Adsorption of fatty acids on iron (hydr)oxides from aqueous solutions

The interaction of iron (hydr)oxides with fatty acids is related to many industrial and natural processes. To resolve current controversies about the adsorption configurations of fatty acids and the conditions of the maximum hydrophobicity of the minerals, we perform a detailed study of the adsorption of sodium laurate (dodecanoate) on 150 nm hematite (α-Fe(2)O(3)) particles as a model system. The methods used include in situ FTIR spectroscopy, ex situ X-ray photoelectron spectroscopy (XPS), measurements of the adsorption isotherm and contact angle, as well as the density functional theory (DFT) calculations. We found that the laurate adlayer is present as a mixture of inner-sphere monodentate mononuclear (ISMM) and outer-sphere (OS) hydration shared complexes independent of the solution pH. Protonation of the OS complexes does not influence the conformational order of the surfactant tails. One monolayer, which is filled through the growth of domains and is reached at the micellization/precipitation edge of laurate, makes the particles superhydrophobic. These results contradict previous models of the fatty acid adsorption and suggest new interpretation of literature data. Finally, we discovered that the fractions of both the OS laurate and its molecular form increase in D(2)O, which can be used for interpreting complex spectra. We discuss shortcomings of vibrational spectroscopy in determining the interfacial coordination of carboxylate groups. This work advances the current understanding of the oxide-carboxylate interactions and the research toward improving performance of fatty acids as surfactants, dispersants, lubricants, and anticorrosion reagents.     

Vibrational characteristics of outer-sphere surface complexes: example of sulfate ions adsorbed onto metal (hydr)oxides

The vibrational characteristics of outer-sphere complexes of sulfate at several mineral oxide-water interfaces were investigated by in situ attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy. In the IR spectra obtained from surface outer-sphere complexes, only one peak of the asymmetric stretching vibrational mode υ(3) similar to that of free sulfate ion SO(4)(2-) in aqueous solution is observed. However, on the investigated (hydr)oxide surfaces of Al(3+), Ti(4+), Fe(2+/3+), Cr(3+), Ce(4+), Cu(2+), Y(3+), Zn(2+), and Nd(3+), a shift of up to 14 cm(-1) was found, which was correlated to the polarizing power of the metal cations. A high polarizing power was found to result in a stronger shift of υ(3) compared to that of the aqueous SO(4)(2-) ion. Furthermore, the impact of the metal oxide structure on the characteristics of the formed outer-sphere complex was negligible because different Al and Fe (hydr)oxides did not show any changes in the respective IR spectra. Finally, the ionic strength (1-10(-4) M) and pH (6.8-3.1) have been modified to change the surface potential, showing no direct influence on the spectra (i.e., on the geometry of the outer-sphere complex).     

Biosorption of tetracycline onto dried alligator weed root: effect of solution chemistry and role of metal (hydr)oxides

Research on Chemical Intermediates - Dried powder of alligator weed root (AWR), a promising biosorbent, was employed to remove tetracycline (TC) from aqueous solution, using acid-pretreated AWR...     

Effects of a heavy metal (zinc) on organic adsorption capacity and organic removal in activated sludge

Applied Biochemistry and Biotechnology - Effects of a common heavy metal (zinc) on activated sludge were studied with a sequencing batch reactor (SBR). Organic removal in activated sludge was...     

The mechanism of the protonation of metal (hydr)oxides in aqueous solutions studied for various interfacial/surface ionization models and physicochemical parameters: a critical review and a novel approach

The mechanism of the protonation of solid metal (hydr)oxides in aqueous media was investigated using simulation and experimental work. It was found that the apparent acidity/basicity of each kind of surface sites of metal (hydr)oxides in aqueous suspensions is strongly influenced by the overall surface charge of the (hydr)oxide and thus by the electrical potential smeared out at the interfacial region. Depending on its sign this increases or decreases the hydrogen ion concentration on the surface, thus promoting or hindering protonation. This is manifested by the shifts of the protonation peaks of the various kinds of sites with respect to the -pK values of the corresponding intrinsic protonation constants and the appearance of an extra peak in the d[H+cons,surf]/dpH vs. pH curves. Potentiometric titrations experiments performed for four technologically important oxides showed that the proposed protonation mechanism describes indeed the protonation of polycrystalline (hydr)oxides in aqueous media.     

How metal (hydr)oxides are protonated in aqueous media: the (n+1) rule and the role of the interfacial potential

The mechanism of the protonation of solid metal (hydr)oxides in aqueous media, which is closely interrelated to many processes of great technological and environmental importance, has been elucidated using simulation and experimental work. The electrical potential, smeared out at the interfacial region, changes the concentration of the H+ ions on the surface of the (hydr)oxide, thus promoting or hindering protonation. This is manifested by the shifts of the protonation peaks of the various kinds of surface sites and the appearance of an extra peak in the differential potentiometric titration curve.     

Rational design of interfacial properties of ferric (hydr)oxide nanoparticles by adsorption of fatty acids from aqueous solutions

Notwithstanding the great practical importance, still open are the questions how, why, and to what extent the size, morphology, and surface charge of metal (hydr)oxide nanoparticles (NPs) affect the adsorption form, adsorption strength, surface density, and packing order of organic (bio)molecules containing carboxylic groups. In this article, we conclusively answer these questions for a model system of ferric (hydr)oxide NPs and demonstrate applicability of the established relationships to manipulating their hydrophobicity and dispersibility. Employing in situ Fourier transform infrared (FTIR) spectroscopy and adsorption isotherm measurements, we study the interaction of 150, 38, and 9 nm hematite (α-Fe(2)O(3)) and ～4 nm 2-line ferrihydrite with sodium laurate (dodecanoate) in water. We discover that, independent of morphology, an increase in size of the ferric (hydr)oxide NPs significantly improves their adsorption capacity and affinity toward fatty acids. This effect favors the formation of bilayers, which in turn promotes dispersibility of the larger NPs in water. At the same time, the local order in self-assembled monolayer (SAM) strongly depends on the morphological compatibility of the NP facets with the geometry-driven well-packed arrangements of the hydrocarbon chains as well as on the ratio of the chemisorbed to the physically adsorbed carboxylate groups. Surprisingly, the geometrical constraints can be removed, and adsorption capacity can be increased by negatively polarizing the NPs due to promotion of the outer-sphere complexes of the fatty acid. We interpret these findings and discuss their implications for the nanotechnological applications of surface-functionalized metal (hydr)oxide NPs.     

Surface acid-base properties and hydration/dehydration mechanisms of aluminum (hydr)oxides

In this paper, surface physiochemical properties of three typical aluminas, gamma-Al(OH)3, gamma-Al2O3, and alpha-Al2O3, were investigated by means of XRD, SEM, TEM, BET surface area, TG/DTA, and potentiometric titration techniques. Based on the titration data, surface protonation and deprotonation constants were determined using the constant capacitance model (CCM). The emphasis of this research was laid on the comparison of the crystal structure, surface hydration/dehydration and acid-base properties of these three typical alumina minerals. The calculation results revealed that the surface acidity of the aluminas is in the order of alpha-Al2O3>gamma-Al(OH)3>gamma-Al2O3 after being hydrated for 1 h. The correlation between the hydration/dehydration mechanisms of alumina and its acid/base properties is discussed.     

Nonclassical nucleation towards separation and recycling science: Iron and aluminium (Oxy)(hydr)oxides

Separation, analysis and recycling technologies are of high interest for our modern societies, where colloidal iron and aluminium (hydr)oxides have important applications. However, there are significant gaps in the fundamental understanding of how these phases form in real systems. Classical nucleation theory cannot account for many experimental observations, and there is a dichotomy between the chemistry of hydrolysing/condensating systems and the physical notion of supersaturation. Reviewing parts of the established and recent literature, we demonstrate that concepts of nonclassical nucleation pathways can overcome these issues. This broader, chemistry-based conceptual framework has a high potential for advancing current applications, and developing new strategies towards separation, analysis and recycling applications, which seem to be urgently required for the future.     

Photooxidation of nucleic acids on metal oxides: physico-chemical and astrobiological perspectives

Photocatalytic oxidation of nucleic acid components on aqueous metal oxides (TiO(2), α-FeOOH, and α-Fe(2)O(3)) has been studied. The oxidation of purine nucleotides results in the formation of the purine radical cations and sugar-phosphate radicals, whereas the oxidation of pyrimidine nucleotides other than thymine results in the oxidation of only the sugar-phosphate. The oxidation of the thymine (and to a far less extent for the 5-methylcytosine) derivatives results in deprotonation from the methyl group of the base. Some single stranded (ss) oligoribonucleotides and wild-type ss RNA were oxidized at purine sites. In contrast, double stranded (ds) oligoribonucleotides and DNA were not oxidized. These results account for observations suggesting that cellular ds DNA is not damaged by exposure to photoirradiated TiO(2) nanoparticles inserted into the cell, whereas ss RNA is extensively damaged. The astrobiological import of our observations is that the rapid degradation of monomer nucleotides make them poor targets as biosignatures, whereas duplex DNA is a better target as it is resilient to oxidative diagenesis. Another import of our studies is that ds DNA (as opposed to ss RNA) appears to be optimized to withstand oxidative stress both due to the advantageous polymer morphology and the subtle details of its radical chemistry. This peculiarity may account for the preference for DNA over RNA as a "molecule of life" provided that metal oxides served as the template for synthesis of polynucleotides, as suggested by Orgel and others.     

Indirect radiotracer study of the adsorption of organic compounds at platinized platinum electrodes

The possibility of the use of an indirect radiotracer method for the study of the adsorption of organic species has been discussed. It has been shown that by study of the adsorption of Cl-36 labelled chloride ions in the presence of organic species such as maleic, benzoic and m-nitrobenzoic acids there is a possibility of obtaining information concerning the adsorption of the latter compounds. Change in the adsorption behaviour of organic species connected with their electroreduction were detected and followed by indirect tracer measurements. In the light of the experimental results, some mechanistic aspects of the reduction of aromatic nitro compounds are discussed.     

In situ radiotracer study of thiourea adsorption on n-Si (100) and p-Si (100) electrodes

The application of a radiotracer method to in situ studies of the adsorption of thiourea labelled with either C-14 or S-35 nuclides on smooth n-type and p-type Si (100) electrodes and on rough p-Si electrodes is described. The adsorption takes place over the whole potential range studied, i.e. −0.5 to 1.2 V. It was found that during the interaction of thiourea with the silicon surface, two different products are formed. The dependence of the surface concentration of the adsorbates on the electrode potential and on the bulk concentration of thiourea was determined. Two different species are proposed to be present on the electrode surface as a result of surface processes: physically adsorbed thiourea molecules and sulphur atoms which are chemically bonded to the surface. Different activities of smooth and rough silicon electrodes towards the adsorption of thiourea were demonstrated.     

The electrical double layer on oxides: Specific adsorption of chloride and methylviologen on ruthenium dioxide

The double-layer properties of colloidal RuO₂, prepared by thermal decomposition of RuCl₃ at 420°C, have been studied by potentiometric acid-base titrations in combination with electrophoretic mobility measurements. The point of zero charge (pzc) in KNO₃ solutions was found to be pH 5.75 ± 0.05, and the isoelectric point (iep) is positioned at pH 5.8. From the total capacitance of the double layer at the pzc an electrochemical surface area of 21.5 m²/g has been found, which is equal to the BET surface area. The capacitance of the inner part of the double layer (C_i) is 300 μF/cm², which is high compared to C_i on AgI and Hg, but of the same order as that commonly found for oxides. This subject is briefly discussed. The surface charge (σ₀) as a function of pH could be fitted satisfactorily with a simple double-layer model. In the presence of KCl the pzc and the iep are shifted to higher and lower pH, respectively, indicating specific adsorption of Cl⁻ ions. The ionic composition of the double layer as a function of σ₀ and the specific adsorption of Cl⁻ at the pzc have been calculated by a straightforward thermodynamic analysis combined with diffuse double-layer theory. Methylviologen (MV²⁺) also adsorbs specifically and at negative surface charges superequivalent adsorption can take place. In the presence of an excess of KNO₃, specific adsorption of MV²⁺ is no longer noticeable. Some consequences for the catalytic reduction of water by RuO₂ in the presence of MV²⁺ are considered.     

Water adsorption and hydrolysis on molecular transition metal oxides and oxyhydroxides

Addition of water to molecular transition metal oxides (TiO2(g) and CrO3(g)) and oxyhydroxides (ScO(OH)(g), VO2(OH)(g), and MnO3(OH)(g)) was studied by means of quantum chemistry. In the investigated reactions, each reaction step comprised the breaking of one M=O bond and the formation of two OH groups. Exothermicity was observed when the product had tetrahedral or lower oxygen coordination. The reactions were found to involve stable water complexes as intermediates. The stabilities of such complexes were accentuated in the addition reaction Sc(OH)3(g) + H2O(g), in which the formation of a tetrahedral complex was found exothermic. For VO(OH)3(g), CrO2(OH)2(g), and MnO3(OH)(g), water addition to the remaining M=O bonds was found endothermic, whereas the formation of water complexes, using hydrogen bonds and preserving the oxyhydroxide kernel, was preferred. Thus, the sequence of such kernels for water clustering in the investigated reactions was found to be Sc(OH)3.H2O(g), Ti(OH)4(g), VO(OH)3(g), CrO2(OH)2(g), and MnO3(OH)(g). These stability considerations are important, as CrO2(OH)2(g) is believed to be the product of water-induced degradation of the protective chromium oxide scale on stainless steel at elevated temperatures.     

Association of humic acid with metal (hydr)oxide-coated sands at solid-water interfaces

Mineral-bound humic acid (HA) can significantly modify the physicochemical properties of the mineral surfaces and vice versa, thereby influencing the fate and transport of organic pollutants in the subsurface. The effect of various mineral surfaces on the adsorption-desorption of dissolved bulk, terrestrial HA was evaluated using three model sorbents [uncoated, alpha-FeO(OH)-coated, and Al2O3-coated sands] at two equilibrium pH values. The results of SEM/EDS and XPS analyses revealed relatively uniform and stable metal (hydr)oxide coatings on quartz surface and the presence of the HA coating. Strong hysteresis effects were observed for both metal (hydr)oxide-coated sands whereas a weaker hysteresis effect was observed for uncoated sand, suggesting that the adsorption-desorption of HA to model sorbents is dependent on the affinity of chemical interactions between the HA and surface composition of model sorbents. Adsorption of HA molecules onto metal (hydr)oxide-coated sands can be attributed to ligand exchange for lower molecular weight (MW) HA fractions and hydrophobic interaction for higher MW HA fractions, illustrating that both kinetic and fractional adsorption-desorption of HA subcomponents are important considerations.     

Uniform metal (hydr)oxide particles from water/ionic liquid precursor (ILP) mixtures

We have recently shown that the hydrated ionic liquid tetrabutylammonium hydroxide (TBAH) is an efficient ionic liquid precursor (ILP) for the fabrication of ZnO/carbohydrate materials (D. Mumalo-Djokic, W. B. Stern, A. Taubert, Cryst. Growth Des. 2008, 8, 330). The current paper shows that ZnO is just one example out of the large group of technologically important metal (hydr)oxides that can be made using TBAH. Simply by using different metal acetates as precursors in TBAH, it is possible to make a wide variety of metal (hydr)oxides with well-defined size, morphology, and chemical composition. It is also possible to dope metal oxide particles or to synthesize mixed metal oxide particles, and therefore to control properties like magnetism.     

A new radiotracer method of adsorption studies at metal oxide/aqueous electrolyte interface

Adsorption of inorganic ions at the titania/electrolyte solution interfaces has been studies using a radioisotopic technique. Adsorption evaluated from uptake of radioactivity from the solution is compared with that obtained from sediment radioactivity.     

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides. I. Effects of pH

The study of mercury sorption products in model systems using appropriate in situ molecular-scale probes can provide detailed information on the modes of sorption at mineral/water interfaces. Such studies are essential for assessing the influence of sorption processes on the transport of Hg in contaminated natural systems. Macroscopic uptake of Hg(II) on goethite (alpha-FeOOH), gamma-alumina (gamma-Al(2)O(3)), and bayerite (beta-Al(OH)(3)) as a function of pH has been combined with Hg L(III)-edge EXAFS spectroscopy, FTIR spectroscopy, and bond valence analysis of possible sorption products to provide this type of information. Macroscopic uptake measurements show that Hg(II) sorbs strongly to fine-grained powders of synthetic goethite (Hg sorption density Gamma=0.39-0.42 micromol/m(2)) and bayerite (Gamma=0.39-0.44 micromol/m(2)), while sorbing more weakly to gamma-alumina (Gamma=0.04-0.13 micromol/m(2)). EXAFS spectroscopy on the sorption samples shows that the dominant mode of Hg sorption on these phases is as monodentate and bidentate inner-sphere complexes. The mode of Hg(II) sorption to goethite was similar over the pH range 4.3-7.4, as were those of Hg(II) sorption to bayerite over the pH range 5.1-7.9. Conversion of the gamma-Al(2)O(3) sorbent to a bayerite-like phase in addition to the apparent reduction of Hg(II) to Hg(I), possibly by photoreduction during EXAFS data collection, resulted in enhanced Hg uptake from pH 5.2-7.8 and changes in the modes of sorption that correlate with the formation of the bayerite-like phase. Bond valence calculations are consistent with the sorption modes proposed from EXAFS analysis. EXAFS analysis of Hg(II) sorption products on a natural Fe oxyhydroxide precipitate and Al/Si-bearing flocculent material showed sorption products and modes of surface attachment similar to those for the model substrates, indicating that the model substrates are useful surrogates for the natural sediments.     

Immobilization of nanofibrous metal oxides on microfibers: a macrostructured catalyst system functionalized with nanoscale fibrous metal oxides

Nanofibrous LaMnO(3) can be immobilized on macrostructured materials using carbon nanofibers as templates; their application as macro-nanostructured catalysts are also presented.