Adsorption of methyl orange using activated carbon prepared from lignin by ZnCl2 treatment

Lignocellulosic materials are good and cheap precursors for the production of activated carbon. In this study, activated carbons were prepared from the lignin at different temperatures (200 to 500°C) by ZnCl₂. The effects influencing the surface area of the resulting activated carbon are activation temperature, activation time and impregnation ratio. The optimum condition, are found an impregnation ratio of 2, an activation temperature of 450°C, and an activation time of 2 h. The results showed that the surface area and micropores volume of activated carbon at the experimental conditions are achieved to 587 and 0.23 cm³ g^?1, respectively. The adsorption behavior of methyl orange dye from aqueous solution onto activated lignin was investigated as a function of equilibrium time, pH and concentration. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. A maximum adsorption capacity of 300 mg g^?1 of methyl orange by activated carbon was achieved.     

Intensity enhancement in cross-beam pulsed laser ablation using two orthogonal targets

In this work we investigated a novel configuration of the orthogonal geometry for double pulse laser ablation. In this arrangement, a laser is focused onto a target generating a highly directed plume; after that, an additional laser produces a second plasma onto another perpendicular target. In this way, the second plume is expanded through the first plume region. Ablation of carbon was carried out in vacuum (10^− 4 Pa) by two delayed lasers. The first pulse corresponds to a Nd:yttrium–aluminum–garnet (YAG) (1064 nm) and the second one to an excimer (248 nm) laser. Results show that plasma interactions produce different species emission enhancement depending on the delay between lasers, laser fluences and the spatial overlapping between plumes. Approximately an 100-fold increase in emission signal was measured as the observation distance grows.     

InAsSb/InAsSbP double heterostructure lasers for 3-4 micrometer spectral range

InAsSb/InAsSbP double heterostructure diode lasers for the spectral range of 3-4 microm grown by liquid phase epitaxy have been investigated. The laser tuning was studied as a function of the stripe width. The temperature and current tuning of such lasers was measured. Emission spectra, far-field patterns and wavelength tuning versus current have been studied in the wide current range from threshold, Ith, up to 6Ith at liquid nitrogen temperature. Current wavelength tuning in single-mode lasing has been obtained both towards the shorter wavelengths (up to 4.56 cm-1) and towards the longer wavelengths (up to 0.9 cm-1) at the temperature T=77K. Comparison of the emission properties of the lasers, driven by different types of current pulses showed the same quantum-mechanical nature of current tuning. The theoretical model of this nonlinear optical phenomenon is proposed. The estimated times of current tuning defined mainly by the photon lifetime in the cavity are about 10(-9) to 10(-12) s. The emission line-width was determined to be 20 MHz. Optimal conditions were found for the use of the lasers and were employed for the detection of NH3, CH3Cl, OCS and atmospheric water.     

Surface microstructure formation by ps‐ and fs‐laser ablation of an elastomer composite

We investigated the laser ablation of an elastomer composite with picosecond‐ (ps‐) and femtosecond‐ (fs‐) pulsed UV lasers (ps‐laser: λ = 263 nm, τ = 8 ps; fs‐laser: λ = 248 nm, τ = 500 fs). Upon laser irradiation, a unique microstructure on the surface of the elastomer composite (acrylate polymer) containing carbon black (particle size: 18–30 nm) was observed. The laser‐ablated surfaces were analyzed by scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The formation mechanism is discussed in terms of thermal effects induced by the different pulse durations of the lasers.     

Laser desorption fast gas chromatography–Mass spectrometry in supersonic molecular beams

A novel method for fast analysis is presented. It is based on laser desorption injection followed by fast gas chromatography-mass spectrometry (GC-MS) in supersonic molecular beams. The sample was placed in an open air or purged laser desorption compartment, held at atmospheric pressure and near room temperature conditions. Desorption was performed with a XeCl Excimer pulsed laser with pulse energy of typically 3 mJ on the surface. About 20 pulses at 50 Hz were applied for sample injection, resulting in about 0.4 s injection time and one or a few micrograms sample vapor or small particles. The laser desorbed sample was further thermally vaporized at a heated frit glass filter located at the fast GC inlet. Ultrafast GC separation and quantification was achieved with a 50-cm-long megabore column operated with a high carrier gas flow rate of up to 240 mL/min. The high carrier gas flow rate provided effective and efficient entrainment of the laser desorbed species in the sweeping gas. Following the fast GC separation, the sample was analyzed by mass spectrometry in supersonic molecular beams. Both electron ionization and hyperthermal surface ionization were employed for enhanced selectivity and sensitivity. Typical laser desorption analysis time was under 10 s. The laser desorption fast GC-MS was studied and demonstrated with the following sample/matrices combinations, all without sample preparation or extraction: (a) traces of dioctylphthalate plasticizer oil on stainless steel surface and the efficiency of its cleaning; (b) the detection of methylparathion and aldicarb pesticides on orange leaves; (c) water surface analysis for the presence of methylparathion pesticide; (d) caffeine analysis in regular and decaffeinated coffee powder; (e) paracetamol and codeine drug analysis in pain relieving drug tablets; (f) caffeine trace analysis in raw urine; (g) blood analysis for the presence of 1 ppm lidocaine drug. The features and advantages of the laser desorption fast GC-MS are demonstrated and discussed.     

Laser-induced shape transformation of gold nanoparticles below the melting point: the effect of surface melting

Relatively large gold nanoparticles (mean diameter of major axis 38.2 nm, mean aspect ratio 1.29) in aqueous solution were found to undergo shape transformations from ellipsoids to spheres at ca. 940 degrees C, which is much lower than their melting point, ca. 1060 degrees C. The shape transformation of gold nanoparticles induced by a single pulse of a Nd:YAG laser (lambda = 355 nm, pulse width = 30 ps) was directly observed by a transmission electron microscope (TEM). Analysis of the experimental data showed that the threshold energy for photothermally induced shape transformation was on the order of 40 fJ for a particle, which is smaller than the energy, 67 fJ, required for its complete melting. Estimations based on the heat balance and surface melting model revealed that the temperature which particles reach after a single laser pulse was about 940 degrees C, with the thickness of the liquid layer on the surface of the solid core being 1.4 nm. We also examined thermally induced shape transformation of gold nanoparticles on Si substrates; above 950 degrees C they changed their shapes to spheres, which supported our estimation. Due to the surface melting of particles, their shape transformation occurs at a temperature much lower than their melting point.     

Laser photochemistry of aromatic substituted cyclobutanes and cyclobutenes

The photochemical ring opening and ring cleavage reactions of 6b,8a-dihydrocyclobut[a]acenaphthylene (1) and two similar compounds are described. These reactions occur at room temperature only if the irradiating light intensity is greater than MW/cm², easily obtained with excimer and dye lasers. This is rationalized in terms of a consecutive two-photon absorption to reach higher-lying reactive states. The mechanism proposed for the reaction of 1 also describes the product distribution, which depends on irradiation parameters such as laser pulse length, wavelength, intensity, and oxygen content of the solvent.     

Temperature-Responsive Electrocatalysis Based on Poly(N-Isopropylacrylamide)-Modified Graphene Oxide (PNIPAm-GO)

Poly(N-isopropylacrylamide)-modified graphene oxide (PNIPAm-GO), which is a type of thermally responsive GO, was designed and synthesized through a covalent “grafting-from” strategy. The as-prepared modified nanosheets integrated the individual advantages of two components, such as the thermal sensitivity of the PNIPAm terminal as well as the conductivity and the open 2D structure of the GO substrate. PNIPAm-GO was able to perform the reversible regulation of hydrophilicity/hydrophobicity in aqueous solution upon variations in the temperature. Such a unique property might also lead to the utilization of PNIPAm-GO as an intelligent electrode material to achieve a switchable electrochemical response toward a [Fe(CN)₆]^3−/4− probe. The PNIPAm-GO modified glassy carbon electrode (PNIPAm-GO/GC electrode) was able to exhibit better electrochemical performance in an ON/OFF switching effect than the PNIPAm-modified glassy carbon electrode (PNIPAm/GC electrode) without GO owing to the intrinsic properties and large surface area of the introduced GO. Moreover, it was found that the PNIPAm-GO/GC electrode also displayed excellent thermally responsive electrocatalysis toward the detection of 1,4-dihydro-β-nicotinamide adenine dinucleotide (NADH) and dopamine (DA), which resulted in two different catalytic statuses on the same electrode. This kind of switchable catalytic performance of the PNIPAm-GO/GC electrode might greatly enhance the flexibility of its application, and thus it is expected to have wide potential for applications in the fields of biosensors and biocatalysis.     

Optimization and Characterization of Mesoporous Sulfonated Carbon Catalyst and Its Application in Modeling and Optimization of Acetin Production

In this study, an optimized mesoporous sulfonated carbon (OMSC) catalyst derived from palm kernel shell biomass was developed using template carbonization and subsequent sulfonation under different temperatures and time conditions. The OMSC catalyst was characterized using acid-base titration, elemental analysis, XRD, Raman, FTIR, XPS, TPD-NH₃, TGA-DTA, SEM, and N₂ adsorption–desorption analysis to reveal its properties. Results proved that the OMSC catalyst is mesoporous and amorphous in structure with improved textural, acidic, and thermal properties. Both FTIR and XPS confirmed the presence of -SO₃H, -OH, and -COOH functional groups on the surface of the catalyst. The OMSC catalyst was found to be efficient in catalyzing glycerol conversion to acetin via an acetylation reaction with acetic acid within a short period of 3 h. Response surface methodology (RSM), based on a two-level, three-factor, face-centered central composite design, was used to optimize the reaction conditions. The results showed that the optimized temperature, glycerol-to-acetic acid mole ratio, and catalyst load were 126 °C, 1:10.4, and 0.45 g, respectively. Under these optimum conditions, 97% glycerol conversion (GC) and selectivities of 4.9, 27.8, and 66.5% monoacetin (MA), diacetin (DA), and triacetin (TA), respectively, were achieved and found to be close to the predicted values. Statistical analysis showed that the regression model, as well as the model terms, were significant with the predicted R² in reasonable agreement with the adjusted R² (<0.2). The OMSC catalyst maintained excellent performance in GC for the five reaction cycles. The selectivity to TA, the most valuable product, was not stable until the fourth cycle, attributable to the leaching of the acid sites.     

Surface structural characterization of highly porous activated carbon prepared from corn grain

A novel corn grain precursor was used for the preparation of activated carbon by chemical activation. The detailed investigation of the porosity development in the prepared activated carbon was done by altering the various activation conditions such as the activation temperature, activation time and ratio between the powdered form of carbonized corn grain char and KOH. The surface characteristics including the surface roughness of all the activated carbon samples were evaluated from the analysis of nitrogen (N₂) adsorption isotherm data. At the maximum of 2978 m²/g, a super surface area having the corn grain‐based activated carbon (CG‐AC) was synthesized by using the following conditions: 1/4 ratio of powdered form of carbonized corn grain char/KOH; 800 °C; and 4 h. The possibility of preparing highly porous activated carbons with controlled porosity by varying different activation conditions was found from the pore size distribution results. In particular, the domination of the ratio between the powdered form of carbonized corn grain char and KOH on the porosity development was high compared to the activation temperature and activation time. In addition, the surface roughness calculated from the surface fractal dimension indicates the decrease of surface roughness with increasing activation conditions. Copyright © 2009 John Wiley & Sons, Ltd.     

A New Approach for Controlling Mesoporosity in Activated Carbon by the Consecutive Process of Air Oxidation,Thermal Destruction of Surface Functional Groups,and Carbon Activation (the OTA Method)

A new and simple method, based entirely on a physical approach, was proposed to produce activated carbon from longan fruit seed with controlled mesoporosity. This method, referred to as the OTA, consisted of three consecutive steps of (1) air oxidation of initial microporous activated carbon of about 30% char burn-off to introduce oxygen surface functional groups, (2) the thermal destruction of the functional groups by heating the oxidized carbon in a nitrogen atmosphere at a high temperature to increase the surface reactivity due to increased surface defects by bond disruption, and (3) the final reactivation of the resulting carbon in carbon dioxide. The formation of mesopores was achieved through the enlargement of the original micropores after heat treatment via the CO₂ gasification, and at the same time new micropores were also produced, resulting in a larger increase in the percentage of mesopore volume and the total specific surface area, in comparison with the production of activated carbon by the conventional two-step activation method using the same activation time and temperature. For the activation temperatures of 850 and 900 °C and the activation time of up to 240 min, it was found that the porous properties of activated carbon increased with the increase in activation time and temperature for both preparation methods. A maximum volume of mesopores of 0.474 cm³/g, which accounts for 44.1% of the total pore volume, and a maximum BET surface area of 1773 m²/g was achieved using three cycles of the OTA method at the activation temperature of 850 °C and 60 min activation time for each preparation cycle. The two-step activation method yielded activated carbon with a maximum mesopore volume of 0.270 cm³/g (33.0% of total pore volume) and surface area of 1499 m²/g when the activation temperature of 900 °C and a comparable activation time of 240 min were employed. Production of activated carbon by the OTA method is superior to the two-step activation method for better and more precise control of mesopore development.     

Recycling of carbon fibre reinforced polymeric waste for the production of activated carbon fibres

Composite waste composed of carbon fibres and polybenzoxazines resin has been pyrolysed in a fixed bed reactor at temperatures of 350, 400, 450, 500 and 700 °C. Solid residues of between 70 and 83.6 wt%, liquid yields 14 and 24.6 wt% and gas yields 0.7 and 3.8 wt% were obtained depending on pyrolysis temperature. The derived pyrolysis liquids contained aniline in high concentration together with oxygenated and nitrogenated aromatic compounds. The pyrolysis gases consisted mainly of CO₂, CO, CH₄, H₂ and other hydrocarbons. The carbon fibres used in the composite waste were separated from the char of the solid residue via oxidation of the char at two different temperatures and investigated for their mechanical strength properties. The carbon fibres recovered from the sample pyrolysed at 500 °C and oxidised at 500 °C exhibited mechanical properties which were 90% of that of the original virgin carbon fibres. Steam activation of the recovered carbon fibres was carried out at 850 °C at different times of activation. The effect of activation time on BET surface area, activated carbon fibres yield, porosity and the morphological structure of activated carbon fibres was evaluated. A maximum BET surface area of over 800 m² g⁻¹ was obtained for the activated carbon fibres produced at 850 °C for 5 h of activation. Nitrogen adsorption-desorption isotherms showed that the adsorption capacity increased as the activation time increased up to 5 h of activation and then after that decreased.     

Carbon‐Supported Pt Particles as a Catalyst for Electrooxidation of Methanol and Cyclic Voltammetry Studies Under Acidic Conditions

Electrooxidation of methanol on glassy carbon (GC) electrode modified by optimum carbon supported Pt electrocatalyst (Pt‐C/GC) in acid media is investigated. The catalyst is prepared by ultrasonicating Pt/C powders in aqueous media. The activity of prepared Pt‐C/GC electrode is studied in potential range of 0–1000 mV (versus SCE) by cyclic voltammetry. The results showed that the Pt/C dispersed layer at the surface of glassy carbon electrode, behaves as an electrocatalyst for the oxidation of methanol in acid medium by optimum loading of Pt (0.2 mg cm^?2). The electrochemical properties of prepared electrode are studied under various conditions. However the effect of various parameters in the catalytic enhancement of Pt/C, such as platinum loading, sulfuric acid concentration, different scan rates, different final potentials, and medium temperature are considered and examined.     

Kinetics of nitric oxide reduction with pure and potassium-doped carbon

Summary The kinetics of the reduction of nitric oxide with pure and potassium-doped carbon, NO+C=1/2 N₂+CO, were investigated. For the reaction of NO with pure carbon, measurements were made in the temperature range from 1750 K to 2130 K and at initial NO pressures between 5×10^–3 Pa and 7×10^–2 Pa. The reaction was first order with respect to nitric oxide at NO pressures below 3×10^–2 Pa. The activation energy was 54 kJ/mol for temperatures below 2000 K, while at higher temperatures a second (parallel) reaction became noticeable with a definitely higher activation energy. Potassium-doped carbon was prepared by a molecular beam technique. AES studies verified that potassium was intercalated into the graphite surface and that the potassium-to-carbon ratio changed continuously with sample temperature. The reduction of NO with K-doped carbon was investigated in the temperature range from 710 K to 1080 K and at initial NO pressures between 7×10^–5 Pa and 6×10^–4 Pa while monitoring, in-situ using AES the K/C-ratio of the surface. The NO reduction rate rose linearly with K/C. Compared to pure carbon, the reaction rate for the NO reduction with K-doped carbon increased by a factor in the range of 10⁴. The activation energy for the NO reduction with K-doped carbon was found to be 82 kJ/mol.     

Observation of In vivo Morphologic Changes after Carbon Dioxide Ablative Fractional Laser in a Mouse Model Using Noninvasive Imaging Modalities and Comparison with Histologic Examination

Ablative fractional carbon dioxide (CO₂) lasers have been widely used for several types of cosmetic dermatosis. A number of previous studies have evaluated this technique in animals or human beings by observing morphologic changes using an invasive modality such as skin biopsy. In this study, we assessed in vivo skin changes after CO₂ ablative fractional laser treatment in a mouse model using noninvasive imaging modalities (Folliscope^® and Visioscan 98^®), and each results was compared with data from histologic examination. An ablative fractional CO₂ laser was applied with different pulse energy between 7 to 35 mJ/microspot. As results of above methods, we also confirmed that the CO₂ ablative fractional laser generated injuries with increasing width and depth with increasing pulse energy. Although numerous papers have described application of this laser in vivo skin specimens, our study evaluated the feasibility of using relative noninvasive imaging modalities for assessing the outcome of laser ablation. Based on our data, we suggest that these technologies may be useful alternative modalities for assessing laser ablation that are easier to perform and less invasive than skin biopsy.     

Effect of Sample Temperature on Radiation Characteristics of Nanosecond Laser-Induced Soil Plasma

An Nd:YAG single pulse nanosecond laser of 532 nm wavelength with an 8 ns pulse width was projected on the soil samples collected from the campus of Bengbu College under 1 standard atmospheric pressure. Laser-induced breakdown spectroscopy at different sample temperatures was achieved. The intensity and signal-to-noise ratio (SNR) changes of different characteristic spectral lines could be analyzed when the sample temperature changes. The evolution of plasma electron temperature and electron density with the sample temperature was analyzed through Boltzmann oblique line method and Stark broadening method. The cause of the radiation enhancement of laser-induced metal plasma was discussed. Experimental results demonstrated that the spectral intensity, SNR, the electron temperature and electron density of plasma are positively related to the sample temperature, and reach saturation at 100 ℃.     

Surface characterization and electrical property of carbon fibers modified by air oxidation

Polyacrylonitrile‐based carbon fibers were modified by oxidation in air, and a systematic study of surface groups and surface resistance at different treated temperatures was made. Progressive fiber weight loss occurred with increasing extents of air oxidation, and it was approximately proportional to the extent of air oxidation from the onset of oxidation up to 400 °C. At this point 4.4% of the initial fiber weight had been lost. A faster loss of weight occurred as the extent of air oxidation increased from 400 °C to 700 °C. X‐ray photoelectron spectroscopy studies (C 1s and O 1s) indicated that the oxygen/carbon atomic ratio rose rapidly from 2.64% (as‐received carbon fiber) to 42.83% as the oxidation temperature was increased to 400 °C. Fourier transform infrared spectra showed the relative intensity of the peaks at about 3440 cm^?1 from ―OH stretching vibrations and at 1634 cm^?1 from ―C?O stretching vibrations increased significantly at 400 °C. FESEM micrographs showed that as‐received fibers show relatively smooth surface. With oxidation temperature increasing, the fiber surface was rougher. The surface resistance of treated carbon fibers decreased obviously with increasing oxidation temperatures. The most decrease was about 100% at 400 °C. Copyright © 2014 John Wiley & Sons, Ltd.     

Ultra high density carbon fiber derived from isotactic polypropylene fiber without skin-core structure

Polypropylene (PP)-based carbon fibers were prepared by sulfonation process of isotactic PP fibers with concentrated sulfuric acid, followed by stress-less carbonization under nitrogen atmosphere. The stabilization behaviors of PP fiber under different sulfonation temperatures and time were discussed. The carbonization behavior of the stabilized PP fibers under different carbonization temperatures, as well as the mechanical performance of the obtained carbon fibers were investigated. The results indicated that linear PP molecule were effectively converted into thermally stable structure at higher temperature (≥130°C) in short time (2 h) through sulfonation-desulfonation reaction, among which ordered graphite structure has been formed prior to the carbonization process. Meanwhile, the carbon fibers were considerably densified by increasing the sulfonation temperature and carbonization temperature, and a bulk density of 1.96 g/cm³ was achieved. Moreover, the temperature and time of the sulfonation process as well as the temperature of the carbonization process were regulated, and carbon fibers with tensile strength of 262.3 MPa was obtained, which was superior to that of 208.1 MPa for the linear low density polyethylene-based carbon fibers reported previously. Isotactic PP was proved to be a promising candidate to develop carbon fibers with tunable graphite structure and mechanical performance.     

Characterisation of diamond coatings with different morphologies by Raman spectroscopy using various laser wavelengths

Since the beginning of low-pressure diamond synthesis, Raman spectroscopy has been widely used to identify and characterise the quality of diamonds. The diamond crystal is characterised by a Raman peak at about 1,332 cm^-1. Other peaks are associated with miscellaneous carbon structures, e.g. graphite and amorphous phases. In recent years, both well-faceted crystalline diamonds and nanocrystalline and ultrananocrystalline diamonds have been investigated. For these fine-grained materials, the diamond peak at 1,332 cm^-1 disappears and the intensities of peaks at other wavelengths increase. To study the influence of the Raman laser wavelength, three lasers were used (472.681 nm, blue; 532.1 nm, green; 632.81 nm, red). For well-faceted diamonds, the Raman spectra with blue and green laser light were similar. A shift of the peak maxima and different intensities were observed. With use of the red laser, a strong luminescence peak and low peak intensities for the various carbon-related peaks occurred. When the diamond morphology changes from well-faceted to fine-grained ballas diamond, the spectra are similar for all three lasers.     

The role of the laser pulse duration in infrared matrix-assisted laser desorption/ionization mass spectrometry

The role of the laser pulse duration in matrix-assisted laser desorption/ionization mass spectrometry with infrared lasers (IR-MALDI-MS) emitting in the 3 microm wavelength range has been evaluated. Mass spectrometric performance and characteristics of the IR-MALDI process were examined by comparing a wavelength-tuneable mid-infrared optical parametric oscillator (OPO) laser of 6 ns pulse duration, tuned to wavelengths of 2.79 and 2.94 microm, with an Er:YAG laser (lambda = 2.94 microm) with two pulse durations of 100 and 185 ns, and an Er:YSGG laser (lambda = 2.79 microm) with a pulse duration of 75 ns. Threshold fluences for the desorption of cytochrome C ions were determined as a function of the laser pulse duration for various common IR-MALDI matrices. For the majority of these matrices a reduction in threshold fluence by a factor of 1.2-1.9 was found by going from the 75-100 ns long pulses of the Erbium lasers to the short 6 ns OPO pulse. Within the experimental accuracy threshold fluences were equal for the 100 and the 185 ns pulse duration of the Er:YAG laser. Some pronounced pulse duration effects related to the ion formation from a glycerol matrix were also observed. The effect of the laser pulse length on the duration of ion emission was furthermore investigated.