Cationic starch as a precursor to prepare porous activated carbon for application in supercapacitor electrodes

Three activated carbons (ACs) for the electrodes of supercapacitor were prepared from cationic starch using KOH, ZnCl₂ and ZnCl₂/CO₂ activation. The BET surface area, pore volume and pore size distribution of the ACs were evaluated using density functional theory method, based on N₂ adsorption isotherms at 77 K. The surface morphology was characterized with SEM. Their electrochemical performance in prototype capacitors was determined by galvanostatic charge/discharge characteristics and cyclic voltammetry, and compared with that of a commercial AC, which was especially prepared for use in supercapacitors. The KOH-activated starch AC presented higher BET surface area (3332 m² g⁻¹) and larger pore volume (1.585 cm³ g⁻¹) than those of the others, and had a different surface morphology. When used for the electrodes of supercapacitors, it exhibited excellent capacitance characteristics in 30 wt% KOH aqueous electrolytes and showed a high specific capacitance of 238 F g⁻¹ at 370 mA g⁻¹, which was nearly twice that of the commercial AC.     

Fabrication and application of highly ordered mesoporous Co3O4, NiO, and their metals

Highly ordered mesoporous Co₃O₄, NiO, and their metals were synthesized by nanocasting method using there corresponding mesoporous SBA-15 silica as a template. The obtained porous metal oxides have high surface areas, large pore volume, and a narrow pore size distribution. The N₂-adsorption data for mesoporous metal oxides have provided the BET area of 257.7 m² g⁻¹ and the total pore volume of 0.46 cm³ g⁻¹. The mesoporous metals were employed as a catalyst in the synthesis of (S)-3-pyrrolidinol from chiral (S)-4-chloro-3-hydroxybutyronitrile, and a high yield to (S)-3-pyrrolidinol-salt was obtained on the mesoporous Co metal catalyst.     

Direct synthesis of mesoporous carbon from the carbonization of hydroxypropyl-β-cyclodextrin/silica composite and its catalytic performance

A simple and efficient route is reported for the synthesis of mesoporous carbon materials by directly carbonizing hydroxypropyl-β-cyclodextrin-silica composites. The resulting carbon materials, with uniform wormlike mesoporous structure and certain degree graphitic phase characteristics in porous wall, possess narrow pore size distribution, high surface area (>1000 m² g⁻¹) and pore volume (>1.2 cm³ g⁻¹). It is worth mentioning that the carbon materials have high catalytic activity for the reduction of p-nitrotoluene using hydrazine hydrate as the reducing agent; moreover, the catalytic activity is not reduced notably after being reused for six times.     

Preparation and characterization of carbons for the retention of halogens in the condenser vacuum system of a thermonuclear plant

Activated carbons were prepared by air and carbon dioxide activation, from almond tree pruning, with the aim of obtaining carbons that reproduce the textural and mechanical properties of the carbons currently used in the filtering system of the condenser vacuum installation of a Thermonuclear Plant (CNA; Central Nuclear de Almaraz in Caceres, Spain), produced from coconut shell. The variables studied in non-catalytic gasification series with air were the temperature (215-270 °C) and the time (1-16 h) and the influence of the addition of one catalyst (Co) and the time (1-2 h) in catalytic gasification. In the case of activation with CO₂, the influence of the temperature (700-950 °C) and the time (1-8 h) was studied. The resulting carbons were characterized in terms of their BET surface, porosity, and pore size distribution. The N₂ adsorption isotherms at 77 K for both series showed a type I behaviour, typical of microporous materials. The isotherms showed that with both gasificant agents the temperature rise produced an increase in the carbon porosity. With regards to the activation time, a positive effect on the N₂ adsorbed volume on the carbons was observed. The best carbons of each series, as well as the CNA (carbon currently used in the CNA), were characterized by mercury porosimetry and iodine solution adsorption isotherms. The results obtained allowed to state that several of the carbons produced had characteristics similar to the carbon that is target of reproduction (which has S_BET of 741 m² g⁻¹, V_mi of 0.39 cm³ g⁻¹ and a iodine retention capacity of 429.3 mg g⁻¹): carbon C (gasification with CO₂ at 850 °C during 1 h), with S_BET of 523 m² g⁻¹, V_mi of 0.33 cm³ g⁻¹ and a iodine retention capacity of 402.5 mg g⁻¹, and carbon D (gasification with CO₂ at 900 °C during 1 h), whose S_BET is 672 m² g⁻¹, V_mi is 0.28 cm³ g⁻¹ and has a iodine retention capacity of 345.2 mg g⁻¹.     

High specific surface area TEOS-based aerogels with large pore volume prepared at an ambient pressure

The experimental results on the synthesis of tetraethoxysilane (TEOS)-based silica aerogel with high specific surface area and large pore volume, via ambient pressure drying (APD) route, are reported. The silica aerogels were prepared by the acid-base sol-gel polymerization of TEOS precursor followed by the drying of the alcogels at an ambient pressure. The solvent present in the alcogel (i.e. ethanol) was replaced by a non-polar solvent such as hexane prior to the surface modification step. In order to minimize the drying shrinkage, the surface of the gels was modified using trimethylchlorosilane (TMCS) before the APD. The FTIR spectra of the surface modified aerogels showed Si-CH₃ peaks at 2965 and 850 cm⁻¹. The effect of the base catalyst (NH₄OH) addition to the sol, at different time intervals (T), on the physical and textural properties of the resulting aerogels has been investigated. It has been observed that the surface area and the cumulative pore volume of the aerogels enhanced considerably from 819 to 1108 m² g⁻¹ and 2.65 to 4.7 cm³ g⁻¹, respectively with an increase in the T value from 6 to 48 h. Silica aerogels with very low bulk density (0.06 g cm⁻³), extremely high specific surface area (1108 m² g⁻¹) and large cumulative pore volume (4.7 cm³ g⁻¹) could be synthesized by drying the alcogels at the ambient pressure. The aerogels were mesoporous solids with the average pore size ranging from 12 to 17 nm. The results have been discussed by taking into consideration the hydrolysis and condensation reactions during the sol-gel polymerization of the TEOS precursor.     

Synthesis and utilization of Mg/Al hydrotalcite for removing dissolved humic acid

It has been synthesized Mg/Al layered double hydroxide anionic clay (Mg/Al hydrotalcite) through direct precipitation by adding 0.5 M NaOH solution into a mixed solution containing Mg(NO₃)₂ and Al(NO₃)₃ with molar ratio of 0.1:0.05 until the medium acidity reached pH 10.1. The synthesized Mg/Al hydrotalcite was then utilized to remove dissolved humic acid in aqueous medium. The humic acid was isolated from peat soil taken in Gambut District, South Kalimantan, Indonesia using the recommended procedure of IHSS (International Humic Substances Society). The removal of humic acid was mostly occurred through simple sorption process without accompanied by significant intercalation. The sorption was optimum at pH 9.0, with the first order rate constant, capacity and energy of sorption were 5.50 × 10⁻³ min⁻¹, 0.12 mmol g⁻¹ (69 mg g⁻¹), and 28.32 kJ mol⁻¹, respectively.     

Surface-modified zeolite-filled chitosan membranes for pervaporation dehydration of ethanol

Surface-modified zeolite-filled chitosan (CS) membranes were prepared by incorporating 3-mercaptopropyltrimethoxysilane (MPTMS)-modified H-ZSM-5 zeolite into chitosan for pervaporation dehydration of aqueous ethanol solution. The physicochemical characterization by XPS, FT-IR, XRD, DMA and SEM showed that -SO₃H group was readily grafted on the surface of H-ZSM-5 with the mediation of MPTMS and hydrogen peroxide, and the accompanying ion-ion interaction between -SO₃H group on surface-modified H-ZSM-5 and -NH₃⁺ group on chitosan substantially eliminated the nonselective voids at the chitosan-H-ZSM-5 interface of the filled membranes. The experimental results also revealed that H-ZSM-5 exhibited desirable size-selective and preferential adsorption effects for aqueous ethanol solution. As a result, modified H-ZSM-5 filled membranes showed higher swelling degree and permeation flux, and improved selectivity for aqueous ethanol solution. In comparison between chitosan control membrane (permeation flux 54.18 g/(m² h) and separation factor 158.02 for 90 wt.% aqueous ethanol solution at 80 °C), the modified H-ZSM-5 filled membrane with 8 wt.% filling content exhibited a remarkably improved pervaporation performance with permeation flux 278.54 g/(m² h) and separation factor 274.46 under the identical experimental condition.     

A novel one-step synthesis of mesostructured silica-pillared clay with highly ordered gallery organic-inorganic hybrid frame

A new class of organic-inorganic hybrid mesostructured silica-pillared clay (HSPC) has been prepared through the surfactant directed assembly of organosilica in the galleries of montmorillonite. The surfactant templates were removed from the pores by solvent-extraction. The products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), nitrogen adsorption-desorption measurements, solid-state ²⁹Si and ¹³C NMR, and Fourier-transform infrared (FT-IR) spectra. XRD patterns indicated a regular interstratifications of the clay layers for HSPCs. Depending on loading of phenyl groups, HSPCs had BET surface areas of 395-602 m² g⁻¹, pore volumes of 0.34-0.79 cm³g⁻¹, and the framework pore sizes in the supermicropore to small mesopore range (1.3-2.6 nm). HSPCs were hydrophobic and acidic. The number of silanol groups on the surface of HSPC materials has been titrated by a surface reaction with hexamethyldisilazane, followed by quantification of the liberated NH₃. Based on this method extracted HPCHs have high silanol numbers, a very important feature with respect to the amount of catalytic sites that can eventually be grafted onto the surface.     

Electrodeposition of nanostructured Pt films from lyotropic liquid crystalline phases on α-Al2O3 supported dense Pd membranes

Using the lyotropic liquid crystalline templating strategy, the nanostructured platinum film was electrochemically deposited on the α-Al₂O₃ supported dense palladium membrane. The XRD and TEM results of the Pt film revealed a hexagonal array of cylindrical pores with a uniform pore diameter of ca. 3.8 nm and a pore-to-pore separation of ca. 7.6 nm. The structure parameters of the Pt film were almost the same as those of the hexagonal liquid crystalline template. Based on SEM observations, the Pt film was featureless, smooth, and tightly adherent to the dense Pd membrane. The specific surface area of the Pt film, measured by using cyclic voltammetry, was ca. 13.8 m² g⁻¹, which was in accord with the theoretical value of 14.5 m² g⁻¹ for a perfect hexagonal nanostructure with the same structure parameters. By combining the dense Pd membrane for selective permeation to hydrogen with the Pt film of high specific surface area for catalysis, the as-synthesized two-layer film will be a promising catalytic membrane to intensify hydrogen-related reaction processes.     

Highly active Ce1−xCuxO2 nanocomposite catalysts for the low temperature oxidation of CO

A series of Ce_1−xCu_xO₂ nanocomposite catalysts with various copper contents were synthesized by a simple hydrothermal method at low temperature without any surfactants, using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxide nanocomposites were characterized by means of XRD, TEM, HRTEM, EDS, N₂ adsorption, H₂-TPR and XPS. The influence of Cu loading (5-25 mol%) and calcination temperature on the surface area, particle size and catalytic behavior of the nanocomposites have been discussed. The catalytic activity of Ce_1−xCu_xO₂ nanocomposites was investigated using the test of CO oxidation reaction. The optimized performance was achieved for the Ce_0.80Cu_0.20O₂ nanocomposite catalyst, which exhibited superior reaction rate of 11.2 × 10⁻⁴ mmol g⁻¹ s⁻¹ and high turnover frequency of 7.53 × 10⁻² s⁻¹ (1% CO balanced with air at a rate of 40 mL min⁻¹, at 90 °C). No obvious deactivation was observed after six times of catalytic reactions for Ce_0.80Cu_0.20O₂ nanocomposite catalyst.     

Highly selective epoxidation of styrene over mesoporous Au-Ti-SBA-15 via photocatalysis process: Synthesis, characterization, and catalytic application

Highly ordered Au-Ti-SBA-15 mesoporous molecular sieves were successfully synthesized by one-pot hydrothermal synthesis in acid medium, and were characterized by XRD, UV-vis, SEM, element-mapping, HRTEM, N₂ adsorption, XPS, ²⁹Si MAS NMR, NH₃-TPD and FT-IR. The as-prepared Au-Ti-SBA-15 samples were possessed of highly ordered mesostructures with larger pore diameter, pore volume and uniform mesopore size distribution. In the oxidation of styrene with H₂O₂ as the oxidant over Au-Ti-SBA-15 catalyst under photo-irradiation, reaction parameters, such as molar ratio of H₂O₂ to styrene, reaction time, solvent, the amount of catalyst, catalyst species, and the amount of 3% NaOH, were conditioned at length. As a result, highly selective epoxidation of styrene over catalyst was carried out perfectly for 10 min with high TOF of 4.75 × 10³ min⁻¹.     

Preparation and characterization of activated carbon produced from pomegranate seeds by ZnCl2 activation

In this study, pomegranate seeds, a by-product of fruit juice industry, were used as precursor for the preparation of activated carbon by chemical activation with ZnCl₂. The influence of process variables such as the carbonization temperature and the impregnation ratio on textural and chemical-surface properties of the activated carbons was studied. When using the 2.0 impregnation ratio at the carbonization temperature of 600 °C, the specific surface area of the resultant carbon is as high as 978.8 m² g⁻¹. The results showed that the surface area and total pore volume of the activated carbons at the lowest impregnation ratio and the carbonization temperature were achieved as high as 709.4 m² g⁻¹ and 0.329 cm³ g⁻¹. The surface area was strongly influenced by the impregnation ratio of activation reagent and the subsequent carbonization temperature.     

A novel method to synthesize LiVPO4F/C composite materials and its electrochemical Li-intercalation performances

Triclinic LiVPO₄F/C composite materials were prepared from a sucrose-containing precursor by one-step heat treatment. As-prepared composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurements. XRD studies showed that Li₃PO₄ impurity phase appeared in the sample synthesized at 600 °C and pure LiVPO₄F samples could be obtained when the sintered temperature was higher than 650 °C. The sample synthesized at 650 °C presents the highest initial discharge capacity of 132 mAh g⁻¹ at 0.2 C rate, and exhibited better cycling stability (124 mAh g⁻¹ at 50th cycle at 0.2 C rate) and better rate capability (100 mAh g⁻¹ at 50th cycle under 1 C rate) in the voltage range 3.0-4.4 V.     

Electrochemical properties of α-Fe2O3 /MWCNTs as anode materials for lithium-ion batteries

α-Fe₂O₃/MWCNTs composites were prepared by a simple hydrothermal process. The crystalline structure and the electrochemical performance of the as-synthesized samples were investigated. Results show that as anode materials for lithium-ion batteries, the α-Fe₂O₃/MWCNTs exhibit an initial discharge capacity of 1256 ± 5 mAh g⁻¹ and a stable specific discharge capacity of 430 ± 5 mAh g⁻¹ at ambient temperature, for up to 100 cycles with no noticeable capacity fading, while the initial discharge capacity of the bare Fe₂O₃ is 992.3 mAh g⁻¹, and the discharge capacity is 146.6 mAh g⁻¹ after 100 cycles. Moreover, the α-Fe₂O₃/MWCNTs composites also exhibit excellent rate performance.     

Synthesis and properties of side-chain-type ion exchange membrane PEEK-g-StSO3Na for bipolar membranes

Side-chain-type ion exchange membranes (PEEK-g-StSO₃Na) were prepared by grafting poly (ether ether ketone) (PEEK) containing propenyl groups with sodium sulfonic styrene (StSO₃Na) and KH570. PEEK was synthesized by the aromatic nucleophilic polycondensation reaction of 4,4′-difluorobenzophenone, bisphenol A and diallylbisphenol A. The synthesized copolymers with the -SO₃Na group on the side chain of polymers possessed high molecular weights. The cross-linking reaction was carried out through a sol-gel reaction of the trimethoxysilane group. The copolymer membranes exhibited excellent mechanical properties due to their aromatic structure extending through the backbone and flexible StSO₃Na aliphatic chains. The ion exchange capacities (IECs) of the membranes ranged from 2.27 to 2.50 mmol g⁻¹ and the water content ranged from 107.2 to 126.1%, with both parameters increasing with StSO₃Na grafting degree. The H⁺ permeability of copolymer membranes increased with increasing IEC, reaching value above 0.3056 mol/L at 2 h, which is higher than that of Nafion^® 117 at the same measurement condition. They displayed reasonably high H⁺ permeability due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water occupation, and the lower AC impedance of the bipolar membrane.     

Characterization of deep level defects in sublimation grown p-type 6H-SiC epilayers by deep level transient spectroscopy

In this study deep level transient spectroscopy has been performed on boron–nitrogen co-doped 6H-SiC epilayers exhibiting p-type conductivity with free carrier concentration (N_A–N_D)∼3×10¹⁷ cm⁻³. We observed a hole H₁ majority carrier and an electron E₁ minority carrier traps in the device having activation energies E_v+0.24 eV, E_c −0.41 eV, respectively. The capture cross-section and trap concentration of H₁ and E₁ levels were found to be (5×10⁻¹⁹ cm², 2×10¹⁵ cm⁻³) and (1.6×10⁻¹⁶ cm², 3×10¹⁵ cm⁻³), respectively. Owing to the background involvement of aluminum in growth reactor and comparison of the obtained data with the literature, the H₁ defect was identified as aluminum acceptor. A reasonable justification has been given to correlate the E₁ defect to a nitrogen donor.     

Preparation of activated carbons from cherry stones by activation with potassium hydroxide

Using cherry stones, the preparation of activated carbon has been undertaken in the present study by chemical activation with potassium hydroxide. A series of KOH-activated products was prepared by varying the carbonisation temperature in the 400-900 °C range. Such products were characterised texturally by gas adsorption (N₂, −196 °C), mercury porosimetry, and helium and mercury density measurements. FT-IR spectroscopy was also applied. The carbons prepared as a rule are microporous and macroporous solids. The degree of development of surface area and porosity increases with increasing carbonisation temperature. For the carbon heated at 900 °C the specific surface area (BET) is 1624 m² g⁻¹, the micropore volume is 0.67 cm³ g⁻¹, the mesopore volume is 0.28 cm³ g⁻¹, and the macropore volume is 1.84 cm³ g⁻¹.     

Structural and electrochemical properties of Nd-doped LiFePO4/C prepared without using inert gas

To further improve the electrochemical performance of LiFePO₄/C, Nd doping has been adopted for cathode material of the lithium ion batteries. The Nd-doped LiFePO₄/C cathode was synthesized by a novel solid-state reaction method at 750 °C without using inert gas. The Li_0.99Nd_0.01FePO₄/C composite has been systematically characterized by X-ray diffraction, EDS, SEM, TEM, charge/discharge test, electrochemical impedance spectroscopy and cyclic stability. The results indicate that the prepared sample has olivine structure and the Nd³⁺ and carbon modification do not affect the structure of the sample but improve its kinetics in terms of discharge capacity and rate capability. The Li_0.99Nd_0.01FePO₄/C powder exhibited a specific initial discharge capacity of about 161 mAh g^− 1 at 0.1 C rate, as compared to 143 mAh g^− 1 of LiFePO₄/C. At a high rate of 2 C, the discharge capacity of Li_0.99Nd_0.01FePO₄/C still attained to 115 mAh g^− 1 at the end of 20 cycles. EIS results indicate that the charge transfer resistance of LiFePO₄/C decreases greatly after Nd doping.     

Effects of carbonization temperature on microstructure and electrochemical performances of phenolic resin-based carbon spheres

Activated phenol resin-based carbon spheres (APCS) electrodes with high double layer capacitance and good rate capability were prepared from phenol resin-based spheres (PS) at different carbonization temperatures prior to KOH activation. The carbonization temperature has a marked effect on both the pore structure and the electrochemical performances of the APCS in 6 M KOH electrolyte. APCS carbonized at 600 °C results in higher specific surface area and larger pore size, and hence higher capacitance and better rate capability. The specific capacitance of the APCS in 6 M KOH aqueous solution can be as high as 282 F g⁻¹. It remains 252 F g⁻¹ as the current density increases to 1000 mA g⁻¹.     

Heat capacity of paramagnetic nickelocene: Comparison with diamagnetic ferrocene

Nickelocene [bis(η⁵-cyclopentadienyl)nickel: Ni(C₅H₅)₂, electron spin S=1, the ground state configuration ³A_2g] is paramagnetic and belongs to a typical molecule-based magnet. Heat capacities of nickelocene have been measured at temperatures in the 3−320 K range by adiabatic calorimetry. By comparing with those of diamagnetic ferrocene crystal, a small heat capacity peak centered at around 15 K and a sluggish hump centered at around 135 K were successfully separated. The low-temperature peak at 15 K caused by the spin is well reproduced by the Schottky anomaly due to the uniaxial zero-field splitting of the spin S=1 with the uniaxial zero-field splitting parameter D/k=45 K (k: the Boltzmann constant). The magnetic entropy 9.7 J K⁻¹ mol⁻¹ is substantially the same as the contribution from the spin-manifold R ln 3=9.13 J K⁻¹ mol⁻¹ (R: the gas constant). The sluggish hump centered at around 135 K arises from rotational disordering of the cyclopentadienyl rings of nickelocene molecule. The enthalpy and entropy gains due to this anomaly are 890 J mol⁻¹ and 6.9 J K⁻¹ mol⁻¹, respectively. As the hump spreads over a wide temperature region, separation of the hump from the observed heat capacity curve involves a little bit ambiguity. Therefore, these values should be regarded as being reasonable but tentative. The present entropy gain is comparable with 5.5 J K⁻¹ mol⁻¹ for the sharp phase transition at 163.9 K of ferrocene crystal. This fact implies that although the disordering of the rings likewise takes place in both nickelocene and ferrocene, it proceeds gradually in nickelocene and by way of a cooperative phase transition in ferrocene. A reason for this originates in loose molecular packing in nickelocene crystal. Molar heat capacity and the standard molar entropy of nickelocene are larger than those of ferrocene beyond the mass effect over the whole temperature region investigated. This fact provides with definite evidences for the loose molecular packing in nickelocene crystal.