Heterogeneous catalytic ozonation process for removal of 4-chloro-2-nitrophenol from aqueous solutions

This research investigated the efficiency of nanosized ZnO in the catalytic ozonation of 4-chloro-2-nitrophenol and determined the effect of pH on heterogeneous catalytic ozonation. Use of ozone with ZnO catalyst leads to conversion of 98.7% of 4-chloro-2-nitrophenol during 5 min. In addition, it was found that in ZnO catalytic ozonation, the degradation efficiency of 4-chloro-2-nitrophenol was higher at low pH conditions (pH 3.0) than high pH (pH 7–9). This result was not in accordance with ozonation alone, following which higher pH had positive effect on the degradation of 4-chloro-2-nitrophenol. During the catalytic ozonation of 4-chloro-2-nitrophenol, an increase of nitrate ions in water sample solution was observed. At pH = 3, the concentration of nitrate formed during nano-ZnO catalytic ozonation was 7.08 mg L⁻¹ and the amount of total organic carbon was 54.9% after 30 min.     

Evaluation of an activated carbon from olive stones used as an adsorbent for heavy metal removal from aqueous phases

The performance of a microporous activated carbon prepared chemically from olive stones for removing Cu(II), Cd(II) and Pb(II) from single and binary aqueous solutions was investigated via the batch technique. The activated carbon sample was characterized using N₂ adsorption–desorption isotherms, SEM, XRD, FTIR, and Boehm titration. The effect of initial pH and contact time were studied. Adsorption kinetic rates were found to be fast and kinetic experimental data fitted very well the pseudo-second-order equation. The adsorption isotherms fit the Redlich–Peterson model very well and maximum adsorption amounts of single metal ions solutions follow the trend Pb(II) > Cd(II) > Cu(II). The adsorption behavior of binary solution systems shows a relatively high affinity to Cu(II) at the activated carbon surface of the mixture with Cd(II) or Pb(II). An antagonistic competitive adsorption phenomenon was observed. Desorption experiments indicated that about 59.5% of Cu(II) and 23% of Cd(II) were desorbed using a diluted sulfuric acid solution.     

Production of activated carbon from sludge of food processing industry under controlled pyrolysis and its application for methylene blue removal

The present work aims to conduct a process optimization for the production of activated carbon from sludge of food processing industry. The significant feature of this sludge based activated carbon that makes it unique and economic is that it can be produced from waste material. The carbonaceous nature of this sludge does not allow its direct disposal to land because of excess organic and nutrient load contents, however, can be converted to a value added product. This process not only eliminates the need for further treatment of sludge but also reduce the cost of its handling, land filling, and transportation as well as the utilization in the same industry in the purification system.In the present work, activated carbon produced from pyrolysis of sludge was chemically activated by various activating agents. Optimization of impregnation ratio, impregnation time, activation temperature, and activation time was studied. The product was characterized through its iodine value and yield percentage. It was observed that the product had maximum iodine value of 624 mg g⁻¹ with ZnCl₂ as an activating agent. The FT-IR analysis depicts the presence of a variety of functional groups attached on the surface of activated carbon which are used in the interaction with the adsorbate during the process of adsorption. The XRD analysis reveals that the produced activated carbon has low content of inorganic constituents compared with the precursor. The product formed was applied for methylene blue adsorption. The adsorption equilibrium of methylene blue dye was examined at room temperature. Adsorption isotherm was drawn by applying Langmuir and Freundlich models fitting the data indict, with an adsorption capacity of 23.6 mg g⁻¹ and 14.2 mg g⁻¹, respectively. The data show that methylene blue adsorption is best suited to Langmuir equation.     

Effects of calcination and activation temperature on dry reforming catalysts

The effect of calcination temperatures on dry reforming catalysts supported on high surface area alumina Ni/γ-Al₂O₃ (SA-6175) was studied experimentally. In this study, the prepared catalyst was tested in a micro tubular reactor using temperature ranges of 500, 600, 700 and 800 °C at atmospheric pressure, using a total flow rate of 33 ml/min consisting of 3 ml/min of N₂, 15 ml/min of CO₂ and 15 ml/min of CH₄. The calcination was carried out in the range of 500–900 °C. The catalyst is activated inside the reactor at 500–800 °C using hydrogen gas. It was observed that calcination enhances catalyst activity which increases as calcination and reaction temperatures were increased. The highest conversion was obtained at 800 °C reaction temperature by using catalyst calcined at 900 °C and activation at 700 °C. The catalyst characterization conducted supported the observed experimental results.     

Synthesis of CuO/SBA-15 adsorbents for SOx removal applications,using different impregnation methods

In this paper, SBA-15 mesoporous silica based adsorbents were synthesized for the desulfurization of flue gas streams, by several methods (wet impregnation, incipient wetness impregnation and ion exchange). The influence of the drying and calcination conditions on the porous texture and the dispersion of the active phase (CuO), as well as the efficiency of the adsorbents for SO_x trapping, were studied. Depending on the synthesis conditions, copper species are present as large CuO particles (1 μm) and/or as homogeneously dispersed species, undetectable by XRD/TEM. The SO_x adsorption efficiency seems to be closely related to the undetected copper species.     

Power generation using an activated carbon and metal mesh cathode in a microbial fuel cell

An inexpensive activated carbon (AC) air cathode was developed as an alternative to a platinum-catalyzed electrode for oxygen reduction in a microbial fuel cell (MFC). AC was cold-pressed with a polytetrafluoroethylene (PTFE) binder to form the cathode around a Ni mesh current collector. This cathode construction avoided the need for carbon cloth or a metal catalyst, and produced a cathode with high activity for oxygen reduction at typical MFC current densities. Tests with the AC cathode produced a maximum power density of 1220 mW/m² (normalized to cathode projected surface area; 36 W/m³ based on liquid volume) compared to 1060 mW/m² obtained by Pt catalyzed carbon cloth cathode. The Coulombic efficiency ranged from 15% to 55%. These findings show that AC is a cost-effective material for achieving useful rates of oxygen reduction in air cathode MFCs.     

Effects of pyrolysis conditions on the physical characteristics of oil-palm-shell activated carbons used in aqueous phase phenol adsorption

Oil-palm shells, a biomass by-product from palm-oil mills, were converted into activated carbons by vacuum or nitrogen pyrolysis, followed by steam activation. The effects of pyrolysis environment, temperature and hold time on the physical characteristics of the activated carbons were studied. The optimum pyrolysis conditions for preparing activated carbons for obtaining high pore surface area are vacuum pyrolysis at a pyrolysis temperature of 675 °C and 2 h hold time. The activation conditions were fixed at a temperature of 900 °C and 1 h hold time. The activated carbons thus obtained possessed well-developed porosities, predominantly microporosities. For the pyrolysis atmosphere, it was found that significant improvement in the surface characteristics of the activated carbons was obtained for those pyrolysed under vacuum. Adsorption capacities of activated carbons were determined using phenol solution. For the activated carbons pyrolysed under optimum vacuum conditions, a maximum phenol adsorption capacity of 166 mg/g of carbon was obtained. A linear relationship between the BET surface area and the adsorptive capacity was shown.     

The effect of copper content on the reactivity of Cu/Co6Al2 solids in the catalytic steam reforming of methane reaction

The steam reforming of methane over Cu/Co₆Al₂ mixed oxides with different copper contents was studied. The Co₆Al₂ support was prepared via the hydrotalcite route. It was thermally stabilized at 500 °C, impregnated with 5 wt.%, 15 wt.% or 25 wt.% copper using copper (II) nitrate Cu(NO₃)₂·3H₂O precursor and then calcined again at 500 °C under an air flow. The impregnation of copper enhanced significantly the reactivity of the solids in the considered reaction. The 5Cu/Co₆Al₂ solid was the most reactive one, with a methane conversion of 96% at 650 °C. The selectivities of H₂ and CO₂ were also better for the catalyst containing 5 wt.% copper compared to higher copper loadings. The decrease in the catalytic reactivity with increasing the copper content was attributed to the formation of agglomerated and less reactive CuO species, which were detected by XRD and TPR analyses.     

Thermodynamics’ study of the adsorption process of methylene blue on activated carbon at different ionic strengths

The adsorption constant of aqueous solution of methylene blue (MB), (800 · 10⁻⁶ mol · dm³) on activated carbon (AC) has been investigated by means of UV–Visible spectroscopy. The adsorption process is very fast and is physical in nature; however, it is complicated by the factors inherent in the structures of both the MB solution and AC, such as tendency of MB to form molecular aggregates in solution. In this work, the effects of various experimental parameters such as temperature and ionic strength have been investigated, using a batch adsorption technique to obtain information on treating effluents from the dye industry. Utilizing the van’t Hoff relation, which describes the dependence of equilibrium constant on temperature, as a constraint, we determine the spectral responses of the free and adsorbed amounts, as well as the enthalpy of the adsorption equilibrium.     

[Cu(bpdo)2·2H2O]2+-supported SBA-15 nanocatalyst for efficient one-pot synthesis of benzoxanthenone and benzochromene derivatives

A novel [Cu(bpdo)₂·2H₂O]²⁺-supported SBA-15 catalyst (bpdo = 2,2′-bipyridine,1,1′-dioxide) was prepared by the impregnation method. The catalyst was characterized by XRD, TEM, and BET nitrogen adsorption–desorption method, FT-IR, UV–vis, and chemical analysis. XRD patterns and TEM analysis of [Cu(bpdo)₂·2H₂O]²⁺/SBA-15 showed highly ordered hexagonal mesoporous silica, even after immobilization. Also, nitrogen adsorption–desorption isotherms exhibited type-IV isotherms and H1 hysteresis loops according to the IUPAC classification of mesoporous materials. This green support was tested for the synthesis of benzoxanthenone and benzochromene derivatives under solvent-free conditions, with high yield of products via a simple experimental and work-up procedure.     

Adsorption of strontium from aqueous solution using activated carbon produced from textile sewage sludges

Different types of activated carbons were prepared by changing the activation temperatures (400–700 °C) and impregnation ratio (sewage sludge: KOH; 1:1, 1:2) and the removal of Sr⁺² from aqueous solution was determined. The maximum adsorption yield (12.11 mg/g) was obtained at 500 °C for 1 h carbonization conditions with impregnation ratio of 1:1. The affecting parameters were analyzed by using central composite design method. The selected parameters were initial pH, temperature, initial strontium concentration and carbon dosage. The analysis of variance was performed in 95% confidence level and checked to fitting of experimental value and predicted value. The significant F was P < 0.05 with a model F value of 19.94 which revealed that this regression is statistically significant. The results of regression analysis indicated that pH and temperature parameters were not individually statistically significant for Sr⁺²sorption. However, the efficiency of strontium sorption increases with the increase in carbon dosage and decreases with the Sr⁺² concentration. Influences of initial pH and temperature, pH and Sr⁺² concentration, temperature and carbon dosage and Sr⁺² concentration and carbon dosage on the adsorption process were considered statistically significant. Adsorption of strontium was described by Freundlich isotherm as a physical adsorption (E = 7.2 kJ/mol). The adsorption reactions were calculated as endothermic, spontaneous and favorable reactions.     

Poly(vinyl alcohol) separators improve the coulombic efficiency of activated carbon cathodes in microbial fuel cells

High-performance microbial fuel cell (MFC) air cathodes were constructed using a combination of inexpensive materials for the oxygen reduction cathode catalyst and the electrode separator. A poly(vinyl alcohol) (PVA)-based electrode separator enabled high coulombic efficiencies (CEs) in MFCs with activated carbon (AC) cathodes without significantly decreasing power output. MFCs with AC cathodes and PVA separators had CEs (43%–89%) about twice those of AC cathodes lacking a separator (17%–55%) or cathodes made with platinum supported on carbon catalyst (Pt/C) and carbon cloth (CE of 20%–50%). Similar maximum power densities were observed for AC-cathode MFCs with (840 ± 42 mW/m²) or without (860 ± 10 mW/m²) the PVA separator after 18 cycles (36 days). Compared to MFCs with Pt-based cathodes, the cost of the AC-based cathodes with PVA separators was substantially reduced. These results demonstrated that AC-based cathodes with PVA separators are an inexpensive alternative to expensive Pt-based cathodes for construction of larger-scale MFC reactors.     

Understanding the nature of vanadium species supported on activated carbon and its catalytic properties in the aerobic oxidation of aromatic alcohols

Vanadium oxide catalysts supported on activated carbon (V/AC) with V loadings ranging from 1 to 20 wt.% were prepared by a wet-impregnation method. Various physicochemical characterization techniques, including nitrogen physisorption, X-ray diffraction (XRD), Raman spectroscopy, X-ray absorption (XANES and EXAFS), X-ray photoelectron spectroscopy (XPS), and electron spin resonance (ESR), were employed to understand the nature of vanadium species on activated carbon. The results revealed that vanadium oxide mainly existed in a highly dispersed state for 10 wt.% or less vanadium loadings; a large amount of vanadium resulted in aggregated microcrystalline phase. Vanadium species on activated carbon surface showed a similar local coordination structure to that of NH₄VO₃ with a distorted tetrahedral symmetry at low vanadium loadings, whereas octahedral coordination was dominant at high vanadium loadings (>10 wt.%). All V/AC samples showed V⁵⁺ as the major oxidation state. Nevertheless, V⁴⁺ centered in a distorted tetrahedral symmetry could be detected at a vanadium loading greater than 4 wt.%. The catalytic activity for the benzyl alcohol oxidation largely depended on the dispersion, oxidation state, and local coordination of vanadium oxides on activated carbon. Highly dispersed vanadium (5+) species with a distorted tetrahedral coordination were postulated to account for the excellent catalytic performances of V/AC catalysts (TOF = 39.1 h^?1).     

表面改性对Cu/活性炭催化剂表面Cu物种和催化活性的影响

通过对活性炭表面改性,研究了醋酸铜溶液浸渍后热分解制备的Cu/AC无氯催化剂对甲醇氧化羰基化合成碳酸二甲酯催化性能的影响。通过低温氮吸附－脱附、FTIR等表征对改性前后活性炭的比表面积及表面官能团变化进行了分析,发现氨水改性的活性炭比表面积略有增大,表面不饱和还原性官能团(C≡N、C≡C)增加,而KMnO₄改性的活性炭比表面积减小7%,表面C=O、-COOH显著增加。进一步通过XRD、H₂-TPR、XPS等表征分析了催化剂表面铜物种(Cu⁰/Cu^I/Cu^Ⅱ)的形态,发现表面铜物种的价态和配比与活性炭表面性质密切相关,影响催化剂活性。活性炭改性后,表面微观结构和表面化学性质的变化对浸渍醋酸铜的表面分布和热分解过程产生明显影响,导致催化剂表面活性Cu物种发生变化。和其它表面改性方法相比,氨水改性的活性炭更有利于催化剂活性的提高,碳酸二甲酯的时空收率及甲醇转化率分别达到了152.8 mg·g^-1·h^-1和7.4%。     

Simultaneous removal of copper(II), lead(II), zinc(II) and cadmium(II) from aqueous solutions by multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were used successfully for the removal of heavy metals from aqueous solution. Characterization techniques showed the carbon as nanotubes with an average diameter between 40 and 60 nm and a specific surface area of 61.5 m² g^?1. The effect of carbon nanotubes mass, contact time, metal ions concentration, solution pH, and ionic strength on the adsorption of Cu(II), Pb(II), Cd(II) and Zn(II) by MWCNTs were studied and optimized. The adsorption of the heavy metals from aqueous solution by MWCNTs was studied kinetically using different kinetic models. A pseudo-second order model and the Elovich model were found to be in good agreement with the experimental data. The mechanism of adsorption was studied by the intra-particle diffusion model, and the results showed that intra-particle diffusion was not the slowest of the rate processes that determined the overall order. This model also revealed that the interaction of the metal ions with the MWCNTs surface might have been the most significant rate process. There was a competition among the metal ions for binding of the active sites present on the MWCNTs surface with affinity in the following order: Cu(II) > Zn(II) > Pb(II) > Cd(II).     

Decomposition of methane over alumina supported Fe and Ni–Fe bimetallic catalyst: Effect of preparation procedure and calcination temperature

Catalytic decomposition of methane has been studied extensively as the production of hydrogen and formation of carbon nanotube is proven crucial from the scientific and technological point of view. In that context, variation of catalyst preparation procedure, calcination temperature and use of promoters could significantly alter the methane conversion, hydrogen yield and morphology of carbon nanotubes formed after the reaction. In this work, Ni promoted and unpromoted Fe/Al₂O₃ catalysts have been prepared by impregnation, sol–gel and co-precipitation method with calcination at two different temperatures. The catalysts were characterized by X-ray diffraction (XRD), N₂ physisorption, temperature programmed reduction (TPR) and thermogravimetric analysis (TGA) techniques. The catalytic activity was tested for methane decomposition reaction. The catalytic activity was high when calcined at 500 °C temperature irrespective of the preparation method. However while calcined at high temperature the catalyst prepared by impregnation method showed a high activity. It is found from XRD and TPR characterization that disordered iron oxides supported on alumina play an important role for dissociative chemisorptions of methane generating molecular hydrogen. The transmission electron microscope technique results of the spent catalysts showed the formation of carbon nanotube which is having length of 32–34 nm. The Fe nanoparticles are present on the tip of the carbon nanotube and nanotube grows by contraction–elongation mechanism. Among three different methodologies impregnation method was more effective to generate adequate active sites in the catalyst surface. The Ni promotion enhances the reducibility of Fe/Al₂O₃ oxides showing a higher catalytic activity. The catalyst is stable up to six hours on stream as observed in the activity results.     

Optimization of preparation conditions for activated carbon from palm oil fronds using response surface methodology on removal of pesticides from aqueous solution

Palm oil fronds were used to prepare activated carbon using the physiochemical activation method, which consisted of potassium hydroxide (KOH) treatment and carbon dioxide (CO₂) gasification. The effects of variable parameters activation temperature, activation time and chemical impregnation ratios (KOH: char by weight) on the preparation of the activated carbon and for the removal of pesticides: bentazon, carbofuran and 2,4-Dichlorophenoxyacetic acid (2,4-D) were investigated. Based on the central composite design (CCD), two factor interaction (2FI) and quadratic models were respectively employed to correlate the effect of variable parameters on the preparation of activated carbon used for the removal of pesticides with carbon yield. From the analysis of variance (ANOVA), the most influential factor on each experimental design response was identified. The optimum conditions for preparing the activated carbon from oil palm fronds were found as follows: activation temperature of 750 °C, activation time of 2 h and chemical impregnation ratio of 2.38. The percentage error between predicted and experimental results for the removal of bentazon, carbofuran and 2,4-D were 8.2, 1.3 and 9.2%, respectively and for the yield of the palm oil frond activated carbon was 5.6.     

Kinetics of copper UPD on stepped platinum single crystals in the presence of acetonitrile

The kinetics of copper underpotential deposition on stepped Pt(h k l) electrodes with controlled width of (1 1 1) terraces in acidic solutions of copper sulfate with 0–200 mM of acetonitrile (AcN) has been studied by means of cyclic voltammetry. In the presence of AcN Cu UPD process is hindered both at (1 0 0) steps and (1 1 1) terraces of Pt(17 15 15) and Pt(7 5 5) faces due to blocking of the electrode surface with organic molecules, strongly adsorbed at the steps and nearby ones. The decoration of (1 1 0) steps with copper adatoms is slightly accelerated for Pt(7 7 5) electrode in the solution with 0.04 mM AcN. Increase in AcN concentration leads to inhibition of the UPD process. The difference in behavior of the stepped platinum electrodes is controlled by competitive adsorption of AcN, (bi)sulfate and Cu atoms at the step sites. AcN adsorption at (1 0 0) steps is stronger as compared with (1 1 0) ones.     

Synthesis and characterization of high surface area TiO2/SiO2 mesostructured nanocomposite

Recently titania synthesis was reported using various structuration procedures, leading to the production of solid presenting high surface area but exhibiting moderate thermal stability. The study presents the synthesis of TiO₂/SiO₂ nanocomposites, a solid that can advantageously replace bulk titania samples as catalyst support. The silica host support used for the synthesis of the nanocomposite is a SBA-15 type silica, having a well-defined 2D hexagonal pore structure and a large pore size. The control of the impregnation media is important to obtain dispersed titania crystals into the porosity, the best results have been obtained using an impregnation in an excess of solvent. After calcination at low temperature (400 °C), nanocomposites having titania nanodomains (～2–3 nm) located inside the pores and no external aggregates visible are obtained. This nanocomposite exhibits high specific surface area (close to that of the silica host support, even with a titania loading of 55 wt.%) and a narrow pore size distribution. Surprisingly, the increase in calcination temperature up to 800 °C does not allow to detect the anatase to rutile transition. Even at 800 °C, the hexagonal mesoporous structure of the silica support is maintained, and the anatase crystal domain size is evaluated at ～10 nm, a size close to that of the silica host support porosity (8.4 nm). Comparison of their physical properties with the results presented in literature for bulk samples evidenced that these TiO₂/SiO₂ solids are promising in term of thermal stability.     

Surface patterning using scanning electrochemical microscopy to locally trigger a “click” chemistry reaction

We report on the surface micropatterning of conductive surfaces via the electrochemical triggering of a click reaction, the copper(I) catalyzed azide–alkyne cycloaddition reaction (CuAAC) by SECM via a two-step approach: (i) functionalization on the entire surface with azido-aryl groups by using the diazonium approach followed by (ii) the covalent linkage of alkyne-bearing ferrocene by CuAAC within a local area by SECM. More precisely, the click reaction was triggered by Cu(I) catalyst generation for 30 min at the SECM tip positioned ≈ 10 μm above the azido-aryl modified surface. The dimension of the spot obtained under these conditions was ≈ 75 μm. The electrochemical imaging by SECM of the ultra thin area locally clicked with ferrocene moieties was made thanks to the electrocatalytic properties of the ferrocene modified surface towards ferrocyanide electrooxidation. This local clicking procedure opens the gate to further controlled functionalization of restricted small substrates.