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.     

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.     

Hydrogen production from catalytic decomposition of methane over ordered mesoporous carbons (CMK-3) and carbide-derived carbon (DUT-19)

This paper presents a thermogravimetric analysis of catalytic methane decomposition using ordered mesoporous carbon nanorods (CMK-3) and ordered mesoporous carbide-derived carbon (DUT-19) as catalysts. X-ray diffraction and N₂ physisorption analyses were performed for both fresh catalysts. Threshold temperatures for methane decomposition with DUT-19 and CMK-3 were estimated by three different methods found in literature. Carbon formation rate and carbon weight gain as a function of time at various temperatures and methane partial pressures were studied, and the kinetics of CMK-3 and DUT-19 as catalysts for methane decomposition were investigated. Arrhenius energy values of 187 kJ/mol for CMK-3 and 196 kJ/mol for DUT-19 with a reaction order of 0.5 were obtained for both catalysts. Results show that carbon deposition on the catalyst during the reaction lead to catalyst deactivation with significant surface modification. Scanning electron microscope studies of fresh and deactivated catalyst samples show the blocking of catalyst pores and the formation of agglomerates on the outer surface of the catalyst during the course of reaction. DUT-19 catalytically outperforms CMK-3 because of a lower threshold temperature, higher surface area, and higher pore volume. These results show that ordered mesoporous carbons are promising catalysts for methane decomposition.     

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.     

Impact of framework structure of ordered mesoporous carbons on the performance of supported Pt catalysts for oxygen reduction reaction

Ordered mesoporous carbons (OMCs) are investigated as support materials for Pt catalysts for oxygen reduction reaction (ORR). Three types of OMCs (CMK-3, CMK-3G, and CMK-5) are prepared by a nanocasting method using ordered mesoporous silica, SBA-15, as a template. These OMCs with the same hexagonal mesostructure have different carbon frameworks and graphiticity, which can affect their surface area and microporosity. Pt nanoparticles with an average size of 1 nm are uniformly supported on the three OMCs and Ketjenblack® and their electrochemical performance and durability are evaluated. Pt/CMK-3G exhibits the highest electrochemically active surface area, kinetic current density, mass activity, and half-wave potential, whereas Pt/CMK-3 shows the lowest values. Pt/CMK-3G also shows the highest ORR activity after an accelerated durability test, with a minimal shift in half-wave potential. The higher ORR activity of Pt/CMK-3G is attributed to the formation of highly crystalline Pt particles as well as its highly graphitic, crystalline carbon structure, which causes the weak adsorption of surface oxide and a strong interaction between the Pt particles and the support. Moreover, we can establish that the mass activity of the catalysts is nearly inversely proportional to the micropore volume of the carbon supports.     

Hydrothermal Solubilization–Hydrolysis–Dehydration of Cellulose to Glucose and 5-Hydroxymethylfurfural Over Solid Acid Carbon Catalysts

Solid acid catalysts based on graphite-like mesoporous carbon material Sibunit were developed for the one-pot solubilization–hydrolysis–dehydration of cellulose into glucose and 5-hydroxymethylfurfural (5-HMF). The catalysts were produced by treating Sibunit surface with three different procedures to form acidic and sulfo groups on the catalyst surface. The techniques used were: (1) sulfonation by H₂SO₄ at 80–250 °C, (2) oxidation by wet air or 32 v/v% solution of HNO₃, and (3) oxidation-sulfonation what meant additional sulfonating all the oxidized carbons at 200 °C. All the catalysts were characterized by low-temperature N₂ adsorption, titration with NaOH, TEM, XPS. Sulfonation of Sibunit was shown to be accompanied by surface oxidation (formation of acidic groups) and the high amount of acidic groups prevented additional sulfonation of the surface. All the Sibunit treatment methods increased the surface acidity in 3–15 times up to 0.14–0.62 mmol g^?1 compared to pure carbon (0.042 mmol g^?1). The catalysts were tested in the depolymerization of mechanically activated microcrystalline cellulose at 180 °C in pure water. The main products 5-HMF and glucose were produced with the yields in the range of 8–22 wt% and 12–46 wt%, respectively. The maximal yield were achieved over Sibunit sulfonated at 200 °C. An essential difference in the composition of main products obtained with solid acid Sibunit carbon catalysts (glucose, 5-HMF) and soluble in water H₂SO₄ catalysts (formic and levulinic acids) as well as strong dependence of the reaction kinetics on the morphology of carbon catalysts argue for heterogenious mechanism of cellulose depolymerization over Sibunit.     

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   

Sorption of reactive dyes from aqueous solutions by ordered hexagonal and disordered mesoporous carbons

In the present study two synthetic mesoporous carbons, a highly ordered CMK-3 sample with hexagonal structure and a disordered mesoporous carbon (denoted DMC) were investigated for the sorption of Remazol Red 3BS (C.I. 239) dye in comparison to three commercial activated carbons and a HMS mesoporous silica with a wormhole pore structure. The structural, porosity and surface characteristics of the materials were evaluated using XRD, TEM, N₂ porosimetry, FT-IR spectroscopy and zeta-potential measurements. Optimal dye sorption occurred at pH ～2. Equilibrium sorption data followed the Langmuir model and showed that the two synthetic mesoporous carbons exhibit higher sorption capacities (q_max ～ 500–580 mg/g at 25 °C) in comparison to the commercial activated carbons which possessed either microporous (Takeda 5A and Calgon carbon) or combined micro-/mesoporous (Norit SAE-2) structures and to the HMS mesoporous silica. Thermodynamic parameters as the change in free energy, enthalpy, and entropy of sorption were also estimated. Kinetic studies were carried out and showed a rapid sorption of dye in the first ca. 30 min while equilibrium was reached after ca. 3 h. The sorption kinetics of dye was best described by a second-order kinetic model. A surfactant enhanced carbon regeneration (SECR) technique was used to regenerate the dye-loaded carbon sorbents.     

磺酸化碳材料负载Ru催化剂催化纤维素水解/加氢反应

采用纤维素衍生碳、活性炭和介孔碳材料CMK-3为不同碳源前驱体,在不同磺酸化条件下制备磺酸化碳材料负载Ru的双功能催化剂,并用FTIR光谱、XRD、元素分析、热重分析、N₂物理吸附 脱附进行了表征,考察了其对纤维素加氢反应的催化活性。结果表明：相比于纤维素衍生化碳,活性炭和介孔碳CMK-3为碳源经过磺酸化后制备的催化剂具有较强的结合-SO₃H的能力和较高的催化活性,对多元醇具有良好的选择性,170 ℃下反应10 h六元醇的收率可高达84.0%。在循环使用时,磺酸化活性炭负载Ru催化剂催化活性有所降低,但可以保持对多元醇的选择性;而磺酸化介孔碳负载Ru催化剂存在少量S流失,转化率基本不变,但产物的选择性有所降低。     

Carbon dioxide reforming of methane over nickel catalysts supported on mesoporous MgO

In this paper, ordered mesoporous MgO nanocrystals [MgO(M)] were synthesized, and the nickel catalysts supported on MgO(M) were facilely prepared by impregnation method. The obtained Ni/MgO(M) catalysts with advantageous textural properties were investigated as the catalysts for the carbon dioxide reforming of methane reaction. It was found that compared with the Ni/MgO(C) catalyst [MgO(C): commercial MgO], the mesoporous pore structure of MgO(M) could effectively limit the growth of the activity metal, and the Ni/MgO(M) catalysts showed high catalytic activities as well as long catalytic stabilities toward this reaction. The results showed that the conversions of CH₄ and CO₂ were only decreased <5 % after 100 h of reaction at 650 °C. The improved catalytic performance was suggested to be closely associated with both the advantageous structural properties, such as large specific surface area, uniform pore size, and the “confinement effect” of the mesoporous matrixes contributed to stabilize the Ni active sites during the reaction. The carbon species deposited on the spent Ni/MgO(M) catalyst were analysized by TG and Raman, and the results exhibited that the carbon species after 100 h of reaction were mainly active carbon species.     

Remarkable effect of ordered mesoporous carbon support in tantalum oxide-catalyzed selective epoxidation of cyclooctene

The olefin epoxidation is one of the most important reactions in chemical industry. Metal oxide supports often cause drawbacks in catalytic activity and selectivity, which has been overcome by introducing hydrophobic organic groups onto the oxide supports. The present study utilizes ordered mesoporous carbon (CMK-3 and CMK-1) as structurally defined hydrophobic catalyst support. Well-dispersed tantalum oxides supported on the ordered mesoporous carbon were prepared. Their application in catalytic epoxidation of cyclooctene demonstrates that the tantalum oxide catalysts on the ordered mesoporous carbon supports show higher performances than those of the catalysts supported on activated carbon and ordered mesoporous silica SBA-15.     

Solvothermal polycondensation of novolacs phenolic-resin to nanopowders and their derived activated nanocarbons as efficient adsorbents for water cleaning

Novolacs phenolic-resin (PF) was easily polycondensed into polymeric powders with sizes and morphologies ranging from microspheres to nanoparticles by a simple solvothermal process without adding any crosslinking agent. Activating the highly divided PF powders by CO₂ resulted in nanosize activated carbons with high specific surface area (2092 m² g^?1) and large pore volume (1.33 cm³ g^?1) while preserving a high carbon yield of about 38 wt%. As for adsorption tests, the micropore-dominated activated nanocarbons exhibited fast and high adsorption capabilities towards both Cr(VI) ions and bulky rhodamine B molecules due to their much improved external surface area and the greatly shortened intra-particle diffusion distance. The equilibrium adsorption amounts of Cr(VI) and RB on the activated nanocarbons as estimated by the Langmuir model were 200 and 990 mg g^?1, achieved within an adsorption time of 30 and 360 min, respectively.     

Mesoporous copper–cerium–oxygen hybrid nanostructures for low temperature catalytic oxidation of carbon monoxide

Mesoporous copper–cerium–oxygen hybrid nanostructures were prepared by one-pot cetyltrimethylammonium bromide surfactant-assisted method, and were characterized by thermogravimetry, X-ray diffraction, transmission electron microscopy, nitrogen adsorption–desorption, X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Low temperature carbon monoxide oxidation was used as probe reaction to investigate the application of the prepared mesoporous copper–cerium–oxygen hybrid nanostructures in catalysis. The product calcined at 400 °C, with disordered wormlike mesoporous structure, high specific surface area (SSA) of 117.4 m²/g and small catalyst particle size of 8.3 nm, shows high catalytic activity with the 100 % CO conversion at 110 °C, indicating its potential application in catalysis. Catalytic activity results from the samples calcinied at different temperature suggested that high SSA, small catalyst particle size, finely dispersed CuO species and synergistic effect between CuO and CeO₂ were responsible for the high catalytic activity of the catalysts.     

Synthesis of Ordered Mesoporous Carbon Materials with Semi-Graphitized Walls via Direct In-situ Silica-Confined Thermal Decomposition of CH4 and Their Hydrogen Storage Properties

Ordered mesoporous carbons with semi-graphitized walls (OMCs-SGW) were successfully obtained by in situ silica-confined thermal decomposition of methane at low temperatures (800–1000 °C). This novel method, adopting ordered mesoporous silicas (OMSs) as hard templates, impregnating OMSs with small amounts of group VIII metal (Fe, Co, Ni) nitrates as catalysts, combining pore infiltration and carbonization/graphitization processes into a single step, provides an efficient way for the synthesis of OMCs-SGW. Methane, a special carbon precursor with small molecular size, is adopted because it allows complete penetration, and full carbon deposition inside the mesopores and is an easy graphitization process at low temperature assisted by catalysts. Two mesoporous silica materials, SBA-15 with hexagonal structure (p6m) and KIT-6 with cubic bicontinuous structure (Ia3d), were used as hard templates. SAXS patterns and TEM results show that the obtained carbon materials are faithfully replicated from the mesostructures of silica templates. Their pore walls are semi-graphitized and little structural shrinkage and negligible micropores are observed. The textural, structural properties and degree of graphitization of the OMCs-SGW can be conveniently tuned by controlling the temperature, namely, higher temperatures (e.g. 1000 °C) lead to products with more ordered and graphitized frameworks, but lower surface areas and pore volumes (about 390 m²/g and 0.45 cm³/g), while lower temperature (800 °C) results in products with less ordered and graphitized structures, but very high surface areas and pore volumes (up to 1200 m²/g and 2.08 cm³/g). OMCs-SGW can also be synthesized without catalysts. They have higher surface areas and pore volumes but much lower graphitized structures than the counterparts synthesized with catalysts. These OMCs-SGW show good hydrogen uptake capabilities (up to ~2 wt% at 10 bar and 77 K).     

Synthesis and characterization of activated carbon and bioactive adsorbent produced from paper mill sludge

Adsorption capacity and bioactivity of a novel mesoporous activated carbon (IIT Carbon) and bioactive (BAC_IIT) catalyst produced from papermill sludge were evaluated. Conversion of paper mill sludge to useful activated carbons and biocatalysts is a significant process since it reduces environmental problems associated with disposal of waste sludge, enhances wastewater treatment using carbons produced from industrial waste itself, and promotes conservation of the naturally available primary resources currently used to make activated carbons. Analysis was conducted using synthetic wastewater containing phenol and a commercially available activated carbon, sorbonorite 4 (used as reference carbon). Phenol removal was accomplished in batch and fluidized bed reactors containing mesoporous activated carbon, sorbonorite 4, and the produced bioactive catalysts. Isotherm adsorption data indicated that mesoporous activated carbon has a higher adsorption capacity and molecular surface coverage than sorbonorite 4 for phenol concentrations less than 10 mg/l. The mass transfer limitation was accounted for the lower adsorption capacity of the microporous carbon (sorbonorite 4) in dilute solutions. The fluidized bed reactor study, however, indicated similar but slightly lower phenol removal capability for the produced mesoporous carbon. While phenol removal efficiency of the carbons studied was in the range 65–70%, the produced bioactive catalysts were able to remove up to 97% of phenol during first few hours of operation. These results suggest that mesoporous carbon will feasibly be a good substitute for other commercially available activated carbons produced from natural resources, not only in physical adsorption processes, but also in fluidized bed bioreactors (FBB), used in biodegradation processes.     

Adsorption of selected environmentally important metals by poultry manure‐based granular activated carbons

Water quality and public health impacts of mass produced poultry manure have prompted the need for viable conversion and reuse solutions. Conversion of poultry manure to value‐added granular activated carbons for environmental remediation can be such a solution. The objective of this study was to compare the effectiveness of poultry manure‐based carbons for the adsorption of selected metal ions (copper, cadmium, nickel, zinc) from solutions containing individual ions or the four metal ions present together. Adsorption properties for poultry manure‐based carbons were compared with those of two commercial carbons, PūR RF and Minotaur, and carbons from three traditional precursors, coal, coconut and wood. Pelletized samples were pyrolyzed at 700 °C for 1 h followed by 800 °C steam activation at 1, 3 and 5 mL min^?1 water flow rate, for 30 and 45 min, under nitrogen. The carbon's ability to adsorb the metals was influenced by the activation strategy, increasing for longer activation times and higher water flow rates, in the presence of a single metal solution. Saturation conditions were achieved at 20 mM and, at 5 mM , almost all metal ion in solution was adsorbed, except for nickel. Carbons showed similar affinity towards copper, cadmium and zinc, individually. However, when in competition, at 5 mM of each metal, manure‐based carbons showed a preference for Cu²⁺ followed by Zn²⁺ and Cd²⁺. Poultry manure‐based carbons outperformed all reference carbons and PūR RF, and, except for Ni²⁺, Minotaur was also outperformed. Experiments showed that the highest removal rate in a competition situation was obtained for broiler‐cake carbon activated for 45 min at 3 mL min^?1, with 93.1%, 50.9% and 85.2% for copper, cadmium and zinc ions, respectively. Published in 2005 for SCI by John Wiley & Sons, Ltd.     

Synthesis of an ordered mesoporous carbon with graphitic characteristics and its application for dye adsorption

An ordered mesoporous carbon (OMC) was prepared by a chemical vapor deposition technique using liquid petroleum gas (LPG) as the carbon source. During synthesis, LPG was effectively adsorbed in the ordered mesopores of SBA-15 silica and converted to a graphitic carbon at 800 °C. X-ray diffraction and nitrogen adsorption/desorption data and high-resolution transmission electron microscopy (HRTEM) of the OMC confirmed its ordered mesoporous structure. The OMC was utilized as an adsorbent in the removal of dyes from aqueous solution. A commercial powder activated carbon (AC) was also investigated to obtain comparative data. The efficiency of the OMC for dye adsorption was tested using acidic dye acid orange 8 (AO8) and basic dyes methylene blue (MB) and rhodamine B (RB). The results show that adsorption was affected by the molecular size of the dye, the textural properties of carbon adsorbent and surface-dye interactions. The adsorption capacities of the OMC for acid orange 8 (AO8), methylene blue (MB) and rhodamine B (RB) were determined to be 222, 833, and 233 mg/g, respectively. The adsorption capacities of the AC for AO8, MB, and RB were determined to be 141, 313, and 185 mg/g, respectively. The OMC demonstrated to be an excellent adsorbent for the removal of MB from wastewater.     

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.     

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.     

CMK-3 nanostructured carbon: Effect of temperature and time carbonization on textural properties and H2 storage

Abstract

CMK-3 carbons were synthesized varying the carbonization conditions and studying the effect of the templates calcined at different temperatures. The textural characterization of different SBA-15 templates calcined at 350, 450, and 550?°C shows a variation of the specific surface area below 10%. Based on the results, the SBA-15 obtained at 350?°C (the more affordable condition) was used as the final template for the CMK-3 synthesis. The results show that varying the time (from 2 to 6?h) and the temperature (from 600 to 900?°C) on the carbonization step, the textural, structural, and morphological properties of the carbons do not vary in a meaningful way. Thus, a CMK-3 carbon synthesized (using as template an SBA-15 calcined at 350?°C) obtained at 600?°C during 2?h was chosen to be used as adsorbent in hydrogen storage in order to stablish the relationship between the textural properties and its performance. Regarding the hydrogen storage, capacities of 15?mg H₂ g^?1 (1.5% w/w), and up to 28?mg H₂ g^?1 (2.8% w/w) were obtained at 1 and 10?bar, respectively. At high pressure, an important influence of the large micropores and narrow mesopores on the hydrogen adsorption was found.