Ethylenediamine-modified activated carbon for aqueous lead adsorption

This study is to develop a carbon-based adsorbent containing multiple functional ligands for effective removal of lead ions from aqueous media. Activated carbon was oxidized by nitric acid, followed by chlorination with thionyl chloride and reaction with ethylenediamine. Modified activated carbon (MAC) was characterized using scanning electron microscopy in conjunction of energy dispersive spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FT-IR), and potentiometric titration. Surface characterizations confirmed that carboxyl, amine, and chlorine functional groups were effectively introduced onto the carbon surface by the treatments. The modifications lowered the pH at the point of zero charge (pH_pzc) from 9.6 to 2.55 and resulted in more negatively charged surfaces. Adsorptive experiments showed that aqueous Pb removal by MAC was faster, with a 62% higher capacity than the original activated carbon (60.2 vs. 37.2 mg g⁻¹).     

Synthesis, physicochemical characterizations and catalytic performance of Pd/carbon-zeolite and Pd/carbon-CeO2 nanocatalysts used for total oxidation of xylene at low temperatures

In this work, xylene removal from waste gas streams was investigated via catalytic oxidation over Pd/carbon-zeolite and Pd/carbon-CeO₂ nanocatalysts. Activated carbon was obtained from pine cone chemically activated using ZnCl₂ and modified by H₃PO₄. Natural zeolite of clinoptilolite was modified by acid treatment with HCl, while nano-ceria was synthesized via redox method. Mixed supports of carbon-zeolite and carbonceria were prepared and palladium was dispersed over them via impregnation method. The prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Brunauer-Emmett-Teller surface area (BET), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric (TG) techniques. Characterization of nanocatalysts revealed a good morphology with an average particle size in a nano range, and confirmed the formation of nano-ceria with an average crystallite size below 60 nm. BET analysis indicated a considerable surface area for catalysts (～1000 m²·g^?1). FTIR patterns demonstrated that the surface groups of synthesized catalysts are in good agreement with the patterns of materials applied in catalyst synthesis. The performance of catalysts was assessed in a low-pressure catalytic oxidation pilot in the temperature range of 100° C-250°C. According to the reaction data, the synthesized catalysts have been shown to be so advantageous in the removal of volatile organic compounds (VOCs), representing high catalytic performance of 98% for the abatement of xylene at 250°C. Furthermore, a reaction network is proposed for catalytic oxidation of xylene over nanocatalysts.     

改性活性炭的表面特性及其对金属离子的吸附性能

本文主要研究了改性对活性炭的表面物理化学特征和对其吸附金属离子性能的影响。研究发现,硝酸氧化可显著增加活性炭表面酸性基团的含量,提高活性炭的表面亲水性,降低pHpzc值,并造成活性炭的结构塌陷和比表面积的减少,因而对活性炭吸附性能产生明显影响,可明显提高对Pb^2 等金属离子的吸附容量。     

Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen

The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH₄) over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Brønsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Brønsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NO_y species and the corresponding reaction routes were determined by the overall acidity strength of the support. The reaction routes where NO₂ moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts, reactions between appropriate couples of active NO_y species and activated hydrocarbon intermediates should be realized by modification of the support acidity.     

丙酮冲洗法提高纳米零价铁抗氧化性能

纳米零价铁(nanoscale zero valent iron,nZVI)具有还原能力强、便于回收等优势,是目前广泛应用于地下水污染治理的一种活性纳米材料.然而,nZVI易被空气氧化失活及其储存难等问题严重地限制了其应用.为增强nZVI抗氧化能力,本文首次采用丙酮(acetone)对新制备的nZVI样品进行简单冲洗,...     

Pd nanoparticles entrapped in TiO<Subscript>2</Subscript> nanotubes for complete butane catalytic combustion at 130 °C

Air pollution by volatile organic compounds is a major health issue due to increasing industrialization and urbanization, notably in the developing countries. Cleaning organic pollutants by catalytic combustion is a potential solution, but actual methods require relatively high temperatures, thus increasing remediation costs. There is therefore a need for methods that operate at mild temperatures. Here we prepared a novel catalyst made of Pd nanoparticles entrapped in TiO₂ nanotubes by vacuum-assisted impregnation. Then, we tested this catalyst for butane combustion. The catalyst was characterized by N₂ adsorption–desorption isotherms, transmission electronic microscopy, energy-dispersive X-ray analysis coupled with a scanning transmission electron microscope, X-ray photoelectron spectroscopy and temperature programmed oxidation. Results show a complete combustion of butane at 130 °C, which is about 20 °C lower than temperatures required by actual catalysts made of Pd nanoparticles deposited on the exterior surface of TiO₂ nanotubes. Structure characterization suggests that this higher performance at lower temperature is explained by the confinement of TiO₂ nanotubes. Such a confinement could hinder the metal sintering and, in turn, facilitate the formation of PdO during oxidation on the entrapped Pd nanoparticles.     

铁屑法处理含染料废水中铁屑表面化学研究

采用扫描电镜和X射线光电子能谱技术对铁屑法处理含染料废水中铁屑反应前后的表面进行了研究,结果表明：铁屑表面主要由Fe,C,O,S,Si以及其它构成铸铁的微量元素等组成．铁屑表面快速氧化是染料脱色的关键和前提步骤,铁屑表面铁的羟基氧化物增多是铁屑失活的重要原因．超声方法是铁屑再生方法之一,铸铁中的硫有助于染料脱色．     

Deposition of copper nanoparticles on multiwalled carbon nanotubes modified with poly (acrylic acid) and their antimicrobial application in water treatment

A novel hybrid material, Cu-PAA/MWCNTs (copper nanoparticles deposited multiwalled carbon nanotubes with poly (acrylic acid) as dispersant, was prepared and expected to obtain a more effective and well-dispersed disinfection material for water treatment. X-ray energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), the X-ray fluorescence (XRF), X-ray photoelectron spectra (XPS), Fourier transform infrared spectra (FT-IR), Raman spectroscopy, and thermal gravimetric analyzer (TGA) were used to characterize the Cu-PAA/MWCNTs. Escherichia coli (E. coil) was employed as the target bacteria. The cell viability determination and fluorescence imaging results demonstrated that Cu-PAA/MWCNTs possessed strong antimicrobial ability on E. coil. The deposited Cu was suggested to play an important role in the antimicrobial action of Cu-PAA/MWCNTs.     

Thermal treatment of plasma-synthesized goethite improves Fenton-like degradation of orange II dye

Various iron oxides are used for Fenton reactions to degrade organic pollutants. The degradation efficiency may be improved by transforming an iron oxide phase to another. Here, we report on the transformation of goethite into hematite by thermal treatment at 400 °C. The products were analyzed by X-ray diffractometry, Raman spectroscopy, scanning electron microscopy and N₂-physisorption. The catalytic activities were measured for orange II bleaching at initial concentration of 25 mg L^?1, pH 3, catalyst concentration of 0.2 g L^?1; 5 mM H₂O₂, 30 °C. Results show that the synthesized goethite was successfully transformed into hematite, and the specific surface area of the material increased from 134 to 163 m² g^?1. The bleaching efficiency of the orange II dye reached 100 % for the hematite product, versus 78 % for goethite. Therefore, a moderate thermal treatment of a plasma-synthesized goethite improves the catalytic oxidation of organic pollutants.     

Removal of Eu3+, Ce3+, Sr2+, and Cs+ ions from radioactive waste solutions by modified activated carbon prepared from coconut shells

As a biomass agricultural waste material, coconut shells were used for the preparation of high-quality modified activated carbon. Chemical modification of the surface of the prepared activated carbon is done by oxidation using H₂O₂ and HNO₃, respectively. The surface area and pore volume of the coconut shells activated carbon are increased by the chemical modification, and followingly the removal of the metals is improved. The structural morphology and composition of the modified activated carbon coconut shells (MACCS) were evaluated by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis–differential thermal analysis (TGA-DTA), scanning electron microscope (SEM), X-ray diffraction (XRD), surface area analysis (SAA), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis. The prepared MACCS has reasonably good chemical stability. The influence of solution pH, contact time, adsorbent dosage, adsorption temperature, initial metal concentrations, and interfering ions on the adsorption performance of the investigated ions onto the prepared sorbent was examined by a batch method. The selectivity sequence for sorption of Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions on MACCS was found to be Eu^3+?>?Ce^3+?>?Sr^2+?>?Cs⁺. The saturation capacities of MACCS for the studied metal ions were found to be 136.84, 85.55, 69.85, and 60.00?mg?g^?1 for Eu³⁺, Ce³⁺, Sr²⁺, and Cs⁺ ions, respectively. The thermodynamic parameters, ΔH°, ΔS°, and ΔG° were also evaluated.     

改性活性炭对有机物的吸附性能

研究了表面改性对活性炭吸附各种有机物性能的影响,研究发现,硝酸氧化可显著增加活性炭表面酸性基团的含量,提高了活性炭的表面亲水性,降低pHpzc值,并造成活性炭的结构塌陷和比表面积的减少,因而对活性炭吸附水中的苯酚、苯胺、腐殖酸、氯仿、四氯化碳等有机物的性能产生明显影响,以去除水中有机污染物为目的的活性炭表面改性的方向应为：减少表面内酯基及竣基等含氧官能团的含量,增加活性炭表面的疏水性。     

Metal immobilization by sludge-derived biochar: roles of mineral oxides and carbonized organic compartment

Pyrolyzing sludge into biochar is a potentially promising recycling/disposal solution for municipal wastewater sludge, and the sludge-derived biochar (SDBC) presents an excellent sorbent for metal immobilization. As SDBC is composed of both mineral oxides and carbonized organic compartment, this study therefore compared the sorption behaviour of Pb and Zn on SDBC to those of individual and mixture of activated carbon (AC) and amorphous aluminium oxide (Al₂O₃). Batch experiments were conducted at 25 and 45 °C, and the metal-loaded sorbents were artificially aged in the atmosphere for 1–60 days followed by additional sorption experiments. The Pb sorption was generally higher than Zn sorption, and the co-presence of Pb reduced Zn sorption on each studied sorbent. Higher sorption capacities were observed at 45 °C than 25 °C for SDBC and AC, while the opposite was shown for Al₂O₃, indicating the significance of temperature-dependent diffusion processes in SDBC and AC. Nevertheless, metal sorption was more selective on Al₂O₃ that showed a greater affinity towards Pb over Zn under competition, correlating with the reducible fraction of sequential extraction. Furthermore, significant amounts of Pb and Zn were additionally sorbed on SDBC following 30-day ageing. The X-ray diffraction revealed the formation of metal-phosphate precipitates, while the X-ray photoelectron spectroscopy showed a larger quantity of metal–oxygen bonding after 30-day ageing of metal-loaded SDBC. The results may imply favourable long-term transformation and additional sorption capacity of SDBC. In conclusion, SDBC resembles the sorption characteristics of both organic and mineral sorbents in different aspects, presenting an appropriate material for metal immobilization during soil amendment.     

Physicochemical characterization of sterilized muds for pharmaceutics/cosmetics applications

Clays and muds have been used for centuries as cosmetics or pharmaceutical products for various therapies. The suitability of muds and clays for health- and beauty-related applications depends on their physicochemical properties, mineralogical composition, particle characteristics and toxicity. In this work, the physicochemical characterization of 12 mud specimens from different natural spa resorts in Greece and one from Israel (Dead Sea) is presented. All specimens were sterilized at 121 °C for 20 min, because of their intended use. The Greek mud specimens were collected from various locations in Macedonia, Western Greece and Northeast Aegean. All muds were characterized concerning their mineralogical, chemical components as well as their morphological characteristics using appropriate methods [powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), nitrogen absorption specific surface area measurements (BET), scanning electron microscopy and energy dispersive X-ray spectroscopy]. The concentrations of F^?, Cl^?, NO₃^? and SO₄^2? anions at equilibrium with the mud specimens were measured by ion chromatography. Total calcium concentration was measured using atomic absorption spectroscopy, and the concentration of total N, C, H and S in the solids was measured using elemental analysis. Moreover, total phenolic concentration (TPC) in distilled water equilibrated with the mud specimens was measured as an index for their antioxidant properties. Several muds were found to present high TPC. Several of the examined mud specimens were found to have the potential use as pharmaceuticals or cosmetics. Based on the physicochemical characteristics of the mud specimens examined, possible improvement in their use and applicability has been suggested.     

Noncovalent immobilization of manganese peroxidases from P. chrysosporium on carbon nanotubes

Manganese peroxidases (MnP) from Phanerochaete chrysosporium were adsorbed onto multi-walled carbon nanotubes (MWNT). Four different loadings of MnP on MWNTs were investigated, and the maximum enzyme loading of 47.5 μg/mg of MWNTs was obtained in 12 h. The adsorbed MnP showed a catalytic activity of up to 0.1 U/mg of the weight of the system of MnP/MWNTs, with 23% of its original activity retained. The AFM image of the adsorbed enzymes indicated that a layer of MnP covered the surface of the MWNTs and retained its original three-dimensional shape. Amino-based nonspecific interactions may play the dominant role in the adsorption of MnP on MWNTs.     

Treating n-butane by activated carbon and metal oxides

In order to reduce environmental pollution and regulatory issues, the adsorption of n-butane from vehicle exhaust is one of the necessary requirements. When active carbon was mixed with different proportions of metal oxides, the adsorption capacity of n-butane was markedly improved. Infrared spectroscopy data provided information on functional groups derived from activated carbon composite metal oxide indicating that one of the best adsorption capacities for n-butane was obtained by mixing 3 g TiO₂, 2.7 g CuO, and 2.1 g NaBO₃·4H₂O with 30 g activated carbon. However, more effective results were obtained by mixing 6 g TiO₂, 2.1 g CuO, and 0.9 g NaBO₃·4H₂O with 30 g activated carbon. Data suggest that these chemical complexes may be effective in lowering n-butane pollution.     

Heavy Metals in Superficial Sediments from the Ligurian Sea,Italy

In this paper we are presenting the concentrations and the distributions of trace metals (Fe, Ni, Cr, Cu, Pb and Zn) in the coastal area of the Ligurian Sea between Capo Noli and Capo Mele. Fifty-six samples were subjected to textural, organic carbon and chemical analyses. Three different extraction methods were used: 1N NH₂OH.HCl plus 25% CH₃COOH, nitric acid solution, and total attack with HClO₄-HF mixture. The solutions were analysed by atomic absorption spectrophotometry. The results obtained confirm that the extraction methods which are most informative for environmental purposes are the cold or the easily extractable metal techniques. The results also show that for the study area the concentrations of Fe, Ni, Cr, Cu, Pb, and Zn do not indicate traces of anthropogenic inputs.     

Efficient oxidation of sulfides into sulfoxides catalyzed by a chitosan–Schiff base complex of Cu(II) supported on supramagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

Sulfoxides are versatile synthetic intermediates for the preparation of biological products. Therefore, there is a need for efficient methods to oxidize sulfides into sulfoxides. Such oxidation may be catalyzed by magnetic nanocatalysts due to their good stability, easy synthesis, high surface area, low toxicity and easy separation by magnetic forces. Here we prepared a nanocatalyst by immobilization of the chitosan–Schiff base complex on supramagnetic Fe₃O₄ nanoparticles. The chitosan–Schiff base complex has been previously prepared by functionalization of chitosan with 5-bromosalicylaldehyde and metalation with copper(II) acetate. The catalyst was characterized by Fourier transform infrared, powder X-ray diffraction, transmission electron microscope, scanning electron microscopy, energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Results show that the Fe₃O₄ nanoparticles and nanocatalyst were spherical in shape with an average size of 20 nm. Upon the covalently anchoring of chitosan–Schiff base Cu complex on the magnetic Fe₃O₄ nanoparticles, the average size increased to 60 nm. The prepared Fe₃O₄–chitosan–Schiff base Cu complex catalyzed very efficiently the oxidation of sulfides to sulfoxides with 100 % selectivity in all cases under green reaction conditions and excellent yields. Additionally, ease of recovery and reusability up to four cycles without noticeable loss of catalytic activity make the present protocol beneficial from industrial and environmental viewpoint.     

Catalytic ozonation performance and surface property of supported Fe3O4 catalysts dispersions

Fe₃O₄ was supported on mesoporous Al₂O₃ or SiO₂ (50 wt.%) using an incipient wetness impregnation method, and Fe₃O₄/Al₂O₃ exhibited higher catalytic efficiency for the degradation of 2,4-dichlorophenoxyacetic acid and para-chlorobenzoic acid aqueous solution with ozone. The effect and morphology of supported Fe₃O₄ on catalytic ozonation performance were investigated based on the characterization results of X-ray diffraction, X-ray photoelectron spectroscopy, BET analysis and Fourier transform infrared spectroscopy. The results indicated that the physical and chemical properties of the catalyst supports especially their Lewis acid sites had a significant influence on the catalytic activity. In comparison with SiO₂, more Lewis acid sites existed on the surface of Al₂O₃, resulting in higher catalytic ozonation activity. During the reaction process, no significant Fe ions release was observed. Moreover, Fe₃O₄/Al₂O₃ exhibited stable structure and activity after successive cyclic experiments. The results indicated that the catalyst is a promising ozonation catalyst with magnetic separation in drinking water treatment.     

多壁碳纳米管引起白鼠肺部毒性的评价(Comparative Pulmonary Toxic Assessment of Mutil-Wall Carbon Nanotubes in Rats)

以雄性Wistar大白鼠为研究对象,观察了多壁碳纳米管(MWNTs)体内暴露后肺部的病理学变化.采用气管注入方式将直径为40～60nm多壁碳纳米管(40～60MWNTs)和直径小于10nm的多壁碳纳米管(10MWNTs)暴露于大白鼠的体内,同时分别采用纳米二氧化硅(SiO2)和乙炔碳黑(Cb)作为阳性和阴性对照.实验结果表明:实验中采用的纳米颗粒均不同程度地引起了肺部的损伤,同剂量下损伤严重程度顺序为:Cb>10MWNTs>40～60MWNTs>SiO2.多壁碳纳米管对肺部损伤的程度与剂量呈依赖关系,当在低剂量(1mg·kg-1)时,40～60MWNTs仅仅对肺部引起了轻微的炎症损伤,随着剂量的增大,多壁碳纳米管对肺部的损伤越来越严重,出现明显的病理损伤.     

Removing phosphorus from aqueous solutions by using iron-modified corn straw biochar

Iron-modified corn straw biochar was used as an adsorbent to remove phosphorus from agricultural runoff. When agricultural runoffs with a total phosphorus (TP) concentration of 1.86 mg·L⁻¹ to 2.47 mg·L⁻¹ were filtered at a hydraulic retention time of 2 h through a filtration column packed with the modified biochar, a TP removal efficiency of over 99% and an effluent TP concentration of less than 0.02 mg·L⁻¹ were achieved. The isotherms of the phosphorus adsorption by the modified biochar fitted the Freundlich equation better than the Langmuir equation. The mechanism of the phosphorus adsorbed by the modified biochar was analyzed by using various technologies, i.e. scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). The results indicated that the surface of the modified biochar was covered by small iron granules, which were identified as Fe₃O₄. The results also showed that new iron oxides were formed on the surface of the modified biochar after the adsorption of phosphorus. Moreover, new bonds of Fe-O-P and P-C were found, which suggested that the new iron oxides tend to be Fe₅(PO₄)₄(OH)₃. Aside from removing phosphorus, adding the modified biochar into soil also improved soil productivity. When the modified biochar-to-soil rate was 5%, the stem, root, and bean of broad bean plants demonstrated increased growth rates of 91%, 64%, and 165%, respectively.