Activated carbon from sugar cane bagasse by carbonization in the presence of inorganic acids

Dried ground bagasse, impregnated with 50% inorganic acids and carbonized at 500°C, showed the sequence H₃PO₄ > H₂SO₄ > HCl > HNO₃, with respect to the efficiency of activation. Treatment with phosphoric acid of various concentrations (30–50 wt%) was followed by carbonization at 300–500°C for 3 h. Pore structure parameters were determined from the low-temperature adsorption of nitrogen, by applying the BET and α_s methods. Activated carbons obtained at low temperatures are essentially microporous with a low degree of mesoporosity. At higher temperatures products of higher surface area and total pore volume with developed mesoporosity and low microporosity are formed. An increase in the period of carbonization leads to a small decrease in both surface area and pore volume. Activated carbons with surface areas > 1000 m² g^?1 and mean pore dimensions around 2·0 nm, suitable for various purposes, are thus obtained.     

Electron rich porous carbon/silica matrix from rice husk and its characterization

Free electron rich porous carbon/silica matrix (ECS₈₀₀) was prepared from rice husk by carbonization at 400 °C and activation by phosphoric acid (H₃PO₄) at 800 °C. The ratio of H₃PO₄ to pre-carbonized carbon was fixed at 2.3. The surface area, pore volume, and pore size distribution of ECS₈₀₀ was measured, using nitrogen adsorption isotherms at 77 K. The unpaired electron density of ECS₈₀₀ was measured in electron spin resonance spectroscopy, using 4-hydroxy 2,2,6,6-tetramethyl piperidine-1-oxyl as the reference spin probe. ECS₈₀₀ was further characterized, using X-ray diffraction, scanning electron microscope, Fourier transform infrared spectroscope, and ²⁹Si-nuclear magnetic resonance spectroscope to study crystallization, surface morphology, functional group and different types of silicon species.     

A novel method for production of activated carbon from waste tea by chemical activation with microwave energy

This study presents the production of activated carbon from waste tea. Activated carbons were prepared by phosphoric acid activation with and without microwave treatment and carbonisation of the waste tea under nitrogen atmosphere at various temperatures and different phosphoric acid/precursor impregnation ratios. The surface properties of the activated carbons were investigated by elemental analysis, BET surface area, SEM, FTIR. Prior to heat treatment conducted in a furnace, the mixture of the waste tea and H₃PO₄ was treated with microwave heating. The maximum BET surface area was 1157 m²/g for the sample treated with microwave energy and then carbonised at 350 °C. In case of application of conventional method, the BET surface area of the resultant material was 928.8 m²/g using the same precursor and conditions. According to the Dubinin–Radushkevich (DR) method the micropore surface area for the sample treated with microwave energy was higher than the sample obtained from the conventional method. Results show that microwave heating reasonably influenced the micropore surface area of the samples as well as the BET surface area.The samples activated were also characterised in terms of the cumulative pore and micropore volumes according to the BJH, DR and t-methods, respectively.     

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

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

Preparation and pore characterization of activated carbon from Ma bamboo (Dendrocalamus latiflorus) by H3PO4 chemical activation

High specific surface area activated carbon materials have been produced from the naturally occurring Ma bamboo (Dendrocalamus latiflorus) using phosphoric acid (H₃PO₄) as the activating agent. The effects of different sizes of raw materials, H₃PO₄ concentrations, and activation temperatures on the specific surface area, pore morphology, and mass yield of activated carbon are presented. A high specific surface area for activated carbon derived from Ma bamboo was achieved under the optimized conditions of 45 wt% H₃PO₄ impregnation concentration, activation temperature of 400 °C, and a holding time of 120 min. Chemical activation of Ma bamboo by H₃PO₄ is a useful technique for obtaining activated carbon with desired pore size distributions and pore morphologies from low cost precursors and at low activation temperatures.     

Isomer Directed Synthesis of Two 3D Cadmium(II) Compounds: Structure Variation and Energetic Performance

Two inorganic mixtures of copper and sodium compounds have been synthesized and characterized with different measurement techniques. The thermal property of these mixtures has been studied to low temperature up to 223 from 573 K with DSC. The specific heat capacity of this mixture has been measured in atmospheric O₂ at a rate of 10 K min^?1 from 573 to 223 K and vice versa in two thermal cycles. The net specific heat capacity of these mixtures is found endothermic in first and second thermal cycles. The net specific heat capacity of 0.5Cu₂(PO₄)(OH); 3.5CuH(PO₄)₂·H₂O; 2NaHSO₄·H₂O (CuPHS) during first thermal cycle is ?71203.05 J kg^?1 K^?1 and in second thermal cycle is ?73881.67 J kg^?1 K^?1 between temperature range of 303–223 K. The net specific heat capacity of mixture 0.5Cu₂(PO₄)(OH); 3.5CuH(PO₄)₂; 2Na₂SO₄(CuPS) in first thermal cycle is ?21158.37 J kg^?1 K^?1 and in second thermal cycle is?45739.92 J kg^?1 K^?1 between temperature range of 298–573 K. As both mixtures are endothermic in nature in all cycles, it can be used as heat storage material.The average crystallite size of mixture 0.5Cu₂(PO₄)(OH); 3.5CuH(PO₄)₂·H₂O; 2NaHSO₄·H₂O and 0.5Cu₂(PO₄)(OH); 3.5CuH(PO₄)₂; 2Na₂SO₄ is ~47 and ~17.3 nm, respectively.     

Adhesion improvement of electroless copper to PC substrate by a low environmental pollution MnO2–H3PO4–H2SO4–H2O system

A low environmental pollution etching system, MnO₂–H₂SO₄–H₃PO₄–H₂O colloid, was used to investigate surface etching performance of polycarbonate (PC) as a replacement for the chromic acid etching solution. The effects of H₂SO₄ concentrations, H₃PO₄ concentrations and etching times upon the surface topography, surface chemistry and surface roughness were studied. With the appropriate etching treatment, the surface average roughness (R_a) of PC substrates increased from 3 to 177 nm, and the adhesion strength between the electroless copper and PC substrate also reached 1.10 KN m⁻¹. After the etching treatment, the PC surface became hydrophilic and the surface contact angle decreased from 95.2° to 24.8°. The intensity of C–O groups increased and the new functional groups (–COOH) formed on the PC surface with the etching treatment, which improved the adhesion strength between PC substrate and elctroless copper film.     

Methylene blue adsorption by chemically activated waste pork bones

Bone is an inorganic template containing organic material inside which can be converted into hydroxyapatite‐rich material by pyrolysis. Nowadays, there is a growing research interest in the use of hydroxyapatite, the chemical formula of which is Ca₁₀(PO₄)₆(OH)₂. In the present work, pork bone, an abundant biomass source and food waste, has been converted into structured porous hydroxyapatite by a three‐step process including precharring under mild conditions, chemical activation, and thermal activation. The investigated activating agents were NaOH, KOH, K₂CO₃, H₂SO₄, and H₃PO₄. A thorough investigation of the influence of different activating protocols on the chemical and textural properties of the produced material was carried out by nitrogen adsorption–desorption at 77 K, potentiometric titrations, Fourier transform infrared, and X‐ray diffraction techniques. Chemical activation with NaOH, K₂CO₃, and H₂SO₄ increased the specific surface area up to 53%. H₃PO₄ reduced both surface area and pore volume, and KOH showed little influence on the pore structure. The produced materials were evaluated by methylene blue adsorption tests and showed significant improvement as a result of chemical activation. As a main effect, acid treatment increased methylene blue adsorption kinetics, probably owing to an increase in micropororosity, whereas alkali activation enhanced the adsorption capacity of the resultant biochar.     

Preparation and Characterisation of Proton Exchange Membranes Based on Crosslinked Polybenzimidazole and Phosphoric Acid

Crosslinked polybenzimidazole (PBI) was synthesised via free radical polymerisation between N‐vinylimidazole and vinylbenzyl substituted PBI. The degree of crosslinking increases with increasing content of the crosslinker. The phosphoric acid doping behaviour, mechanical properties, proton conductivity and acid migration stability of crosslinked PBI and linear PBI are discussed. The results show that the acid doping ability decreases with increasing degree of crosslinking of PBI. The introduction of N‐vinylimidazole in PBI is beneficial to its oxidation stability. The mechanical stability of crosslinked PBI/H₃PO₄ membrane is better than that of linear PBI/H₃PO₄ membrane. The proton conductivity of the acid doped membranes can reach ∼10^–4 S cm^–1 for crosslinked PBI/H₃PO₄ composite membranes at 150 °C. The temperature dependence of proton conductivity of the acid doped membranes can be modelled by an Arrhenius relation. The proton conductivity of crosslinked PBI/H₃PO₄ composite membranes is a little lower than that of linear PBI/H₃PO₄ membranes with the same acid content. However, the migration stability of H₃PO₄ in crosslinked PBI/H₃PO₄ membranes is improved compared with that of linear PBI/H₃PO₄ membranes.     

Zirconia aerogels and xerogels: Influence of solvent and acid on structural properties

High-surface-area zirconia aerogels with meso- to macroporosity have been prepared by an acid-catalyzed alkoxide-sol-gel route with tetrabutoxyzirconium(IV) and subsequent high-temperature supercritical drying at 578 K. The effect of solvent (ethanol, propanol, butanol, t-amylalcohol), amount of nitric acid, calcination temperature, and drying method was studied by nitrogen physisorption, X-ray diffraction, Fourier transform Raman and diffuse reflectance infrared Fourier transform spectrosopy, scanning electron microscopy, thermal analysis, and temperature-programmed desorption of NH₃. After calcination in air at 573 or 773 K, the aerogels possess specific surface areas of up to 270 or 180 m² · g^–1, respectively. The use of ethanol as solvent resulted in the highest specific surface areas and pore volumes (up to 1.5 cm³ · g^–1) among all samples studied, whereas bulky t-amylalcohol caused a shift of the maxima of the broad pore size distributions from 30 to 70 nm. With the corresponding xerogels, prepared via the same wet-chemical procedure but evaporatively dried at ambient temperature, butanol resulted in a maximum at 3 nm and t-amylalcohol in a bimodal pore size distribution with maxima at 3 and 15 nm. The variation of the acid-to-alkoxide ratio in the range 0.08–0.12 at a hydrolysis level of 4 did not significantly influence the structural properties of aerogels and related xerogels. In contrast to the aerogels, the xerogels had significantly lower specific surface areas and prominent microporosity. All uncalcined aerogels contained crystalline ZrO₂, whereas the corresponding uncalcined xerogels were X-ray amorphous and crystallized only during calcination at 573 K. Both aerogels and xerogels possessed Brønsted-type and Lewis-type acid sites. With the xerogels, the density of acid sites on the surface was significantly lower. This behaviour is attributed to the higher amounts of organic residues which persisted in and on the xerogels up to 773 K and thus blocked the acid sites partially.     

Studies on the identification of the heteropoly acid generated in the H3PO4–WO3–Nb2O5 catalyst and its thermal transformation process

The precursor of the mixed metal oxide catalyst composed of H₃PO₄–WO₃–Nb₂O₅, which exhibits excellent activity in Friedel–Crafts alkylations, was identified with ³¹P NMR. It was revealed that the Keggin-type mixed heteropoly acid, H₄PNbW₁₁O₄₀, was spontaneously generated during preparation of the H₃PO₄–WO₃–Nb₂O₅ catalyst. The partial decomposition of H₄PNbW₁₁O₄₀ occurred in the temperature range of 673–823 K to give an amorphous oxide that had a Brønsted acid character. Based on the results of structural and acidic studies, the active species obtained through the calcination of H₃PO₄–WO₃–Nb₂O₅ was ascribed to the transient state in the course of the thermal decomposition of the H₄PNbW₁₁O₄₀ over the WO₃–Nb₂O₅ support. In fact, the catalyst prepared by mixing H₄PNbW₁₁O₄₀, niobic oxalate, and ammonium tungstate solutions, followed by calcination at 773 K, exhibited excellent activity in the Friedel–Crafts acylation of anisole with carboxylic acids.     

Nanoarchitectonics of Nanoporous Carbon Materials from Natural Resource for Supercapacitor Application

Nanoarchitectonics of nanoporous carbon materials (NCMs) derived from natural resource; Areca Catechu Nut (ACN) with enhanced electrochemical supercapacitance properties is reported. ACN powder is chemically activated in a tubular furnace at 400?°C and the effect of activating agent sodium hydroxide (NaOH), zinc chloride (ZnCl₂) and phosphoric acid (H₃PO₄) on the textural properties, surface functional groups and electrochemical supercapacitance properties was thoroughly examined. We found that ACN derived NCMs are amorphous in nature comprising of macropores, micropores and hierarchical micro- and mesopore architecture depending on the activating agent. Surface area and pore volume are found in the range 25–1985 m² g^?1 and 0.12–3.42 cm³ g^?1, respectively giving the best textural properties for H₃PO₄ activated NCM. Nevertheless, despite the different chemical activating agent used, all the prepared NCMs showed similar oxygen-containing surface functional groups (carboxyl, carboxylate, carbonyl and phenolic groups). The H₃PO₄ activated NCM showed excellent supercapacitance properties giving a high specific capacitance of ca. 342 F g^?1 at a scan rate of 5 mV s^?1 together with the high cyclic stability sustaining capacitance retention of about 97% after 5000 charging/discharging cycles. Electrochemical supercapacitance properties have demonstrated that the ACN derived novel nanoporous carbon material would be a potential material in energy storage application.     

Phosphoric acid doped poly(2,5‐benzimidazole)‐based proton exchange membrane for high temperature fuel cell application

Undoped and doped poly(2,5‐benzimidazole) (ABPBI) membrane was prepared by solvent casting method using methane sulfonic acid as a solvent and phosphoric acid (H₃PO₄) as a doping agent. The concentration of H₃PO₄ was varied from 0 to 60 vol% to enhance the proton conductivity of the ABPBI membrane at higher temperature. Wide angle X‐ray diffraction analysis showed a decrease in crystallinity in ABPBI membrane with increase in H₃PO₄ doping concentration. The molecular signature and the presence of H₃PO₄ was observed in 1000–1500 cm^?1 in the Fourier transform infrared spectra, which was also supported by a corresponding weight loss at 180°C–200°C in the thermogravimetric analysis. Undoped ABPBI membrane registered the Young's modulus (E) and hardness (H) values of 2.46 and 0.92 GPa, respectively, and the corresponding E and H values for 1.65 doping level of 60 vol% H₃PO₄ doped ABPBI membrane were 0.14 and 0.067 GPa, respectively. The 60 vol% H₃PO₄ doped ABPBI membrane with doping level of 1.65 showed highest proton conductivity value of 2.2 × 10^?2 S/cm. The impedance spectroscopic analysis and the equivalent circuit model were discussed to understand the nature of proton conduction in H₃PO₄ doped ABPBI membrane. POLYM. ENG. SCI., 56:1366–1374, 2016. © 2016 Society of Plastics Engineers     

Preparation of ordered porous carbon from tea by chemical activation and its use in Cr(VI) adsorption

Ordered porous carbon was prepared from a new carbon precursor??the tea leaves, the most widely used beverage worldwide by a chemical activation process. We obtained well developed spherical interlinked meso and micro pores with uniform pore morphology and high surface area from green, black and waste tea by NaOH as well as H₃PO₄ activation process. The carbon obtained from green tea by H₃PO₄ activation had the highest BET surface area of 1,285?m²g^?1 with total pore volume of 0.6243?mL?g^?1. The as prepared porous carbon showed high adsorption efficiency of Cr(VI) adsorption from aqueous solution.     

Activation of graphene aerogel with phosphoric acid for enhanced electrocapacitive performance

We present a facile and efficient route to introduce in-plane nanopores on the graphene sheets by activation of graphene aerogel (GA) with phosphoric acid (H₃PO₄). Results from N₂ adsorption and TEM images showed that H₃PO₄ activation created mesopores with pore size of 2–8 nm on the graphene sheets. With such nanopores on graphene sheets, the activated GA exhibits a specific capacitance of 204 F g⁻¹, enhanced rate capability (69% capacitance retention from 0.2 to 30 A g⁻¹), reduced equivalent series resistance (3.8 mΩ) and shortened time constant (0.73 s) when comparing with the hydrothermally-derived pristine GA and thermally annealed GA in the absent of H₃PO₄. The excellent capacitive properties demonstrate that introduction of nanopores on GA by H₃PO₄ activation not only provides large ion-accessible surface area for efficient charge storage, but also promotes the kinetics of electrolyte across the graphene two-dimensional planes.     

Decomposition of H2O2 on activated carbon obtained from olive stones

Activated carbons were prepared from olive oil solid wastes by treatment in different schemes: impregnation with H₃PO₄ followed by pyrolysis at 300–700 °C, by steam pyrolysis at 600–700 °C, or by conventional steam activation at 850 °C. Porosity characteristics were determined by analysis of nitrogen adsorption isotherms, and carbons of widely different properties and surface pH values were obtained. Decomposition of H₂O₂ in dilute unbuffered solution was followed by measuring evolved oxygen volumetrically. First‐order kinetics was followed, and the catalytic rate coefficients were evaluated. The carbons tested showed appreciable activity where evolved oxygen attained ≈10% of the stoichiometric amount in 1 h. The degree of decomposition showed inverse dependence on surface area, pore volume and mean pore dimensions. The chemical nature of the surface, rather than the porosity characteristics, was the principal factor in enhancing the disproportionation of H₂O₂ on the activated carbon surface. © 2001 Society of Chemical Industry     

Vapor-phase alkylation of toluene by benzyl alcohol on H3PO4-modified MCM-41 mesoporous silicas

Several mesoporous aluminosilicate molecular sieves with the MCM-41 structure (SiO₂/Al₂O₃ = 20–200) have been synthesized using different aluminum sources and modifying several synthesis parameters during the preparation process, such as the temperature and the content of water and sulfuric acid in the gel mixture. All samples were characterized by element chemical analysis, X-ray diffraction, N₂ physisorption, thermal analyses, and electron microscopy. These Al-MCM-41 materials have BET surface areas up to 940 m² g⁻¹. The catalytic properties of their H₃PO₄-treated derivatives for Friedel–Crafts alkylation of toluene with benzyl alcohol have been evaluated. Toluene benzylation preferentially gave p-benzyl-toluene. The conversion of toluene to monoalkylated products increased with increasing the H₃PO₄ content in the catalysts and reached a maximum value for a H₃PO₄ loading of 25%, a further increase in H₃PO₄ leading to a decrease in the activity for alkylation. The influence of H₃PO₄ loading and of the operating parameters on the performance of the catalysts was also investigated.     

Activated Carbon Preparation from Lignin by H3PO4 Activation and Its Application to Gas Separation

Activated carbons were produced from corn straw lignin using H₃PO₄ as activating agent. The optimal activation temperature for producing the largest BET specific surface area and pore volume of carbon was 500 °C. The maximum BET specific surface area and pore volume of the resulting carbon were 820 m²g^–1 and 0.8 cm³g^–1, respectively. The adsorption isotherm model based on the Toth equation together with the Peng‐Robinson equation of state for the determination of gas phase fugacity provide a satisfactory representation of high pressure CO₂, CH₄ and N₂ adsorption. The kinetic adsorption results show that the breakthrough difference between CO₂ and CH₄ is not obvious, indicating that its kinetic separation performance is limited.     

Nitrogen in aramid-based activated carbon fibers by TPD, XPS and XANES

Activated carbon fibers were prepared from Nomex® [poly(m-phenylene isophthalamide)] by either H₃PO₄ activation, H₃PO₄-CO₂ activation, or simply CO₂ or steam activation. These treatments converted amide groups from the polymer precursor into complex and heterogeneously distributed nitrogen functionalities. TPD, XPS and XANES were used to study the effects of these treatments on the local bonding environment around nitrogen in the resulting carbons. These analytical techniques showed that nitrogen atoms are present in the 6-membered rings located at the edges of condensed polyaromatic systems as pyridine-like sp² nitrogen (N1 or N2) or in the interior, where nitrogen replaces one carbon atom and is bonded to three carbon neighbors (N3). The occurrence of a species (N2) hypothetically related to a pyridinic cycle bearing oxygen substituents or intracyclic oxygen atoms could be correlated with the degree of oxidation of the carbon surface. Assuming that a relative N3 increase is indicative of aromatization and that the reverse, correlated with a N2 increase, is indicative of surface oxidative denitrogenation, the ratio between these nitrogen species revealed that aromatization and oxidative denitrogenation processes occur sequentially or simultaneously to different extents according to the type of carbon activation and to the burn-off degree. Physical activation involves thermal aromatization reactions during the carbonization stage and the subsequent isothermal activation one. In this second activation stage, co-occurring thermal oxidation reactions lead to a less intense denitrogenation during CO₂ activation than during steam activation. H₃PO₄ activation induces the largest nitrogen retention in the final product in a double process of aromatization and “auto-activation” producing a moderate oxidative attack of nitrogen. However, an increase of the H₃PO₄ ratio fostered the oxidation of the carbon surface and consequently enhanced nitrogen gasification during the subsequent activation.     

Preparation of fibrous porous materials by chemical activation 2. H3PO4 activation of polymer coated fibers

Fibrous porous materials (FPMs) have been prepared by coating a glass fiber with an aqueous solution of poly(vinyl alcohol) (PVA) and H₃PO₄, followed by stabilization and heat treatment in air. The H₃PO₄ was then removed by washing with deionised water and NaOH. The results show that H₃PO₄ acts as a dehydration agent to promote pyrolytic and thermal crosslinking of PVA at a much lower temperature of 170 °C, leading to FPMs having much higher char yields and surface areas. The activation in air is of benefit to achieve higher surface areas as compared to using N₂. Utilizing a fiberglass mat to support coatings of PVA activated with H₃PO₄ results in much higher specific surface areas. The activation temperature, activation time and concentration of H₃PO₄ have strong effects on the surface area, pore size distribution and coating content of FPMs.