Surface control in the adsorption of tebuthiuron on modified silver surfaces tracked by surface-enhanced Raman scattering spectroscopy.

The vibrational assignment of the Raman and surface-enhanced Raman scattering (SERS) spectra of the herbicide tebuthiuron (TBH) was accomplished, which allowed unprecedented propositions for adsorption geometries on the surface of silver nanoparticles (AgNP). Ascribed SERS features allowed suggesting that the adsorption occurred through nitrogen atoms of thiadiazole group, since intense band shift assigned to ring mode was marking of the coordination with the metallic surface. AgNP were treated with different surface modifiers that leaded to substantial changes in TBH adsorption geometries. Spectral changes, as the enhancement of out-of-plane ring modes, were indicative of the presence of tilted thiadiazole geometries in relation to the silver surface. Density Functional Theory (DFT) calculations from TBH molecules, in isolation and in interaction with ten-atom cluster of silver leaded to obtain theoretical spectra that gave support to interpret experimental Raman and SERS spectra.

Exploring the Interplay between Tribocorrosion and Surface Chemistry of the ASTM F139 Surgical Stainless Steel in Phosphate-Buffered Saline Solution.

Surgical ASTM F139 stainless steel is used for temporary fixtures in the biomedical field. Tribocorrosion is a major concern in this application. The aim of the present work was to study the interplay between tribocorrosion behavior and the surface chemistry of the ASTM F139 stainless steel in phosphate-buffered saline solution (PBS). Sliding wear tests were conducted against alumina balls at different electrochemical potentials: open circuit potential (OCP), cathodic potential (-100 mV versus the OCP), and anodic potentials (+200 mVAg/AgCl and +700 mVAg/AgCl). The normal load was 20 N. The wear volume was estimated based on micrographs obtained from the wear tracks using confocal laser scanning microscopy. Moreover, the wear tracks were also examined by scanning electron microscopy (SEM). The surface chemistry of the ASTM F139 specimens was analyzed by X-ray photoelectron spectroscopy (XPS). The wear volume was dependent on the electrochemical potential, being maximized at +700 mVAg/AgCl. Delamination areas and grooves were observed in the wear tracks. Detailed assessment of the surface chemistry inside the wear tracks allowed identification of the main chemical species and their relative quantities, thus enabling correlation of the passive film composition with the observed tribocorrosion behavior.

Single adsorption of diclofenac and ronidazole from aqueous solution on commercial activated carbons: effect of chemical and textural properties.

The importance of the textural and physicochemical characteristics upon the adsorption capacity of the commercial activated carbons (ACs) Coconut, Wood, Merck, Darco, and Norit towards ronidazole (RNZ) and diclofenac (DCF) from water solution was investigated thoroughly in this work. At pH = 7, Coconut AC and Wood AC presented the highest adsorption capacity towards RNZ (444 mg/g) and DCF (405 mg/g). The maximum mass of RNZ adsorbed onto Coconut AC was higher in this study than those outlined previously in other works. Besides, the maximum capacity of Wood AC for adsorbing DCF was comparable to those found for other ACs. The adsorption capacity of all the ACs was increased by surface area and was favored by incrementing the acidic site concentration. The π-π stacking interactions were the predominant adsorption mechanism for the RNZ and DCF adsorption on ACs, and the acidic sites favored the adsorption capacity by activating the π-π stacking. Electrostatic interactions did not influence the adsorption of RNZ on Coconut AC, but electrostatic repulsion decreased that of DCF on Wood AC. The adsorption of DCF on Wood AC was reversible but not that of RNZ on Coconut AC. Besides, the adsorption of RNZ and DCF on the Coconut and Wood ACs was endothermic in the range of 15-25 °C.

The Electronic Origin of the Zeta Potential is Supported by the Redox Mechanism on an Aqueous Dispersion of Exfoliated Graphite.

Herein we have proposed that a redox mechanism can produce surface charges and negative zeta potential on an aqueous graphite dispersion. Graphite was kept in contact with a concentrated ammonia aqueous solution, washed, and exfoliated in water, resulting in a dispersion with lyophobic nature. Ammonia treatment did not provide functional groups or nitrogen doping to graphite. Moreover, this material was washed twice before sonication to remove most hydroxide. Therefore, neither functional groups, nitrogen atoms, nor hydroxide excess is responsible for the zeta potential. Kelvin probe force microscopy has shown that the ammonia-treated and exfoliated graphite has higher Fermi level than the water-treated material, indicating that the contact between ammonia and graphite promotes redox reactions that provide electrons to graphite. These electrons raise the Fermi level of graphite and generate the negative zeta potential, consequently, they account for the colloidal stability.

Surface Bioactivation of Polyether Ether Ketone (PEEK) by Sulfuric Acid and Piranha Solution: Influence of the Modification Route in Capacity for Inducing Cell Growth.

The aim of this study was to promote bioactivity of the PEEK surface using sulfuric acid and piranha solution. PEEK was functionalized by a sulfuric acid treatment for 90 s and by piranha solution for 60 and 90 s. Chemical modification of the PEEK surface was evaluated by infrared spectroscopy, contact angle analysis, cytotoxicity, cell adhesion and proliferation. The spectroscopy characteristic band associated with sulfonation was observed in all treated samples. PEEK with piranha solution 60 s showed an increase in the intensity of the bands, which was even more significant for the longer treatment (90 s). The introduction of the sulfonic acid functional group reduced the contact angle. In cytotoxicity assays, for all treatments, the number of viable cells was higher when compared to those of untreated PEEK. PEEK treated with sulfuric acid and piranha solution for 60 s were the treatments that showed the highest percentage of cell viability with no statistically significant differences between them. The modified surfaces had a greater capacity for inducing cell growth, indicative of effective cell adhesion and proliferation. The proposed chemical modifications are promising for the functionalization of PEEK-based implants, as they were effective in promoting bioactivation of the PEEK surface and in stimulating cell growth and proliferation.

Interfacial behavior of Lactate Oxidase at Air-Subphase interface.

This article investigates the main aspects of the surface chemistry properties of the lactate oxidase (LacOx) enzyme monolayer at the air-subphase interface. Surface chemistry study determined the important properties like the surface packing and stability of the formed layer, whereas the spectroscopic experiments provided information regarding its secondary structure conformation of the enzyme. We have demonstrated that the LacOx in the monolayer form remained active for extended time period. In accordance to the data obtained from the isotherm it was also found that LacOx forms a stable monolayer that does not aggregate at the air-subphase interface. The stability of the monolayer at the air-subphase interface was studied by using compression-decompression cycles which revealed the stability with no significant evidence of aggregates or irreversible domains. This was further confirmed by UV-vis absorption and fluorescence measurements. Spectra from circular dichroism (CD) showed that the LB film retains the characteristic of an α-helix conformation.

Variation in the properties of biochars produced by mixing agricultural residues and mineral soils for agricultural application.

The research and application of biochars enriched with minerals have increased in recent years; however, the mineral fraction used consists of specific minerals, such as clay minerals and synthesized compounds. In this work, the effects of adding two specific soil types (sandy and clayey) to rice and coffee husks in order to generate biochars via pyrolysis was investigated. Chemical, physical-chemical, thermal, spectroscopic and crystallographic analyses were conducted on the produced biochars. The study confirmed that the presence of mineral soils during the pyrolysis process increases the yield, C retention ratio, and specific surface area. It also decreases the pH, cation exchange capacity (CEC), nutrient content, and carbon-to-nitrogen ratio of biochars. However, the biochars produced by mixing coffee husks and mineral soils still demonstrate a capacity to increase the pH and the CEC of tropical soils. In addition, increased C retention demonstrates an environmental benefit of this biochar production method. Biomass pyrolysis combined with clayey soil results in a biochar with a higher degree of aromaticity and higher thermal stability when compared to biomass pyrolysis alone. These characteristics give the biochar a recalcitrant character, without the necessity for steps related to the synthesis of specific mineral compounds, which reduces the economic and energy cost of the process.

Could petroleum work as lubricant oil on slippery lubricated surfaces to prevent inorganic scaling?

The use of nucleation and growth inhibitors at offshore oil industry to avoid inorganic scaling could be replaced by both physical and chemical modifications at surfaces to prevent the scaling. In that way, the slippery lubricated surfaces have been showing promising results as scaling preventers, notably when the lubricants are perfluorinated oils, which are immiscible with almost every kind of compound. Nonetheless, the requirement of periodically refilling these lubricant oils is disadvantageous, especially when dealing with deep sea facilities. Using petroleum as the lubricant oil could skip the refilling step, since it is always present in the extraction medium. So, this work tests the effectiveness of petroleum as the lubricant oil in functionalized textured polyaniline applied as anti-scaling material in conditions that simulate the medium of offshore operation. As result, petroleum as lubricant oil presents effective anti-scaling capacity and works perfectly in slippery lubricated surfaces.

Surface chemistry and spectroscopic studies of the native phenylalanine dehydrogenase Langmuir monolayer at the air/aqueous NaCl interface.

This study investigates the main aspects of the surface behavior of the native phenylalanine dehydrogenase (PheDH) enzyme at the air/aqueous interface employing a saline subphase to induce the enzyme surface activity. Surface chemistry experiments were performed in order to determine the surface packing and stability of the formed layer, while spectroscopic experiments provided information regarding its secondary structure conformation. It was found that the PheDH enzyme forms a fluid film, which is quite homogeneous throughout its entire compression, being stable for long periods of time with no significant evidence of aggregates or irreversible domains during interfacial compression/decompression processes. The main secondary structures of the interfacial PheDH film were accessed via in situ reflectance-absorbance infrared spectroscopy, indicating a majority presence of α-helices, which were maintained after the film transfer to solid muscovite supports. The immobilized films presented a homogeneous and regular deposition, with controlled roughness and a mean thickness in the range of 8-10 nm.

Beyond electrostatic interactions: Ligand shell modulated uptake of bis-conjugated iron oxide nanoparticles by cells.

The effect of the ligand shell on the cellular uptake efficiency was evaluated by a systematic study using fully dispersed 6 nm diameter superparamagnetic iron oxide nanoparticles (SPIONs), mono and bis-conjugated with glycerol phosphate (glyc), dopamine (dopa), 4,5-dihydroxy-1,3-benzenedisulfonic acid (tiron) and phosphorylethanolamine (pea). Negatively charged SPION-glyc was more efficiently incorporated than positively charged SPION-pea and SPION-dopa clearly evidencing that there are strong enough short-range interactions in addition to the long-range electrostatic interactions, as measured by the zeta potential, to reverse our expectation on cellular uptake. Those effects were pursued by correlating the nanoparticles incorporation efficiency as a function of the respective zeta potentials and the molar fractions of glyc and pea ligands co-conjugated on the SPION surface. The possibility of associating different ligands to modulate the physicochemical properties and biological events was demonstrated, showing promising perspectives for the development of multifunctional nanosystems for biomedical applications.

Tracking chemical interactions of folic acid on gold surface by SERS spectroscopy.

Surface-enhanced Raman scattering (SERS) spectroscopy was used in the investigation of the adsorption of folic acid (FA) on the surface of gold nanoparticles (AuNPs) in the absence and presence of surface modifiers hydrochloride acid (HCl) and 1-mercaptoethanol (ME). The proposal for the chemical interactions of FA with the metallic surface was based on vibrational assignment supported by Density Functional Theory (DFT) calculations. In the absence of surface modifiers, FA interacts with the gold surface through the pteridine moiety in a tilted geometry. In the presence of ME, the molecule of FA is anchored through hydrogen bonds with the surface modifier. The presence of HCl induced ion-pair interactions involving chloride ions, adsorbed on gold surfaces, and both the nitrogen N1 of the pteridine ring and the γ-carboxylic acid of the glutamic acid moiety. In this condition, keto-enol equilibrium can be evidenced by a remarkable enhancement of marker bands in the SERS spectra.

Insights on the transport of tamoxifen by gold nanoparticles for MCF-7 breast cancer cells based on SERS spectroscopy.

Gold nanoparticles (AuNP) were synthesized and modified with anti-folate receptor antibody (AB), folic acid (FA), crystal violet (CV), poly (ethyleneglycol) methyl ether thiol and the antineoplastic drug tamoxifen (TAM). Such a preparation was incubated in vitro with MCF-7 human breast cancer cells, showing a decrease in the TAM dosage for the reduction of cell viability. The adsorption of TAM on gold surface was investigated by surface-enhanced Raman scattering (SERS) spectroscopy and the assignment based on Density Functional Theory calculations showed that the ether moiety was involved in the interactions with the metal. Such a chemical affinity was correlated with the carrying of TAM in the biological media. CV was included in the preparation as a molecular probe for SERS spectroscopy, whose signal was monitored to analyse the efficiency of the modified AuNP in the target of neoplastic cells. The results showed AB, FA and TAM components had complementary roles in the cell recognition and, therefore, in the efficiency of the drug carrier nanosystem.

The control of the adsorption of bovine serum albumin on mercaptan-modified gold thin films investigated by SERS spectroscopy.

Nanostructured gold thin films were built from deposition of colloidal gold nanoparticles on silanized glass slides, and used to study the adsorption of bovine serum albumin (BSA) after chemical treatment of gold surface with the mercaptans 2-mercaptoethanol, 3-mercaptoproprionic acid, 1,3-propanedithiol and 1-propanethiol. Surface-enhanced Raman scattering (SERS) spectroscopy was used for investigating the chemical interactions of BSA with the modified gold surfaces. In the presence of the surface modifier 2-mercaptoethanol, a promoter of hydrogen bonds, the stable interactions among BSA and gold surfaces led to high reproducibility of the SERS spectral pattern in the most monitored points of the mapped surface. The vibrational assignment endorsed the assumption that lysine residue, majority present in the molecular structure, were the principal anchor site of BSA involved in the interactions with 2-mercaptoethanol-modified gold surface.

Kinetics, Assembling, and Conformation Control of L-Cysteine Adsorption on Pt Investigated by in situ FTIR Spectroscopy and QCM-D.

A quartz crystal microbalance method with dissipation (QCM-D) and attenuated total reflection Fourier-transform infrared (ATR-FTIRS) spectroscopy were used to study the adsorption of L-cysteine (L-Cys) on Pt. Through QCM-D, it was possible to verify that the viscoelastic properties of the adsorbed species play an important role in the adsorption, rendering Sauerbrey's equation inapplicable. The modelling of QCM-D data exposed two different processes for the adsorption reaction. The first one had an activation time and is fast, whereas the second is slow. These processes were also resolved by ATR-FTIRS and identified to be water and anion adsorption preceded by L-Cys adsorption. Both techniques reveal that the degree of surface coverage is pH dependent. Spectroscopic data indicate that the conformation of L-Cys(ads) changes with pH and that the structures do not fully agree with those proposed in literature for other metallic surfaces. The assembling of the adsorbed monolayer appeared to be very fast, and it was not possible to determine or quantify this kinetics. The conformation is also controlled by applied potential, and the anion adsorption and interfacial water depends on the conformation of the adsorbed molecules.

Insights of adsorption mechanisms of Trp-peptides on plasmonic surfaces by SERS.

The adsorptions of tryptophan (Trp) on silver or gold surfaces were investigated by surface-enhanced Raman scattering (SERS) measurements. In addition, peptides with Trp in different chain positions were studied and the adsorption sites were determined based on marker bands. The indole ring was the main group responsible for the interactions with gold nanoparticles (AuNPs). In the presence of HCl, the SERS spectra suggested that the anchoring of such peptides on AuNPs was reinforced by ionic pair interactions between protonated amine and chloride ions. The adsorptions of Trp and its derivatives on silver nanoparticles (AgNPs) show some variability in the spectral patterns, even though the enhanced carboxilate and amino features were ever ascribed as preferable adsorption site. Based on DFT calculations the vibrational assignment allows the reinterpretation of previous published works. The investigations showed that both the high affinity of indole moiety for the AuNP surfaces make these substrates adequate for studying the adsorption of peptides containing Trp and the proposed SERS assignments could be helpful for further studies of more complex structures.

InP Nanowire Biosensor with Tailored Biofunctionalization: Ultrasensitive and Highly Selective Disease Biomarker Detection.

Electrically active field-effect transistors (FET) based biosensors are of paramount importance in life science applications, as they offer direct, fast, and highly sensitive label-free detection capabilities of several biomolecules of specific interest. In this work, we report a detailed investigation on surface functionalization and covalent immobilization of biomarkers using biocompatible ethanolamine and poly(ethylene glycol) derivate coatings, as compared to the conventional approaches using silica monoliths, in order to substantially increase both the sensitivity and molecular selectivity of nanowire-based FET biosensor platforms. Quantitative fluorescence, atomic and Kelvin probe force microscopy allowed detailed investigation of the homogeneity and density of immobilized biomarkers on different biofunctionalized surfaces. Significantly enhanced binding specificity, biomarker density, and target biomolecule capture efficiency were thus achieved for DNA as well as for proteins from pathogens. This optimized functionalization methodology was applied to InP nanowires that due to their low surface recombination rates were used as new active transducers for biosensors. The developed devices provide ultrahigh label-free detection sensitivities ∼1 fM for specific DNA sequences, measured via the net change in device electrical resistance. Similar levels of ultrasensitive detection of ∼6 fM were achieved for a Chagas Disease protein marker (IBMP8-1). The developed InP nanowire biosensor provides thus a qualified tool for detection of the chronic infection stage of this disease, leading to improved diagnosis and control of spread. These methodological developments are expected to substantially enhance the chemical robustness, diagnostic reliability, detection sensitivity, and biomarker selectivity for current and future biosensing devices.

Oxidación de lassuperficie de carbón activado mdiante hno3 y h2o2: efecto sobrre la remoción de níquel (ii) en solución acuosa / Activated carbon surface oxidatio by hno3 and h2o2: effect on the removal of nicckel (ii) from aqueous solution / Oxdação da superrfície de carvão aivado por meio de hno3 e h2o2: efeito na remoção de níquel (ii) em solução aquosa

Este trabajo analiza el efecto de la modificación de la química superficial de un carbón activado granular, CAG, por oxidación con ácido nítrico, CAG-N, y peróxido de hidrogeno, CAG-P en la adsorción de iones níquel desde solución acuosa. Las muestras obtenidas se caracterizaron a través de diferentes técnicas; la química superficial se evaluó por determinaciones de acidez y basicidad total, punto de carga cero y espectroscopia IR, que muestran el efecto del agente oxidante. Los parámetros texturales, como área superficial BET y volúmenes de poro, se evaluaron mediante adsorción de gases. Los valores de área superficial BET de los sólidos se encuentran entre 816 y 876 m²g-1, adicionalmente se determinaron entalpías de inmersión de los carbones activados en agua y benceno. Finalmente, los resultados experimentales de la adsorción desde solución se ajustaron a los modelos de Langmuir, Freundlich, Redlich-Peterson y Toth, y se encontró el mejor ajuste para este último. Los valores de la capacidad de adsorción determinadas por el modelo de Langmuir están entre 29,68 y 50,97 mg g-1, lo que indica que la capacidad de adsorción depende, en gran medida, de la química superficial del sólido.

In this work is studied the effect in the surface chemistry modification of a granular activated carbon, CAG, by oxidation with nitric acid, CAG-N, and hydrogen peroxide, CAG-P, in the nickel ions adsorption from aqueous solution. The samples were characterized by different techniques, surface chemistry was evaluated by acidity and basicity total determinations, point of zero charge and IR spectroscopy that show the effect of oxidant agent. The textural parameters such as BET surface area and pore volumes were evaluated by gas adsorption. The BET surface area values of the solids are between 816 and 876 m²g-1; additionally were determined immersion enthalpies in water and benzene. Finally, the experimental results of the adsorption from solution were adjusted to the Langmuir's, Freundlich's, Redlich-Peterson's and Toth's models, and were found the best adjustment for the latter. The capacity adsorption determined by Langmuir's model is between 29.68 50.97 mg g-1, which indicates that the adsorption capacity depends to a great extent on the solid surface chemistry.

Neste trabalho se estudou o efeito na da modificação da química superficial de um carvão ativado granular, CAG, por oxidação com ácido nítrico, CAG-N, e peróxido de hidrogênio, CAG-P na adsorção de íons níquel desde solução aquosa. As mostras obtidas foram caracterizadas por diferentes técnicas; a química superficial foi avaliada por determinações de acidez e basicidade total, ponto de ônuszero e espectroscopia IR, que mostram o efeito do agente oxidante. Os parâmetrostexturais, como área superficial BET e volumes de poro se avaliaram mediante adsorção de gases. Os valores de área superficial BET dos sólidos se encontram entre 816 e 876 m²g-1, adicionalmente se determinaram entalpias de imersão dos carvõesativados em água e benzeno. Finalmente, os resultados experimentais da adsorção desde soluçãoforam ajustados aos modelos de Langmuir, Freundlich, Redlich-Peterson e Toth, e se encontrou o melhor ajuste para esse último. Os valores da capacidade de adsorção determinados pelo modelo de Langmuir estão entre 29,68 e 50,97 mg g-1, o que indica que a capacidade de adsorção depende em grande parte da química superficial do sólido.

Modificación dellas características químicas suerficiales de aerogeles de carbbono por tratamientos oxidativos / Modification of the chemistry surface characterisics of carbon aerogels by oxidaative treatments / Modificação de características químicas superficiais de aerogels e carbono por ttratamentos oxidativos

Se prepararon aerogeles de carbono por la carbonización de aerogeles orgánicos sintetizados por el método sol-gel a partir de formaldehído, resorcinol y un catalizador básico; se modificó su superficie por tratamientos con oxígeno (8,8% en nitrógeno) y ácido nítrico. Los materiales se caracterizaron por isotermas de adsorción con nitrógeno a 77 K, descomposición con temperatura programada (DTP) de CO y CO2, punto de carga cero y punto isoeléctrico. Se encontró que los aerogeles modificados presentan micro y mesoporosidad bien desarrollada. Los resultados obtenidos por DTP muestran que la oxidación con oxígeno incrementa la concentración de grupos hidroxilo y carbonilo en la superficie de los aerogeles, mientras que la oxidación con ácido nítrico incrementa la concentración de grupos carboxilo.

Carbon aerogels were prepared by carbonization of organic gels synthesized by the sol-gel methodology from resorcinol, formaldehyde and a basic catalyst. Its surface was modified by treatments with oxygen (8.8% in N2) and nitric acid. The materials were characterized by nitrogen adsorption isotherms at 77 K, temperature programmed decomposition of CO and CO2 (TPD), zero charge point and isoeletric point. It was found that the modified aerogels have a well developed micro and mesoporosity; the TPD results shows that oxidative treatment with oxygen increase the concentration of hydroxyl and carbonyl groups on the surface of aerogels, whereas the oxidation with nitric acid increase the concentration of carboxyl groups.

Foram preparados aerogels de carbono pela carbonização dos geles orgânicos sintetizados pela metodologia sol-gel de resorcinol, de formaldeído e de um catalisador básico. A sua superfície foi modificada por tratamentos com oxigénio (8.8% em nitrogénio) e ácido nítrico. Os materiais foram caracterizados por isotermas de adsorção de nitrogénio a 77 K, pela decomposição com temperatura programada de CO e de CO2 (DTP), pelos pontos de carga zero e pelo ponto isoeléctrico. Encontrou-se que os aerogels modificados apresentaram micro e mesoporosidade bem desarrolhadas. Os resultados obtidos por DTP mostraram que a oxidação com oxigénio aumenta a concentração de grupos hidroxilo e carbonilo na superfície dos aerogels, enquanto que a oxidação com ácido nítrico aumenta a concentração de grupos carboxilo.

Remoción de crooo vi de soluciones acuosas por adsorción sobre carbones activados modificados / Reoval of cromiuum (vi) from aqueous solutions over modified activated aarbons / Remoão de crómioo vi de soluções aqusas por adsorção em carvões acttivados modificados

En este trabajo se determina la adsorción de Cr6+ de disoluciones acuosas en dos carbones activados comerciales en función del grado de modificación (reducción, oxidación) de la superficie de los adsorbentes, con tratamientos térmicos en presencia de hidrógeno, oxígeno y ácido nítrico. La química superficial de los carbones activados originales y modificados se examina por los métodos de titulaciones de Böehm y descomposición con temperatura programada (DTP). Los ensayos de evaluación de la capacidad de adsorción se realizan con soluciones modelo de ión cromato y bajo distintas condiciones de concentración inicial, tiempo de contacto, pH del medio, temperatura y masa de adsorbente. Se comprueba que la modificación de la superficie de los adsorbentes afecta el grado de adsorción del ión cromato en la medida en que los sólidos tratados con H2 muestran la mayor capacidad de remoción. Las variables que afectan favorablemente la extensión de la remoción de cromo son: concentración inicial de 100 ppm, pH inicial de 2,0, temperatura de 25 °C y masa de adsorbente de 100 mg.

In this work, the influence of the degree of surface modification of activated carbons in the adsorption of Cr6+ from aqueous solution was determined modifying two commercial activated carbons by thermal oxidative and reductive treatments (oxygen or nitric acid and hydrogen, respectively). The surface chemistry of the original and modified activated carbons was examined by Böehm’s titrationand thermal programmed decomposition (TPD). The adsorption capacities were tested with model solutions of chromate ion, and under different initial concentrations, contact times, pH, temperature and adsorbent mass. The surface chemistry modifications showed that they have an important influence in the adsorption capacity of the activated carbons, being the hydrogen modified carbons the best for the chromate ion adsorption. The conditions that presented the maximum adsorption capacity were: initial concentration of 100 ppm, initial pH of 2.0, temperature of 25°C and adsorbent mass of 100 mg.

Neste trabalho estudou-se a adsorção de Cr6+ de soluções aquosas em dois carvões activados comerciais em função do grau de modificação (redução, oxidação) da superfície dos adsorventes com tratamentos térmicos na presença de hidrogénio, oxigénio e ácido nítrico. A química superficial dos carvões activados originais e modificados foi examinada pelos métodos de titulação de Böehm e de decomposição a temperatura programada (DTP). Os ensaios de avaliação da capacidade de adsorção realizaram-se com soluções modelo de ião cromato sob diferentes condições de concentração inicial, tempo de contacto, pH do meio, temperatura e massa de adsorvente. Comprovou-se que a modificação da superfície dos adsorventes afecta a extensão da adsorção do ião cromato, sendo que os sólidos tratados com H2 mostram a maior capacidade de remoção. As variáveis que afectam favoravelmente a extensão da remoção do crómio são: concentração inicial de 100 ppm, pH inicial de 2.0, temperatura de 25ºC e massa de adsorvente de 100 mg.

Grupos superficaales en materiales carbonosos. caracterización por diferentes técniass / Surface goups onn carbonaceous materials.characterization by different techniqees / Grupos sperficiaais em materiais de carbono.caracterização por diferentes técnicas

Se modificó la química superficial de dos materiales carbonosos comerciales mediante tratamientos con hidrógeno, oxígeno al 8,8% en nitrógeno y ácido nítrico. Estos tratamientos producen diversas características en la superficie de los materiales, que se confirman por las titulaciones potenciométricas y de Boehm, y análisis de descomposición con temperatura programada (DTP). Los resultados guardan relación con la presencia o ausencia de grupos superficiales oxigenados.

The surface chemistry of two commercial carbonaceous materials was modified by hydrogen, 8.8% oxygen in nitrogen and nitric acid. These treatments produce diverse characteristics on the surface of the carbonaceous materials, which were confirmed by potentiometric and Boehm titrations, and temperature programmed desorption analysis (TPD). The results are related to the presence or absence of oxygenated surface groups.

A química superficial de dois materiais de carbono comerciais foi modificada através de tratamentos com hidrog ê nio, oxig ê nio diluído em azoto (8.8%) e ácido nítrico. Estes tratamentos produzem várias características na superfície dos materiais, confirmadas por titulações potenciométricas e de Boehm e por análises de desorção a temperatura programada (TPD). Os resultados relacionam-se com a presença ou ausência de grupos superficiais contendo oxig ê nio.