The effects of bromine treatment on the hydrogen storage properties of multi-walled carbon nanotubes

The effects of bromine treatment on the properties of multi-walled carbon nanotubes (MWCNTs) such as surface porosity, sp² hybridization, functional groups and hydrogen storage capacity were studied and compared with treated MWCNTs by HCl, HNO₃ and H₂SO₄ acids. The treatments affect the graphitization properties (sp² hybridization) and porous structures of MWCNTs by enlarging the specific surface area and the micro-pore volume. In addition, the hydrogen storage capacity of the treated MWCNTs was also investigated by volumetric technique. It is found that the destroying of sp² hybridization of bromine treated MWCNTs increases hydrogen adsorption sites and decreases hydrogen desorption temperature.     

Oxygen‐modified multiwalled carbon nanotubes: physicochemical properties and capacitor functionality

Multiwalled carbon nanotubes (MWCNTs) have found numerous applications in energy conversion systems. The current work focused on the introduction of oxygen moieties onto the walls of MWCNTs by five different reagents and investigating the associated physicochemical properties. Oxygen‐containing groups were introduced onto MWCNTs using an ultrasound water‐bath treatment with HNO₃, HCl, H₂O₂ or HCl/HNO₃ solution. Physicochemical properties were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman, thermal gravimetric analysis, textural characteristics, cyclic voltammetry and electrochemical impedance spectroscopy. The study focus was mainly on linking the physicochemical properties of oxygen‐functionalised MWCNTs and suitability in electrochemical capacitors using group one sulfates. From the Fourier transform infrared spectroscopy KBr pellet protocol, peaks at 3400, 2370 and 1170 cm^?1 suggest oxygen‐containing functionalities on MWCNTs. HNO₃ treatment introduced highest oxygen‐containing moieties and achieved highest specific capacitance in Li₂SO₄ and Na₂SO₄ electrolytes of 36.200 F g^?1 (77 times better than pristine) and 45.100 F g^?1 (2.5 times enhancement), respectively. For K₂SO₄, it was 33.600 F g^?1 (4.9 times better) with HNO₃/HCl‐treated samples. Oxygen‐functionalised MWCNTs displayed both pseudo and electrochemical double‐layer mechanism of enhanced charge storage and cycle stability in group one sulfates electrolytes. The dominating charge storage mechanism was pseudo, and Na₂SO₄ was the best electrolyte amongst the three group one sulfates investigated. Copyright © 2017 John Wiley & Sons, Ltd.     

The mechanism and sorption kinetic analysis of hydrogen storage at room temperature using acid functionalized carbon nanotubes

The present work investigates the effect of acid functionalization of multiwalled carbon nanotubes (MWCNTs) on the physisorption based mechanism of hydrogen storage at room temperature. For this purpose, a suite of functionalized CNT samples is synthesized and subjected to a comprehensive range of material characterization techniques and hydrogen storage measurements. Nitric acid (HNO₃) and the mixture of sulphuric acid and nitric acid (H₂SO₄:HNO₃) are used for the synthesis at oxidation temperatures of 80 °C and 100 °C. Electron microscopy and X-ray photoelectron spectroscopy results reveal that acid functionalization causes major alternation in the physicochemical properties of the CNTs due to the varied concentration of oxygen functional groups. Particularly, the H₂SO₄:HNO₃ functionalized sample at 100 °C is found to have the highest interlayer spacing, oxygen to carbon ratio (26.09 at. %), defect content, and specific surface area (215.3 m²/g). These features collectively contribute to substantially improved hydrogen storage properties, including a ～150% increase in the hydrogen storage capacity at 298 K and 50 bar. Furthermore, kinetic analysis shows that the desorption follows a multiple diffusion process which is sensitive to the oxygen functional groups and structural defects, hence reducing the rate of desorption; whereas the adsorption is controlled by a more rapid, three-dimensional diffusion process.     

Chemical structure and pyrolysis characteristics of demineralized Zhundong Coal

To investigate the effects of acid treatments on the chemical structure and pyrolysis behavior of coal, we examined the low-rank Zhundong coal pretreated by four single acids (HCl, HF, H₂SO₄, HNO₃) and a combined acid (HCl-HF-HCl). Our results indicated that the carboxylic and phenolic hydroxyl contents of the coal increased, while the aliphatic and aromatic hydrogen contents decreased after leaching. Nitric acid destroyed long aliphatic chains in coal, which caused the key pyrolysis stage to occur at lower temperature, the number of volatiles increased, and the pyrolysis rate improved.     

Enhanced electrochemical hydrogen storage by catalytic Fe-doped multi-walled carbon nanotubes synthesized by thermal chemical vapor deposition

Hydrogen storage capacities of raw, oxidized, purified and Fe-doped multi-walled carbon nanotubes (MWCNTs) were studied by electrochemical method. Based on transmission electron microscopy and Raman spectroscopic data, thermal oxidation removed defective graphite shells at the outer walls of MWCNTs. The analysis results indicated that the acid treatment dissolved most of the catalysts and opened some tips of the MWCNTs. Thermal gravimetric analysis and differential scanning calorimetry results illustrated that by oxidation and purification of MWCNTs, the weight loss peak shifts toward a higher temperature. N₂ adsorption isotherms of the purified and oxidized MWCNTs showed an increase in N₂ adsorption below P/P_o = 0.05, suggesting that microporous structures exist in the purified and oxidized MWCNTs. The electrochemical results revealed that the Fe-doped MWCNTs produced the highest hydrogen storage capacities compared to the other samples in various sweep rates. According to electrochemical analyses, the peak currents of hydrogen adsorption/desorption increased by increasing the catalyst's active surface.     

Effect of the acid type on clinoptilolite-rich tuff for hydrogen storage

Clinoptilolite from Gördes (Turkey) was treated with HCl, HNO₃ and H₂SO₄ solutions of varying concentrations (from 2.0 M to 6.0 M) at 90 °C for 4 h to evaluate its potential for possible applications in hydrogen storage. X-ray diffraction, X-ray fluorescence and nitrogen adsorption techniques were applied for characterization of the zeolites. Hydrogen adsorption capacities of clinoptilolite samples were found in the range between 1.609 and 2.391 mmol/g. The effects of the acid modification process on the structure and hence hydrogen adsorption was evaluated according to the obtained results.     

Enhancing hydrogen storage on carbon nanotubes via hybrid chemical etching and Pt decoration employing supercritical carbon dioxide fluid

Acidic etching and Pt particle decoration were applied to modify the hydrogen absorption behavior of carbon nanotubes (CNTs). Two different acidic solutions, namely H₂SO₄/HNO₃ and FeSO₄/H₂SO₄/H₂O₂, were used for etching treatment. A novel electroless deposition process, incorporating supercritical CO₂ (sc-CO₂) fluid, was used to decorate finely-dispersed nano-sized Pt particles on CNTs. The hydrogen storage capacities of various modified CNTs were measured by using a high pressure thermal gravimetric microbalance (HPTGA). The experimental results showed that acidic etching could increase the surface defect density and lead to open-up of the caps of CNTs, resulting in an increase in the active adsorption site for physical sorption of H_2. The electroless deposition of nano-Pt particles on CNTs, using conventional electrolyte, could promote chemical sorption of hydrogen via spillover mechanism. By employing sc-CO₂ bath, the Pt particle size became much finer and more uniformly distributed on the surfaces of CNTs, giving rise to a high hydrogen storage capacity. When a hybrid process including sc-CO₂ Pt decoration following acidic etching was applied to modify CNTs, a substantial enhancement of hydrogen storage capacity (about 2.7 wt%) was observed.     

Dilute-acid pretreatment of barley straw for biological hydrogen production using Caldicellulosiruptor saccharolyticus

The main objective of this study was to use the fermentability test to investigate the feasibility of applying various dilute acids in the pretreatment of barley straw for biological hydrogen production. At a fixed acid loading of 1% (w/w dry matter) 28–32% of barley straw was converted to soluble monomeric sugars, while at a fixed combined severity of −0.8 30–32% of the straw was converted to soluble monomeric sugars. With fermentability tests at sugar concentrations 10 and 20 g/L the extreme thermophilic bacterium Caldicellulosiruptor saccharolyticus showed good hydrogen production on hydrolysates of straw pretreated with H₃PO₄ and H₂SO₄, and to a lesser extent, HNO₃. The fermentability of the hydrolysate of straw pretreated with HCl was lower compared to the other acids but equally high as that of pure sugars. At sugar concentration 30 g/L the fermentability of all hydrolysates was low.     

Effect of support materials on the performance of direct ethanol fuel cell anode catalyst

Pt–Ru catalysts supported on mesoporous carbon nitride (MCN), multiwall carbon nano tubes (MWCNTs), treated MWCNTs (t-MWCNTS) and Vulcan-XC were prepared using co-impregnation reduction method for the oxidation of ethanol in direct ethanol fuel cell (DEFC) to study the effect of support material. The MCN support was prepared using SBA-15 as template and t-MWCNTs were prepared by refluxing in HNO₃ and H₂SO₄ mixture (1:3) using MWCNTs. XRD shows the formation of Pt–Ru bi-metallic catalyst with size ranges from 7 to 17 nm using different supports. The catalyst and its supports were characterized by physically and electrochemically. Linear sweep voltammetry, cyclic voltammetry and chrono amperometry studies of the above systems reveal that MCN supported Pt–Ru catalyst shows higher electro-catalytic activity towards ethanol oxidation compared to Pt–Ru in treated t-MWCNTs, MWCNts and Vulcan-XC supports. The performance of DEFC based on maximum power density is found to be in the order Pt–Ru/MCN > Pt–Ru/t-MWCNTs > Pt–Ru/MWCNTs > Pt–Ru/Vulcan-XC. The Pt–Ru/MCN shows highest power density of 61.1 mW cm⁻² at 100 °C, 1 bar pressure with catalyst loading of 2 mg cm⁻² using 2 M ethanol feed.     

Effect of acid treatment on the physico-chemical properties of Nafion 117 membrane

In this work, the effect on the physico-chemical properties of Nafion 117 membrane due to the treatment with HCl, H₂SO₄ and HNO₃ was studied. Water uptake, crystallinity, proton conductivity and water dynamics were evaluated on treated and non-treated membranes. An increase in the water uptake and conductivity and a decrease in the crystallinity were observed in treated membranes in comparison with the untreated one. The water dynamics, studied by spin-spin NMR relaxometry, suggests that treated membranes have a more uniform channel size distribution. The treatment with HCl and HNO₃ showed higher conductivity and water uptake than H₂SO₄.     

Cobalt loaded organic acid modified kaolin clay for the enhanced catalytic activity of hydrogen release via hydrolysis of sodium borohydride

Inorganic acids such as hydrochloric acid (HCl), nitric acid (HNO₃) and sulphuric acid (H₂SO₄) are generally used in the acid modification of clays. Here, CoB catalyst was synthesized on the acetic acid-activated kaolin support material (CH₃COOH -kaolin- CoB) with an alternative approach. This prepared catalyst, firstly, was used to catalyze the hydrolysis of NaBH₄ (NaBH₄-HR). The structure of the raw kaolin, kaolin-CH₃COOH, and CH₃COOH-kaolin-CoB samples were characterized by X-ray diffraction spectroscopy (XRD), Fourier transforms infrared spectroscopy (FTIR), scanning electron microscope (SEM), and nitrogen adsorption. At the same time, this catalyst performance was examined by Co loading, NaBH₄ concentration, NaOH concentration, temperature and reusability parameters. The end times of this hydrolysis reaction using raw kaolin-CoB and CH₃COOH-kaolin-CoB were found to be approximately 140 and 245 min, respectively. The maximum hydrogen generation rates (HGRs) obtained at temperatures 30 °C and 50 °C were 1533 and 3400 mL/min/g_catalyst, respectively. At the same time, the activation energy was found to be 49.41 kJ/mol.     

Mineral Matter Identification in Nallıhan Lignite by Leaching with Mineral Acids

Abstract

Coals are heterogeneous, complex noncrystalline macromolecules having both organic and inorganic materials that contain some inorganic constituents. Some techniques have been applied to this fossil fuel in order to remove these undesired inorganic parts from the organic part. Chemical demineralization is one of the suitable methods for removal of inorganic elements although it is an expensive way. But by this method, many elements are leached effectively from the lignite body from the point of economic view because these inorganic parts may cause some undesired deleterious effects. In this study, the demineralization effect of some aqueous acids of 5% such as HCl, H₂SO₄, HNO₃, and HF was studied. The effect of these mineral acids was shown by X-ray spectroscopy.     

Hydrogen storage capacity at high pressure of raw and purified single wall carbon nanotubes produced with a solar reactor

Samples of single wall carbon nanotubes (SWNTs) were prepared using a solar reactor. Graphite targets containing different catalysts (Ni/Co, Ni/Y, Ni/Ce) allowed the synthesis of SWNTs soot in which nanotubes had different diameter distributions. Several consecutive stages of HCl treatment and thermal oxidation in air (HCl protocol) purified the samples. Another protocol involving HNO₃ treatment and H₂O₂ oxidation (HNO₃ protocol) was also used. Isotherms of hydrogen adsorption were volumetrically measured at 253 K under pressures below 6 MPa on raw and treated samples. The highest adsorption capacity (0.7  wt%) was measured on raw soot. HCl protocol clearly increases the BET surface area (_SBET)$(S_{\mathrm{BET}})$ and the microporous volume (_W0(_N2))$(W_0({\mathrm{N}}_2))$ measured by N₂ at 77 K of the treated samples with respect to the as-produced materials, whereas HNO₃ protocol decreases them. A correlation between textural properties and hydrogen storage capacities is discussed.     

The effect of acid treatment on pyrolysis of Longkou oil shale

The effect of acid treatment on mineral removal and pyrolysis of Longkou oil shale were investigated. X-ray diffraction (XRD) and X-ray fluorescence (XRF) indicated that the HCl treatment can remove the calcite, the H₂SO₄ treatment can convert the calcite to CaSO₄, and the HF treatment can remove the quartz and convert the calcite to CaF₂; moreover, all three treatments cannot remove the pyrite in the oil shale. Oil shale was individually treated with HCl, H₂SO₄, and HF before conducted the pyrolysis experiment. The pyrolysis results showed that oil shale treated with H₂SO₄ or HF almost equally enhanced the oil yield, while HCl treatment had a negative effect on the oil yield. Thermogravimetry (TG) analysis indicated that the carbonates had a catalytic effect, sulfates may also had a catalytic effect and the silicates had an inhibitive effect on the decomposition of kerogen. Combining the TG analysis, oil yield and the price of every acid, the H₂SO₄ treatment was considered to be the best method to treat oil shale.Moreover, the carbonate minerals can be removed after H₂SO₄ treatment, so it would reduce the amount of pyrolysis feed to increase production efficiency.     

Evaluation of bio-hydrogen production using rice straw hydrolysate extracted by acid and alkali hydrolysis

This study was conducted to investigate the properties of hydrolysates obtained from acid and alkali hydrolysis and to evaluate the feasibility of employing them for bio-hydrogen production. High sugar concentrations of 16.8 g/L and 13.3 g/L were present in 0.5% and 1.0% H₂SO₄ hydrolysates, respectively. However, H₂SO₄ hydrolysis resulted in large amounts of short-chain fatty acids (SCFAs) and furan derivatives, which were removed by detoxification. In bio-hydrogen production, 1.0% H₂SO₄ hydrolysate showed a 55.6 mL of highest hydrogen production and 1.14 mol-H₂/mol-hexose equivalent_added of hydrogen yield. In control and 1.0% NaOH hydrolysate, 29.7 mL and 36.9 mL of hydrogen were produced, respectively. Interestingly, relatively high acetate and butyrate production resulted in lactate reduction. Also, NH₄OH hydrolysate produced less than 10 mL of hydrogen. Thus, these results indicate that hydrogen production and metabolite distribution can vary depending on the sugars and by-product composition in the hydrolysate.     

Enhanced photoelectrochemical-response in highly ordered TiO2 nanotube-arrays anodized in boric acid containing electrolyte

We examine the photoelectrochemical properties of highly ordered titanium dioxide nanotube-array photoanodes, fabricated by anodization of titanium in a nitric acid/hydrofluoric acid electrolyte, with and without the addition of boric acid. Under UV–Vis illumination the photocurrent densities achieved with TiO₂ nanotube-arrays fabricated in the H₃BO₃–HNO₃–HF electrolyte are a factor of seven greater than the TiO₂ nanotube-array samples obtained in the commonly used HNO₃–HF electrolyte, indicating the ability to control the photoelectrochemical response of the highly ordered nanotube arrays by tailoring the electrolyte composition. For 560 nm long boric-acid fabricated nanotube arrays, a photoconversion efficiency of 7.9% is achieved upon a 320–400 nm illumination at an intensity of 98 mW/cm², with hydrogen generated by water photoelectrolysis at the power-time normalized rate of 1708-μmol/h W (42 ml/h W). The resulting nanotube-arrays demonstrate excellent photocorrosion stability, with no detectable degradation in photoconversion properties over 6 months of testing. While the titania bandgap is not suitable for high visible spectrum efficiencies, the high photoconversion efficiency achieved under UV illumination indicates the suitability of the highly ordered nanotube-array architecture for hydrogen generation by water photoelectrolysis.     

Production of biodiesel from citrus maxima (Chakotara) seed oil,a potential of non-food feedstock and its blends with n butanol-diesel and purification,utilization of glycerol obtained as by-product from biodiesel

The aim of the study is to enhance the production and performance of biodiesel from non-food feedstock seeds of citrus maxima through base catalyzed transesterification process. The Performance of biodiesel was increased by the blends with butanol-diesel (Biodiesel + Butanol + Diesel) in different proportions. The obtained biodiesel and its blends were characterized by ASTM. In this study, Glycerol was obtained as a by-product of citrus maxima biodiesel. Crude glycerol was purified by the H₃PO₄, H₂SO₄, HCl, and HNO₃. The characterization of glycerol included Flash Point, ash Content, alkalinity, FT-IR, etc..     

Development of Pd and Pd-Co catalysts supported on multi-walled carbon nanotubes for formic acid oxidation

Pd-Co and Pd catalysts were prepared by the impregnation synthesis method at low temperature on multi-walled carbon nanotubes (MWCNTs). The nanotubes were synthesized by spray pyrolysis technique. Both catalysts were obtained with high homogeneous distribution and particle size around 4 nm. The morphology, composition and electrocatalytic properties were investigated by transmission electron microscopy, scanning electron microscopy-energy dispersive X-ray analysis, X-ray diffraction and electrochemical measurements, respectively. The electrocatalytic activity of Pd and PdCo/MWCNTs catalysts was investigated in terms of formic acid electrooxidation at low concentration in H₂SO₄ aqueous solution. The results obtained from voltamperometric studies showed that the current density achieved with the PdCo/MWCNTs catalyst is 3 times higher than that reached with the Pd/MWCNTs catalyst. The onset potential for formic acid electrooxidation on PdCo/MWCNTs electrocatalyst showed a negative shift ca. 50 mV compared with Pd/MWCNTs.     

The synthesized nickel-doped multi-walled carbon nanotubes for hydrogen storage under moderate pressures

Hydrogen adsorption capacity of Multiwalled carbon nanotubes (MWCNTs) decorated with Nickel (Ni) nanoparticles has been presented at room temperature and under moderate pressures of 4–20 bar. The functionalization of carbon nanotubes was carried by H₂SO₄-HNO₃ reducing agents and the Ni supported MWCNTs (Ni-MWCNTs) were prepared by wet chemical method. The structure and morphology characterization of samples were performed by XRD, TEM, EDX and SEM analyses. These nanotubes then subjected to hydrogenation step by using Sievert's-like apparatus. The hydrogenation of the Ni-MWCNTs was performed at 298 K and moderate hydrogen pressures of 4–20 bar. The obtained results show that there is a correlation between hydrogen storage capacity and hydrogen pressure that; as the pressure was increased, hydrogen uptake capacity enhanced due to physisorption. In addition, maximum hydrogen storage capacity of Ni-MWCNTs was found to be 0.298 wt % at room temperature and under pressure of 20 bar.     

H2SO4 poisoning of Ru-based and Ni-based catalysts for HI decomposition in SulfurIodine cycle for hydrogen production

The sulfur–iodine (SI) cycle is deemed to be one of the most promising alternative methods for large-scale hydrogen production by water splitting, free of CO₂ emissions. Decomposition of hydrogen iodide is a pivotal reaction that produces hydrogen. The homogeneous conversion of hydrogen iodide is only 2.2% even at 773 K [1]. A suitable catalyst should be selected to reduce the decomposition temperature of HI and attain reaction yields approaching to the thermodynamic equilibrium conversion. However, residual H₂SO₄ could not be avoided in the SI cycle because of incomplete purification. The H₂SO₄ present in the HI feeding stream may lead to the poisoning of HI decomposition catalysts. In this study, the activity and sulfur poisoning of Ru and Ni catalysts loaded on carbon and alumina, respectively, were investigated at 773 K. HI conversion efficiency markedly decreased from 21% to 10% with H₂SO₄ (3000 ppm) present, which was reversible when H₂SO₄ was withdrawn in the case of Ru/C. In the case of Ru/C and Ni/Al₂O₃, catalyst deactivation depends on the concentration of H₂SO₄; the higher the concentration of H₂SO_4, the greater the severity of deactivation. Catalysts before and after sulfur poisoning were characterized by transmission electron microscopy (TEM), energy-dispersive X-Ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Experimental results and characterization of poisoned and fresh catalysts indicate that the catalyst deactivation could be ascribed to the competitive adsorption of sulfur species and change in its surface properties.