequently, catalytic growth of CNTs on the Ni-supported composite surface was carried out using the chemical vapor deposition (CVD) method with benzene as the carbon precursor. Removal of the silica framework and the metal catalyst left behind OMC particles bridged with CNTs. The EC of the OMC was increased from 138 S/m (before bridging) to 645 S/m (after bridging). Because of the significant enhancement of EC and the availability of mesopores, the cyclability of the hybrid carbon materials as a negative electrode used in rechargeable lithium-ion batteries was significantly improved.     

Controlling the textural parameters of mesoporous carbon materials

The mesoporous carbon materials prepared by inorganic templating technique using mesoporous silica, SBA-15 as a template and sucrose as a carbon source, have been systematically investigated as a function of sucrose to mesoporous silica composition, with a special focus on controlling the mesoporous structure, surface morphology and the textural parameters such as specific surface area, specific pore volume and pore size distribution. All the materials have been unambiguously characterized by XRD, N₂ adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron microscopy, and Raman spectroscopy. It has been found that the porous structure, morphology and the textural parameters of the mesoporous carbons materials, CMK-3-x where x represent the sucrose to silica weight ratio, can be easily controlled by the simple adjustment of concentration of sucrose molecules. It has also been found that the specific surface area of the mesoporous carbon materials systematically increases with decreasing the sucrose to silica weight ratio. Moreover, the specific pore volume of the materials increases from 0.57 to 1.31 cm³/g with decreasing the sucrose to silica weight ratio from 5 to 1.25 and then decreases to 1.23 cm³/g for CMK-3-0.8. HRTEM and HR-FESEM also show a highly ordered pore structure and better surface morphology for CMK-3-1.25 as compared to other materials prepared in this study. Thus, it can be concluded that the sucrose to silica weight ratio of 1.25 is the best condition to prepare well ordered mesoporous carbon materials with good textural parameters, pore structure and narrow pore size distribution.     

Synthesis of polyaniline/mesoporous carbon nanocomposites and their application for CO<Subscript>2</Subscript> sorption

Ordered mesoporous carbons (OMC), were synthesized by nanocasting using ordered mesoporous silica as hard templates. Ordered mesoporous carbons CMK-1 and CMK-3 were prepared from MCM-48 and SBA-15 materials with pore diameters of 3.4 nm and 4.2 nm, respectively. Mesoporous carbons can be effectively modified for CO₂ adsorption with amine functional groups due to their high affinity for CO₂. Polyaniline (PANI)/mesoporous carbon nanocomposites were synthesized from in-situ polymerization by dissolving OMC in aniline monomer. The polymerization of aniline molecules inside the mesochannels of mesoporous carbons has been performed by ammonium persulfate. The nanocomposition, morphology, and structure of the nanocomposite were investigated by nitrogen adsorption-desorption isotherms, Fourier Transform Infrared (FT–IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and thermo gravimetric analysis (TGA). CO₂ uptake capacity of the mesoporous carbon materials was obtained by a gravimetric adsorption apparatus for the pressure range from 1 to 5 bar and in the temperature range of 298 to 348 K. CMK-3/PANI exhibited higher CO₂ capture capacity than CMK-1/PANI owing to its larger pore size that accommodates more amine groups inside the pore structure, and the mesoporosity also can facilitate dispersion of PANI molecules inside the pore channels. Moreover, the mechanism of CO₂ adsorption involving amine groups is investigated. The results show that at elevated temperature, PANI/mesoporous carbon nanocomposites have a negligible CO₂ adsorption capacity due to weak chemical interactions with the carbon nanocomposite surface.     

Tubular structured ordered mesoporous carbon as an efficient sorbent for the removal of dyes from aqueous solutions

Tubular structured ordered mesoporous carbon CMK-5 was investigated for the adsorption of the industrial dyes reactive blue 19, acid red 57 and fuchsin basic in aqueous solutions at room temperature. It was found that CMK-5 exhibits an ultrahigh adsorption rate and superior adsorption capacities for these dyes. Its maximum adsorption capacities for reactive blue 19, acid red 57 and fuchsin basic were 733, 1131 and 1403 mg g⁻¹, respectively, and significantly greater than other literature reported results on porous carbons. Following adsorption of reactive blue 19, CMK-5 carbon could be regenerated by either ethanol extraction or thermal annealing at 600 °C, reaching ∼51% and ∼77%, respectively of the adsorption capacity of the original carbon. For comparison, ordered mesoporous carbon CMK-3 (rod structure), polymer based disordered mesoporous carbon, and steam and CO₂ activated commercial coconut carbons were investigated for the adsorption of reactive blue 19. The fast adsorption rate of CMK-5 carbon is due to its unique properties of tubular mesostructure, bimodal mesopore system and high surface area. In the case of requiring emergency removal of large amount of dyes in aqueous solution, CMK-5 would be an ideal choice.     

Detailed structure of the hexagonally packed mesostructured carbon material CMK-3

Detailed investigation of the ordered mesoporous CMK-3 carbon using XRD structural modeling based on the continuous electron density representation and the Rietveld technique allowed deriving comprehensive and consistent information on the material anatomy. The electron density distribution map agrees with carbon ‘bridges’, which seem to be attributed to the material interconnecting carbon nanorods in the CMK-3 mesostructure. These carbon ‘bridges’ are supposed to be derived from former complementary mesopores of the SBA-15 template used.     

Influence of carbon precursor on porosity,surface composition and catalytic behaviour of CMK-3 in oxidative dehydrogenation of propane to propene

Ordered mesoporous CMK-3 carbon replicas were synthesized by infiltration of mesopores present in a SBA-15 silica template with two different carbon precursors, i.e. sucrose and poly(furfuryl alcohol). The obtained composites were carbonized under an inert gas atmosphere at 550, 650, 750 and 850?°C, and the template was etched with a HF solution. The final carbon replicas were analyzed by various physicochemical techniques, including low-temperature N₂ adsorption, X-ray diffraction, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, and tested as catalysts in the oxidative dehydrogenation of propane (ODP) at 450?°C. Both series of materials differed strongly with respect to their porosity, but showed very similar surface composition determined by XPS. Higher porosity of CMK-3 prepared using the sucrose precursor influenced propane conversion and selectivity to propene. Furthermore, oxygen containing groups (e.g. carbonyl-type) were found to be less sensitive to the type of carbon precursor than to the ODP reaction conditions.     

Hierarchical porous carbons with controlled micropores and mesopores for supercapacitor electrode materials

Various porous carbons were prepared by CO₂ activation of ordered mesoporous carbons and used as electrode materials for supercapacitor. The structures were characterized by using X-ray diffraction, transmission electron microscopy and nitrogen sorption at 77 K. The effects of CO₂ treatment on their pore structures were discussed. Compared to the pristine mesoporous carbons, the samples subjected to CO₂ treatment exhibited remarkable improvement in textural properties. The electrochemical measurement in 6 M KOH electrolyte showed that CO₂ activation leads to better capacitive performances. The carbon CS15A6, which was obtained after CO₂ treatment for 6 h at 950 °C using CMK-3 as the precursor, showed the best electrochemical behavior with a specific gravimetric capacitance of 223 F/g and volumetric capacitance of 54 F/cm³ at a scan rate of 2 mV/s and 73% retained ratio at 50 mV/s. The good capacitive behavior of CS15A6 may be attributed to the hierarchical pore structure (abundant micropores and interconnected mesopores with the size of 3-4 nm), high surface area (2749 m²/g), large pore volume (2.09 cm³/g), as well as well-balanced microporosity and mesoporosity.