Adsorption characteristics of N-nitrosodimethylamine from aqueous solution on surface-modified activated carbons

This study investigated the removal of N-nitrosodimethylamine (NDMA) by an adsorption mechanism using commercially available activated carbons and surface-modified activated carbons. The effects of the modification on the properties of the activated carbon were studied by N₂ adsorption/desorption, Diffuse Reflectance Infrared Fourier Transmission (DRIFT) analysis and X-Ray Photoelectron Spectroscopy (XPS). Adsorption experiments revealed that the activated carbons demonstrated a greater capacity for NDMA adsorption capacity than can be achieved using zeolite. The equilibrium data was fitted to the Freundlich equation and it was found that the adsorption capacity was significantly influenced by the micropore size, relative pore volume and surface characteristics. Adsorption experiments were conducted using unmodified and modified activated carbons. The results indicated that the adsorption capacity of NDMA can be significantly improved by heat treatment and doping of TiO₂ particles. This was because the surface treatments yielded more hydrophobic sites and fewer oxygen-containing surface functional groups, and consequently an increased capacity for NDMA adsorption.     

气凝胶在气体吸附净化中的应用研究进展

气凝胶(Aerogels)是一种以空气为介质的轻质多孔性凝聚态物质,由胶体粒子或高聚物分子相互聚集构成独特的纳米多孔三维网络结构。气凝胶的颗粒相和孔隙尺寸均为纳米量级,具有相当高的比表面积和孔隙率、可调控的开放孔隙结构、易于化学修饰的表面以及多样化的种类和形态,其气体吸附量可比同等条件下活性炭吸附量高两个数量级,因此在气体吸附净化领域逐渐受到人们的广泛关注。目前,气体吸附净化领域研究较多的气凝胶主要是SiO_2气凝胶和炭气凝胶。此外,近年来对金属氧化物气凝胶以及SiC气凝胶、石墨烯气凝胶、生物质基气凝胶等新型气凝胶的气体吸附应用也有相应的研究报道。吸附材料对目标气体需要同时具有较高的吸附容量和良好的选择性吸附能力。气凝胶的高比表面积和多孔性质提供了众多的吸附位点,但仅依靠自身物理吸附作用的吸附量有限,对目标气体的选择性不高,在实际吸附应用中,往往由于共存气体组分的竞争吸附影响对目标气体的吸附性能。因此,为了进一步提升气凝胶的吸附容量,提高对目标气体的选择性,研究人员围绕气凝胶修饰改性进行了大量的研究探索工作,并取得了一定的进展。目前,气凝胶吸附净化研究报道的目标气体主要是温室气体CO_2和大气中主要的污染物挥发性有机化合物(VOCs)。针对目标气体的不同可分别通过氨基功能化、氮掺杂等方法引入碱性位点或通过引入非极性官能团对气凝胶进行疏水改性,以提升气凝胶对CO_2或VOCs的吸附量和选择性。所采用的修饰改性方式主要有以下两种:一是在湿凝胶形成后或超临界干燥后通过嫁接、浸渍等手段对气凝胶表面进行功能化改性,通过引入特定的官能团或活性组分提升气凝胶对目标气体的吸附量和选择性;另一种是在溶胶-凝胶反应过程中引入功能化前驱体,在分子或纳米尺度上赋予气凝胶网络特定的性能,进而有效平衡活性组分稳定性和对目标气体的吸附性能。此外,对于炭气凝胶,还可通过活化进一步增大比表面积,改善孔隙结构和表面化学性质,从而实现对目标气体污染物吸附性能的优化。本文归纳了各类气凝胶在CO_2与VOCs吸附净化方面的研究进展,介绍了气凝胶的制备过程和结构特点,讨论并对比了不同气凝胶对目标气体的吸附性能与吸附机理,总结了当前气体吸附净化研究中对气凝胶进行修饰改性的主要方法,最后指出提高气凝胶的结构稳定性和吸附速率、设计可同时吸附多种目标气体的气凝胶、缩短制备周期并降低成本是未来研究工作的重点。     

Adsorption of gaseous p-xylene and m-xylene on NaY,KY, and BaY zeolites: Part 1. Adsorption equilibria of pure xylenes

Isothermal and isobaric adsorptions of p-xylene and m-xylene on NaY, KY, and BaY are studied by thermogravimetry between 25°C and 400°C, and 10 Pa and 1014 Pa. At low filling BaY shows a stronger affinity for xylenes than the other zeolites. At high temperature and low pressure its adsorption capacity is greater than those of NaY and KY. These two zeolites have a similar behavior and adsorb more m-xylene than p-xylene. At low temperature and high pressure KY adsorbs p-xylene like NaY and m-xylene like BaY, and, unlike NaY, the adsorption capacities of KY and BaY are higher for p-xylene than for m-xylene. The substitution of K⁺ or Ba²⁺ for Na⁺ decreases the adsorption capacity of α-cages.     

Enhanced adsorption of metal ions onto functionalized granular activated carbons prepared from cherry stones

Some granular activated carbons (GACs) were prepared from cherry stones (CS), an agricultural waste, by thermal methods following pyrolysis in nitrogen and subsequent activation (with air, carbon dioxide and steam) or single-step activation in steam. A GAC prepared by activation with carbon dioxide was further treated with several oxidizing agents (air, air-ozone mixture, nitric acid and hydrogen peroxide). The non-oxidized GACs produced have surface areas ranged from 508 to 901m(2)/g and show a predominantly micro- and macropores structure. Oxidation treatments, especially with nitric acid and ozone, led to the fixation of high amounts of acidic surface oxygen complexes (SOCs), thus making the carbon surface more hydrophilic. Contrary to oxidation with the other agents, the ozone treatment, at the conditions applied in this work, does not decrease the GAC surface area. Both, the non-oxidized and the oxidized GACs were used as adsorbent to study the adsorption of Cu(II) from aqueous solution. Adsorption isotherms were obtained at 25 degrees C and data were well fitted to the Langmuir equation. The results show that the Cu(II) uptake of the non-oxidized GACs is not great, but similar to that of the commercial grade Filtrasorb 400. The adsorption capacity for Cu(II) could be greatly enhanced by GAC oxidation, especially with nitric acid and ozone treatments. The larger adsorption capacity of the oxidized GACs has been attributed to oxygen functionalities (mainly carboxylic) fixed on the GAC surface, which can remove Cu(II) species from water by both ion-exchange and surface complexation mechanisms. The ozonated GAC was also evaluated for the adsorption of Co(II) species from single solute and Cu(II)-Co(II) binary mixture solutions. The functionalization of GAC by the ozone treatment improved the adsorption of both Cu(II) and Co(II) regardless of the fact that they were in single solute or binary systems.     

Preparation of polyelectrolyte-functionalized mesoporous silicas for the selective adsorption of anionic dye in an aqueous solution

Polyelectrolytes (PDDA, poly (diallydimethylammonium chloride)) functionalized mesoporous silica adsorbent (PDDA/MS) was prepared and characterized by N₂ adsorption, transmission electron microscopy (TEM) and zeta potential. The PDDA/MS showed ordered pore structure and the surface charge was successfully converted from negative to positive by PDDA functionalization. The adsorption capability of the prepared adsorbents was evaluated using nine different dye solutions with positive, neutral and negative charges. For the comparison purpose, commercial silica (CS, Davisil) and granular activated carbon (GAC), which are conventionally used as adsorbents, were also treated by PDDA impregnation. The batch adsorption experiments showed that the PDDA/MS exhibited the highest selective adsorption capacity of negative acid dye dissolved in an aqueous solution. Taken together, the results of this work indicate that polyelectrolyte functionalization of the inorganic surface could be a simple and suitable method for the surface modified adsorbent and the PDDA/MS suggested in this study could be used for the effective removal of acid dye from aqueous solutions.     

Simulataneous pentachlorophenol decomposition and granular activated carbon regeneration assisted by dielectric barrier discharge plasma

An integrated granular activated carbon (GAC) adsorption/dielectric barrier discharge (DBD) process was applied to the treatment of high concentration pentachlorophenol (PCP) wastewater. The PCP in water firstly was adsorbed onto GAC, and then the degradation of PCP and regeneration of exhausted GAC were simultaneously carried out by DBD. The degradation mechanisms and products of PCP loaded on GAC were analyzed by EDX, FT-IR and GC–MS. The results suggested that the CCl bonds in PCP adsorbed by GAC were cleaved by DBD plasma, and some dechlorination and dehydroxylation products were identified. The adsorption capacity of adsorption/DBD treated GAC could maintain relatively high level, which confirmed that DBD treatment regenerated the GAC for subsequent reuse. The adsorption of N₂, Boehm titration and XPS were used to investigate detailed surface characterizations of GAC. It could be found that DBD plasma not only increased the BET surface area and pore volume in micropore regions, but also had remarkably impact on the distribution of the oxygen-containing functional groups of GAC.     

Modified nano-CaCO3 hard template method for hierarchical porous carbon powder with enhanced electrochemical performance in lithium-sulfur battery

Lithium-sulfur (Li-S) battery was the most promising energy storage devices with ultrahigh energy density (2600 Wh kg⁻¹). But it was impeded by poor electronic conductivity, serious shuttle effect, and enormous volume expansion. Herein, hierarchical porous carbons were simply prepared by a modified nano-CaCO₃ hard-template method from glucose. The template-removal step was modified from HCl washing to HCl soaking. This allowed the microstructure of carbon product significantly involved. Furthermore, the mass ratio of CaCO₃ nanoparticles and glucose played an important role in booming of hierarchical porous and specific surface area. When integrated with S, functioned as cathode in Li-S battery, improved electrochemical performances were exhibited, such as high initial discharge capacity and good capacity retention. This modified hard-template method suggested a promising way to fabricate hierarchical porous carbon matrix available to apply in advanced Li-S battery.     

Effect of activated carbons modification on porosity, surface structure and phenol adsorption

The primary objective of this work was the examination of modified activated carbons with tailored adsorption capacity properties. Production of activated carbons with desired properties was accomplished by modification of surface functional groups and introduction of acidic/basic properties. Modification of an activated carbon was performed using partial oxygen gasification, nitric acid treatment, urea impregnation followed by pyrolysis and pyrolysis in a urea saturated stream. The surface properties of the produced samples were estimated by the multibasic titration method of Boehm and by the CO/CO2 gas evolution profiles, while pore structure development was measured by the N2 and CO2 gas adsorption isotherms. Oxygen gasification resulted in samples with surface area slightly lower that the raw activated carbon; the introduction of surface functional groups depended upon the severity of the treatment: carbonylic and phenolic type groups were introduced in all partially gasified samples, while low temperatures and short reaction times enhanced the basic character of the carbon. However, nitric acid treatment resulted in the introduction of high nitrogen amounts in the samples, the reduction of surface area and the development of a surface containing carboxylic, lactonic, phenolic and carbonylic groups with negligible HCl neutralization capacity. Treatment of activated carbon by urea supported the formation of basic groups and carbonyls. The presence of surface functional groups affected the adsorption capacity of the produced samples for the removal of specific pollutants such as phenols. Urea treated samples with a basic character and high nitrogen content presented the highest phenol uptake capacity; nitric acid treated carbons and oxygen gasified samples presented an acidic surface functionality and a low phenol adsorption capacity. The beneficial role of nitrogen on phenol adsorption was attributed to adsorbate-adsorbent interactions.     

A procedure for sorbent pretreatment for the production of high-activity 99Mo/99m Tc generators based on enriched 98Mo

The effect of the acid treatment on the adsorption capacity of aluminum oxides for Mo was examined. The areas of the initial (??_o) and limiting (??_lim) saturation of neutral and acidic aluminum oxides with hydrochloric acid were determined. The Mo adsorption maximum is attained at the limiting saturation, with the subsequent exponential decrease on approaching the point in which the interaction of the oxide with the acid starts to decelerate, after which the adsorption drastically decreases. In the area close to ??_o, the Mo breakthrough to the eluate is observed at any adsorbed amount of Mo. The results obtained allow prediction of the acid amount required for the adsorption of the preset amount of Mo.     

Preparation and photocatalytic activity of porous spherical TiO2 particles comprised of H3PW12O40 in hydrophobic nanopores

Porous TiO₂ sphere particles were prepared by impregnating titanium (IV) oxysulfate solutions into organic monolith particles, with subsequent calcination in air. The powder possessed pores of meso-order. Its crystalline phase was anatase. Then, 12 Tungsto(VI) phosphoric acid (PW₁₂) was present in the mesopores. The entire surface was modified to be hydrophobic by octadecylphosphonic acid (ODP). Subsequent UV illumination in water removed the PW₁₂ and ODP adsorbed onto the outer sphere surface. The obtained spherical TiO₂ particles with hydrophobic acidic nanopores exhibited high photocatalytic performance against the removal of 1,4-dioxane in water. Detailed analysis revealed that this material removed both 1,4-dioxane and ethylene glycol diformate (EGDF), the main intermediate of the photocatalysis of 1,4-dioxane. Results suggest that hydrophobic acidic nanopores enhance adsorption of EGDF in water and play an important role in the overall photocatalytic performance of this system.     

Consequence of chitosan treating on the adsorption of humic acid by granular activated carbon

In this work, equilibrium and kinetic adsorption of humic acid (HA) onto chitosan treated granular activated carbon (MGAC) has been investigated and compared to the granular activated carbon (GAC). The adsorption equilibrium data showed that adsorption behaviour of HA could be described reasonably well by Langmuir adsorption isotherm for GAC and Freundlich adsorption isotherm for MGAC. It was shown that pre-adsorption of chitosan onto the surface of GAC improved the adsorption capacity of HA changing the predominant adsorption mechanism. Monolayer capacities for the adsorption of HA onto GAC and MGAC were calculated 55.8 mg/g and 71.4 mg/g, respectively. Kinetic studies showed that film diffusion and intra-particle diffusion were simultaneously operating during the adsorption process for MGAC.     

Preparation and CO_2 adsorption properties of porous carbon by hydrothermal carbonization of tree leaves

Porous carbon materials were prepared by hydrothermal carbonization(HTC) and KOH activation of camphor leaves and camellia leaves. The morphology, pore structure, chemical properties and CO_2 capture ability of the porous carbon prepared from the two leaves were compared. The effect of HTC temperature on the structure and CO_2 adsorption properties was especially investigated. It was found that HTC temperature had a major effect on the structure of the product and the ability to capture CO_2. The porous carbon materials prepared from camellia leaves at the HTC temperature of 240℃ had the highest proportion of microporous structure, the largest specific surface area(up to 1823.77 m~2/g) and the maximum CO_2 adsorption capacity of 8.30 mmol/g at 25℃ under 0.4 MPa. For all prepared porous carbons, simulation results of isothermal adsorption model showed that Langmuir isotherm model described the adsorption equilibrium data better than Freundlich isotherm model. For porous carbons prepared from camphor leaves, pseudo-first order kinetic model was well fitted with the experimental data. However,for porous carbons prepared from camellia leaves, both pseudo-first and pseudo-second order kinetics model adsorption behaviors were present. The porous carbon materials prepared from tree leaves provided a feasible option for CO_2 capture with low cost, environmental friendship and high capture capability.     

Photocatalytic degradation of phenol and phenolic compounds: Part I. Adsorption and FTIR study

With the goal of predicting the photocatalytic behaviour of different phenolic compounds (catechol, resorcinol, phenol, m-cresol and o-cresol), their adsorption and interaction types with the TiO₂ Degussa P-25 surface were studied.     

Static Adsorption of Xenon on ACF at 257K

The static adsorption of xenon on active carbon fiber(ACF) at 257K was measured with ASAP2010 specific surface area and pore diameter distribution instrument by changing the working gas from nitrogen to xenon.Compared with grain activated carbon(GAC),the results were as follows(1)The adsorption performance of Viscose-based ACF(VACF-As)was the best among all absorbents tested.VACF-A3 was the superior xenon absorbent.The performance of pitch-based ACF(PACF-Cs)approached that of GAC,(2) Due to the difference of aperture distribution ,the adsorption performances of ACF with different radices were different under the same experiment conditions even though the specific surface area was similar,(3)There were some differences of adsorptive capacity among ACF absorbents which had the same radic,however there was not definite relationship between their specific surface area and adsorptive capacity,(4)The adsorption of xenon on all kinds of ACF agrees with Langmuir equation.(5)The adsorptiov curves can be fitted with a binomial equation.     

Adsorption of gaseous p-xylene and m-xylene on NaY,KY, and BaY zeolites. Part 2: Modeling. Enthalpies and entropies of adsorption

The adsorption isotherms of xylenes are described by Henry's law and Langmuir's model on NaY and KY and the Dubinin-Radushkevich model on BaY. The isoteric enthalpies of adsorption show on each zeolite that the adsorbate-adsorbent interactions are nearly the same with both isomers. They are stronger on BaY than on NaY and KY. The adsorbate-adsorbate interactions are stronger with m-xylene than with p-xylene and especially outstanding on KY. The entropies of adsorption show that the mobility of the adsorbate is lower with m-xylene than with p-xylene. The isosteric free enthalpies of adsorption are related to the acidity of each zeolite. BaY has a stronger acidity and a greater ability to adsorb xylenes than NaY and KY.     

Photocatalytic properties of BiVO4 prepared by the co-precipitation method: Degradation of rhodamine B and possible reaction mechanisms under visible irradiation

Bismuth vanadate (BiVO₄) was synthesized by the co-precipitation method at 200 °C. The photocatalytic activity of the oxide was tested for the photodegradation of rhodamine B under visible light irradiation. The analysis of the total organic carbon showed that the mineralization of rhodamine B over a BiVO₄ photocatalyst (∼40% after 100 h of irradiation) is feasible. In the same way, a gas chromatography analysis coupled with mass spectroscopy revealed the existence of organic intermediates during the photodegradation process such as ethylbenzene, o-xylene, m-xylene, and phthalic anhydride. The modification of variables such as dispersion pH, amount of dissolved O₂, and irradiation source was studied in order to know the details about the photodegradation mechanism.     

Removal of lead (II) and nickel (II) ions from aqueous solution using activated carbon prepared from rapeseed oil cake by Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> activation

In this study, rapeseed oil cake as a precursor was used to prepare activated carbons by chemical activation with sodium carbonate (Na₂CO₃) at 600 and 800 °C. The activated carbon with the highest surface area of 850 m² g^?1 was produced at 800 °C. The prepared activated carbons were mainly microporous. The activated carbon having the highest surface area was used as an adsorbent for the removal of lead (II) and nickel (II) ions from aqueous solutions. The effects of pH, contact time, and initial ion concentration on the adsorption capacity of the activated carbon were investigated. The kinetic data of adsorption process were studied using pseudo-first-order, pseudo-second-order kinetic models and intraparticle diffusion model. The experimental data were well adapted to the pseudo-second-order model for both tested ions. The adsorption data for both ions were well correlated with Langmuir isotherm. The maximum monolayer adsorption capacities of the activated carbon for the removal of lead (II) and nickel (II) ions were determined as 129.87 and 133.33 mg g^?1, respectively.     

Improvement of epoxy resin properties by incorporation of TiO2 nanoparticles surface modified with gallic acid esters

Epoxy resin/titanium dioxide (epoxy/TiO₂) nanocomposites were obtained by incorporation of TiO₂ nanoparticles surface modified with gallic acid esters in epoxy resin. TiO₂ nanoparticles were obtained by acid catalyzed hydrolysis of titanium isopropoxide and their structural characterization was performed by X-ray diffraction and transmission electron microscopy. Three gallic acid esters, having different hydrophobic part, were used for surface modification of the synthesized TiO₂ nanoparticles: propyl, hexyl and lauryl gallate. The gallate chemisorption onto surface of TiO₂ nanoparticles was confirmed by Fourier transform infrared and ultraviolet–visible spectroscopy, while the amount of surface-bonded gallates was determined using thermogravimetric analysis. The influence of the surface modified TiO₂ nanoparticles, as well as the length of hydrophobic part of the gallate used for surface modification of TiO₂ nanoparticles, on glass transition temperature, barrier, dielectric and anticorrosive properties of epoxy resin was investigated by differential scanning calorimetry, water vapor transmission test, dielectric spectroscopy, electrochemical impedance spectroscopy and polarization measurements. Incorporation of surface modified TiO₂ nanoparticles in epoxy resin caused increase of glass transition temperature and decrease of the water vapor permeability of epoxy resin. The water vapor transmission rate of epoxy/TiO₂ nanocomposites was reduced with increasing hydrophobic part chain length of gallate ligand. Dielectric constant of examined nanocomposites was influenced by gallate used for the modification of TiO₂ nanoparticles. The nanocomposites have better anticorrosive properties than pure epoxy resin, because the surface modified TiO₂ nanoparticles react as oxygen scavengers, which inhibit steel corrosion by cathodic mechanism.     

One-step hydrothermal synthesis of carbon@Fe3O4 nanoparticles with high adsorption capacity

The magnetic carbon@Fe₃O₄ nanoparticles have been fabricated by a simple one-step hydrothermal method and applied as adsorbents for removal of organic dyes such as Congo red from aqueous solution. The prepared products were characterized by transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectra, thermo-gravimetric analysis, nitrogen adsorption–desorption isotherms, UV–vis spectrum, and vibrating sample magnetometer. The adsorption performances of the products were tested with removal of Congo red from aqueous solution. The carbon@Fe₃O₄ nanoparticles possess high adsorption capacity and excellent magnetic separability by an external magnetic field, which is attributed to its high specific surface area providing more surface active sites.     

Adsorption behaviors of volatile organic compounds (VOCs) on porous clay heterostructures (PCH)

Porous clay heterostructures (PCHs) are capable of adsorbing volatile organic compounds (VOCs). In this study, PCH was synthesized by modifying bentonite (Bent) with cetyltrimethylammonium bromide (CTMAB) and dodecylamine (DDA). Adsorption of six volatile organic compounds (VOCs) including acetone, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene by PCH was investigated. It was observed that adsorption capacities of VOCs were strongly dependent on their properties including cross-sectional area, polarizability, enthalpy of vaporization and critical volume by the multiple linear regression (MLR) approach. Furthermore, PCH had higher adsorption affinity for the aliphatic hydrocarbon compound (acetone) than that for aromatic compounds, which could be attributed to the HOMO energy effects of VOCs. Therefore, PCH could be attractive candidate adsorbents for VOC removal.