Silver-based hybrid materials from meta- or para-phosphonobenzoic acid: influence of the topology on silver release in water.

Three novel silver-based metal-organic frameworks materials, which were synthesized from either 3-phosphono or 4-phosphonobenzoic acid and silver nitrate, are reported. The novel hybrids were synthesized under hydrothermal conditions; the pH of the reaction media was controlled by adding different quantities of urea thereby producing different topologies. Compound 1 (Ag3(4-PO3-C6H4-COO)), synthesized in the presence of urea, exhibits a compact 3D structure in which both phosphonic acid and carboxylic acid functional groups are linked to the silver-based inorganic network. Compound 2 (Ag(4-PO3H-C6H4-COOH)), which was synthesized at lower pH (without urea), has a layered structure in which only the phosphonic acid functional groups from 4-phosphonobenzoic acid moieties are linked to the silver inorganic network; the carboxylic acid groups being engaged in hydrogen bonds. Finally, material 3 (Ag(3-PO3H-C6H4-COOH)) was synthesized from 3-phosphonobenzoic acid and silver nitrate without urea. This material 3 features a layered structure exhibiting carboxylic acid functional groups linked via hydrogen bonds in the interlayer space. After the full characterization of these materials (single X-ray structure, IR, TGA), their ability to release silver salts in aqueous environment was measured. Silver release, determined in aqueous solution by cathodic stripping voltammetry, shows that the silver release capacity of these materials is dependent on the topology of the hybrids. The more compact structure 1 is extremely stable in water with only trace levels of silver ions being detected. On the other hand, compounds 2 and 3, in which only the phosphonic acid functional groups were bonded to the inorganic network, released larger quantities of silver ions into aqueous solution. These results which were compared with the silver release of the previously described compound 4 (Ag6(3-PO3-C6H4-COO)2). The results clearly show that the release capacity of silver-based metal organic framework can be tuned by modifying their topology which, in the present study, is governed by the regio-isomer of the organic precursor and the synthetic conditions under which the hybrids are prepared.

A molecular material based on electropolymerized cobalt macrocycles for electrocatalytic hydrogen evolution.

An electrocatalytic material for the H2 evolution reaction (HER) in acidic aqueous solution has been prepared by electropolymerization of Co(ii) dibenzotetraaza[14] annulene (CoTAA). Chemical analysis by X-ray photoelectron spectroscopy (XPS) confirms that the structural integrity of the [Co(II)-N4] motif is preserved in the poly-CoTAA film. In acetate buffer solution at pH 4.6, an overpotential η = -0.57 V is required to attain a catalytic current density -ik = 1 mA cmgeom(-2). The faradaic efficiency of poly-CoTAA for the HER is 90% over a period of one hour of electrolysis, but there is a decrease of the apparent concentration of Co sites after prolonged H2 production, which we ascribe to partial demetallation of the poly-CoTAA film at negative potentials.

Electrochemistry of cytochrome c immobilized on cardiolipin-modified electrodes: a probe for protein-lipid interactions.

Electrochemistry of cytochrome c (cyt c) immobilized on a cardiolipin (CL)/phosphatidylcholine (PC) film supported on a glassy carbon electrode was investigated using variable-frequency AC voltammetry. At low ionic strength, we observed two redox-active subpopulations characterized by distinct values of potential (E1/2) and electron transfer rate constant (k(ET)). At high ionic strength, only one subpopulation was detected, consistent with the existence of very stable cyt c-CL adducts, most probably formed by hydrophobic interactions between the protein and the fatty acid (FA) chains carried by CL. This subpopulation exhibits a comparatively high k(ET) value (> 300 s(-1)) apparently changing with the structure of the FA chains of CL, i.e. 18:2(n - 6) or 14:0. Our study suggests that electrochemistry can be a useful technique for probing protein-lipid interactions, and more particularly the role played by the specific structure of the FA chains of CL on cyt c binding.

Natural organic matter quantification in the waters of a semiarid freshwater wetland (Tablas de Daimiel, Spain).

Dissolved organic matter (DOM) concentrations have been measured in the waters of a semiarid freshwater wetland, the Tablas de Daimiel, Spain, when the system-characterised by variable hydroperiodicity conditions, was completely flooded (February 2011). Fluxes of DOM from the wetland soils to the overlying waters were measured by using a passive diffusion sampler (peeper). Not only dissolved organic carbon (DOC) concentrations were measured but refractory organic matter (ROM, usually known as humic substances) was also quantified using a novel voltammetric method. Fluorescence spectra were recorded to help in selecting the appropriate standard for ROM quantification, test the homogeneity of DOM in the waters and get an indication of their source. The results obtained show a 7-fold increase in measured ROM concentrations from the Gigüela River to the outlet, which points to a net exportation of ROM from the wetland and to the existence of an internal source of ROM in the system, probably diffusion from the wetland soils. This hypothesis is confirmed by the flux of ROM from the soils to the water column measured with the peeper and by the common fluorescence characteristics of column and interstitial waters. The smaller increase in DOC concentrations along the wetland, in spite of the higher DOC fluxes from soils, suggests that there is significant turnover of organic carbon (OC) in the water column. The system acts as a major carbon sink but, when flooded, exports OC as DOM.

A binuclear iron-thiolate catalyst for electrochemical hydrogen production in aqueous micellar solution.

The substituted iron-thiolate complex [Fe(2)(µ-bdt)(CO)(4){P(OMe)(3)}(2)] (bdt=benzenedithiolate) is an active catalyst for electrochemical hydrogen production in aqueous sodium dodecyl sulfate solution, with a high apparent rate constant of 4×10(6) M(-1) s(-1). The half-peak potential for catalysis of proton reduction is less negative than -0.6 V versus the standard hydrogen electrode at pH 3. Voltammetric data are consistent with the rate of electrode reaction controlled by diffusion. A mechanism that begins with the rapid protonation of the iron-thiolate catalyst is proposed. The Faradaic efficiency in diluted HCl solutions is close to 100%, but the catalytic activity decayed after about twelve turnovers when electrolysis was carried out in the presence of acetic acid.

Electrochemical hydrogen production in aqueous micellar solution by a diiron benzenedithiolate complex relevant to [FeFe] hydrogenases.

The diiron hydrogenase model Fe(2)(bdt)(CO)(6) (1, bdt = benzenedithiolate) was dispersed in aqueous micellar solution prepared from sodium dodecyl sulfate (SDS). Aqueous solution of 1 showed no sign of decomposition when left in contact with air over a period of several days. Current-potential responses recorded at a dropping mercury electrode over pH 7-3 were consistent with reduction of freely diffusing species. Catalysis of proton reduction was observed at pH < 6 with current densities exceeding 0.5 mA cm(-2) at an acid-to-catalyst ratio of 17. Bulk electrolysis at -0.66 V vs. SHE of solution of 1 at pH 3 confirmed the production of hydrogen with a Faradaic efficiency close to 100%. A mechanism involving initial reduction of 1 and subsequent proton-coupled electron transfer is proposed.

A simple method for quantifying the humic content of commercial products.

A method based on an analytical technique, initially developed for quantifying aquatic refractory organic matter (often called humics), has been applied to commercial samples claiming to contain humic-type substances. At present, no method exists for quantifying the humic content on this type of sample. The analytical method is based on measuring the peak current obtained by adsorptive stripping voltammetry of the complex formed by refractory organic matter in the presence of trace amounts of Mo(VI). The quantification procedure requires the response obtained for the unknown sample to be compared with the response obtained with International Humic Substance Society (IHSS) reference humic substances. A very simple procedure that enables the humic content of any sample to be expressed as IHSS standard equivalents is described in detail. The method is highly selective, reproducible and suitable for routine analysis.

Transfer of highly hydrophilic ions from water to nitrobenzene, studied by three-phase and thin-film modified electrodes.

The study by voltammetry of hydrophilic ion transfers across the interface between an aqueous solution and an immiscible organic solvent is limited by the presence of supporting electrolytes in both phases. Such a study is impossible for ions having a higher affinity for water than ions of the electrolytes. Indirectly, methods based on modified solid electrodes can be used; these are obtained by the deposition of an organic phase containing a molecule having redox properties, the modified electrode being in contact with an aqueous solution of the appropriate electrolyte. The three-phase electrode is very convenient for that purpose. However, this experimental tool also has its own limitation, due mainly to the redox species produced in the organic phase. The oxidized, or reduced, form of the redox molecule must have a very low affinity for water, as otherwise its transfer masks that of the ion under study. Ferrocene is almost useless because of the affinity of the ferrocenium cation for water, decamethylferrocene being a better choice. The present work illustrates how the use of lutetium bisphthalocyanines widely expands the possibilities, as these molecular sandwich complexes can be reduced as well as oxidized, the products of the reactions having a very low affinity for water. This made the determination of the Gibbs energy possible for the transfers of highly hydrophilic ions from water to nitrobenzene: Cl(-) (40 kJ mol(-1)), F(-) (57 kJ mol(-1)), H2PO4(-) (64 kJ mol(-1)). Nothing being really known about the transfer of F(-) or H2PO4(-) from water to organic solvents, these are the first values ever published. H(+), OH(-), and HSO4(-) have also been studied, showing that these species, which have a poor affinity for nitrobenzene, are prone to association reactions with the reduced or oxidized forms of the lutetium bisphthalocyanine.

Quantification of refractory organic substances in freshwaters: further insight into the response of the voltammetric method.

A recently published method for quantifying refractory organic matter (often referred to as humic substances) in freshwaters was applied to a wide range of International Humic Substance Society (IHSS) humic compounds in order to (i) gain a better understanding of the mechanism of the voltammetric response which is the basis of the analytical method and (ii) provide guidance on choosing the optimal standard to be used. At the same time, the sensitivity of the technique has been increased by switching from the pulse mode initially proposed to the square-wave mode. The results obtained show that (i) differences in adsorption onto the electrode rather than differences in complexation strength are responsible for the differences in the intensity of the signal obtained for the different humic compounds, (ii) carboxylate, N- and S-containing groups do not play a role in the voltammetric signal.

Sb(III) oxidation by iodate in seawater: a cautionary tale.

Knowledge of antimony redox kinetics is crucial in understanding the impact and fate of antimony in the environment. The oxidation of Sb(III) with iodate was measured in 0.5 mol L(-1) NaCl solutions as a function of pH at environmentally significant concentrations of antimony and iodate. The oxidation of Sb(III) with iodate is pH dependent: no measurable oxidation is observed below pH 9. The undissociated Sb(OH)3 does not react with iodate and the formation of significant amounts of Sb(OH)4- is needed for the reaction to take place. It is thus unlikely that iodate oxidizes Sb(III) in seawater. Our results support that the observed presence of the thermodynamically unstable Sb(III) in oxic waters can be due to the kinetic stabilization of the trivalent state vis-à-vis some common abiotic oxidants at natural pH values. However, caution must be exercised because the presence of iodate in seawater favours fast oxidation of Sb(III) if water samples are acidified, as is the case in many analytical procedures.

Coadsorption of carbofuran and lead at the air/water interface. Possible occurrence of non-volatile pollutant cotransfer to the atmosphere.

The weak solubility of carbofuran allows adsorption at the air/water interface. Carbofuran-rich layers can then induce the coadsorption of metallic salts such as lead nitrate; on the other hand, when carbofuran is missing, no adsorption of this salt takes place. This phenomenon was quantitatively studied through surface tension measurements under concentration conditions close to the environmental ones. Heavy metal salt adsorbed about ten times more than carbofuran. Evidence was then provided that the simultaneous presence of both pollutants in water favours their adsorption and passing from water to the atmosphere through mechanisms such as bubbling.

Lutetium bis(tetra-tert-butylphthalocyaninato): a superior redox probe to study the transfer of anions and cations across the water/nitrobenzene interface by means of square-wave voltammetry at the three-phase electrode.

The redox properties of lutetium bis(tetra-tert-butylphthalocyaninato) (LBPC) have been studied in nitrobenzene that is deposited as a microfilm on the surface of highly oriented pyrolytic graphite electrodes. The behavior of the modified electrode, which is immersed in an aqueous electrolyte solution, is typical for the three-phase electrode (Scholz, F.; Komorsky-Lovric, S.; Lovric, M. Electrochem. Comm. 2000, 2, 112-118). LBPC can be both oxidized and reduced in one electron reversible processes. The oxidation and the reduction of LBPC at the graphite/nitrobenzene interface is accompanied by the transfer of anion or cation, respectively, from the aqueous phase into the organic layer. Thus, using LBPC as a redox probe for the three-phase electrode, the transfer of both anions and cations across the water/nitrobenzene interface can be studied in a single experiment. The hydrophobicity of LBPC is so high that it enables inspection of cations and anions with Delta (nb)(w) (G)(theta)(Cat+) < or = 43 kJ/mol and Delta (nb)(w) (G)(theta)(X-) < or = 50 kJ/mol, respectively. The direct transfer of Na(+) and Li(+) from water to nitrobenzene, mutually saturated, is achieved for the first time at a macroscopic water/nitrobenzene interface.

Comparative study of the thermodynamics and kinetics of the ion transfer across the liquid/liquid interface by means of three-phase electrodes.

A comparative study of the behavior of different sorts of three-phase electrodes applied for assessing the thermodynamics and kinetics of the ion transfer across the liquid/liquid (L/L) interface is presented. Two types of three-phase electrodes are compared, that is, a paraffin-impregnated graphite electrode at the surface of which a macroscopic droplet of an organic solvent is attached and an edge pyrolytic graphite electrode partly covered with a very thin film of the organic solvent. The organic solvent contains either decamethylferrocene or lutetium bis(tetra-tert-butylphthalocyaninato) as a redox probe. The role of the redox probe, the type of the electrode material, the mass transfer regime, and the effect of the uncompensated resistance are discussed. The overall electrochemical process at both three-phase electrodes proceeds as a coupled electron-ion transfer reaction. The ion transfer across the L/L interface, driven by the electrode reaction of the redox compound at the electrode/organic solvent interface, is independent of the type of redox probe. The ion transfer proceeds without involving any chemical coupling between the transferring ion and the redox probe. Both types of three-phase electrodes provide consistent results when applied for measuring the energy of the ion transfer. Under conditions of square-wave voltammetry, the coupled electron-ion transfer at the three-phase electrode is a quasireversible process, exhibiting the property known as "quasireversible maximum". The overall electron-ion transfer process at the three-phase electrode is controlled by the rate of the ion transfer. It is demonstrated for the first time that the three-phase electrode in combination with the quasireversible maximum is a new tool for assessing the kinetics of the ion transfer across the L/L interface.

Direct determination of tellurium and its redox speciation at the low nanogram level in natural waters by catalytic cathodic stripping voltammetry.

Tellurium is one of the elements recently identified as technologically critical and is becoming a new emergent contaminant. No reliable method exists for its determination in environmental samples such as natural waters. This gap is filled by the method described here; it allows the rapid detection of trace concentrations of Te(IV) and Te(VI) in surface waters by differential pulse cathodic stripping voltammetry. It is based on the proton reduction catalysed by the absorption of Te(IV) on the mercury electrode. Under our conditions (0.1 mol L(-1) HCl) a detection limit of about 5 ng L(-1) for a deposition time of 300 s is achieved. Organic matter does not represent a problem at low concentrations; higher concentrations are eliminated by adsorptive purification. Tellurium occurs primarily as Te(IV) and Te(VI) in natural waters. Thus, determining total Te requires the reduction of Te(VI) that it is not electroactive. A number of reduction procedures have been carefully evaluated and a method based on the addition of TiCl3 to the acidified samples has been proven to reduce Te(VI) at the trace level to Te(IV) reliably and quantitatively. Therefore, the procedure described allows the direct determination of total Te and its redox speciation. It is flexible, reliable and cost effective compared to any possible alternative method based on the common preconcentration-ICPMS approach. It is readily implementable as a routine method and can be deployed in the field with relative ease.

Photocatalytic hydrogen production using models of the iron-iron hydrogenase active site dispersed in micellar solution.

Iron-thiolate complexes of the type [Fe2 (µ-bdt)(CO)6-x P(OMe3 )x ] (bdt=S2 C6 H4 =benzenedithiolate, x≤2) are simplified models of iron-iron hydrogenase enzymes. Recently, we have shown that these water-insoluble organometallic complexes, when included into micelles formed by sodium dodecyl sulfate (SDS), are good catalysts for the electrochemical production of hydrogen in aqueous solutions at pH<6. We herein report that the all-CO derivative [Fe2 (µ-bdt)(CO)6 ] (1), owing to its comparatively low reduction potential, is also a robust molecular catalyst for visible-light-driven production of H2 in aqueous SDS solutions at pH 10.5. Irradiation at λ=455 nm of a system consisting of complex 1, Eosin Y as a sensitizer, and triethylamine as an electron donor produced up to 0.86 mL of H2 in 4.5 h, corresponding to a turnover number of 117 mol of H2 per mol of catalyst. In the presence of a large excess of sensitizer, the production of H2 lasted for more than 30 h, stressing the relative stability of complex 1 under the photocatalytic conditions used herein. Thermodynamic considerations and UV/Vis spectroscopy experiments suggest that the catalytic cycle begins with the photo-driven reduction of complex 1. The reduced intermediate reacts with a proton source to yield iron hydride. Subsequent reduction and protonation steps produce H2 , regenerating the starting complex. As a result, the iron-thiolate complex 1 is a versatile proton reduction catalyst that can utilize either solar or electrical energy inputs, providing a starting point for the construction of noble metal-free molecular systems for renewable H2 production.

Simple and simultaneous determination of glutathione, thioacetamide and refractory organic matter in natural waters by DP-CSV.

Although reduced sulphur substances, such as thiol compounds, contain extremely reactive functional groups in the cell, and influence metal speciation and solubility, very few techniques have been developed to quantify such substances in natural waters. In this paper we present a novel method that allows for the simultaneous identification and quantification of glutathione (GSH), thioacetamide-like compounds (TA), and refractory organic matter (ROM) by differential pulse cathodic stripping voltammetry (DP-CSV). Organic compounds are initially deposited on a mercury drop electrode at 0.000 V, pH 1.95, in the presence of ~200 nmol L(-1) Mo(VI), and then stripped, creating reduction peak currents at specific potentials. Using a 60-s deposition time, limits of detection (LODs) are 1 nmol L(-1), 81 nmol L(-1) and 14 µg C L(-1) for GSH, TA and ROM, respectively. By increasing the deposition time to 300 s, LOD is decreased to 0.2 nmol L(-1), 22 nmol L(-1) and 2 µg C L(-1), respectively. This method has a number of advantages in terms of its rapidity, low cost, and relative simplicity (due to the lack of derivatization and pre-concentration steps) and is also an effective method for simultaneously analysing GSH, TA and ROM in water. When not mixed in solution, GSH, L-cysteine and N-acetyl-L-cysteine, as well as TA-like compounds and thiourea, can be detected and identified by measuring their peak potential and standard addition, due to the acidic pH, which also allows for a longer preservation of the filtered sample. The new method described in this paper was tested along an entire river-seawater gradient of the Aulne Estuary (Brittany, France) to assess its capability in terms of determining these natural organic compounds in various surface waters.

Electrocatalytic hydrogen evolution from neutral water by molecular cobalt tripyridine-diamine complexes.

A cobalt complex with a tripyridine-diamine pentadentate ligand was found to be a highly active catalyst for electrochemical H2 production from neutral water, with an activity of 860 mol H2 (mol cat)(-1) h(-1) (cm(2) Hg)(-1) over 60 h CPE experiment at -1.25 V in a pH 7 phosphate buffer solution, without considerable deactivation.

Natural attenuation processes applying to antimony: a study in the abandoned antimony mine in Goesdorf, Luxembourg.

The processes leading to the attenuation of the antimony concentration in the water draining from the abandoned antimony mine in Goesdorf, Luxembourg, have been studied. Antimony has been mined in Goesdorf since Roman times from a stibnite-rich mesothermal vein system hosted in metasedimentary schist. The draining waters have pH values between 7 and 8 because the mineralization itself contains calcite and dolomite. This study combines the identification of minerals in the supergene zone with the application of bulk techniques (e.g., measurement of antimony in the waters of the adit and the creek draining the mine, sediment sequential extractions) over a period of five years. Antimony concentrations in the water that leaves the supergene zone are controlled by the dissolution of stibnite and the subsequent formation of Sb(III) oxides and sulphates. The relative proportions of the main secondary minerals can be qualitatively estimated as follows: 70% valentinite, 15% senarmontite and 12% sulphates (coquandite, klebelsbergite and peretaite). Further antimony attenuation along the adit and the creek that drain the mine waters is due partly to dilution, through mixing with waters that have not been in contact with the ore, and partly to sorption onto amorphous iron and manganese oxides present in the colluvial sediments.

A comparative study of the anion transfer kinetics across a water/nitrobenzene interface by means of electrochemical impedance spectroscopy and square-wave voltammetry at thin organic film-modified electrodes.

The kinetics of the transfer of a series of hydrophilic monovalent anions across the water/nitrobenzene (W/NB) interface has been studied by means of thin organic film-modified electrodes in combination with electrochemical impedance spectroscopy and square-wave voltammetry. The studied ions are Cl-, Br-, I-, ClO4-, NO3-, SCN-, and CH3COO-. The electrode assembly comprises a graphite electrode (GE) covered with a thin NB film containing a neutral strongly hydrophobic redox probe (decamethylferrocene or lutetium bis(tetra-tert-butylphthalocyaninato)) and an organic supporting electrolyte. The modified electrode is immersed in an aqueous solution containing a supporting electrolyte and transferring ions, and used in a conventional three-electrode configuration. Upon oxidation of the redox probe, the overall electrochemical process proceeds as an electron-ion charge-transfer reaction coupling the electron transfer at the GE/NB interface and compensates ion transfer across the W/NB interface. The rate of the ion transfer across the W/NB interface is the limiting step in the kinetics of the overall coupled electron-ion transfer reaction. Moreover, the transferring ion that is initially present in the aqueous phase only at a concentration lower than the redox probe, controls the mass transfer regime in the overall reaction. A rate equation describing the kinetics of the ion transfer that is valid for the conditions at thin organic film-modified electrodes is derived. Kinetic data measured with two electrochemical techniques are in very good agreement.

The effect of the presence of trace metals on the oxidation of Sb(III) by hydrogen peroxide in aqueous solution.

Despite its importance for understanding the behaviour of antimony in the environment, the oxidation kinetics of Sb(III) with natural oxidants is still not well understood. We have studied the oxidation of Sb(III) by hydrogen peroxide on a time scale of hours in the presence of some trace metals, Cu(II), Mn(II), Zn(II) and Pb(II), under pH and concentration conditions close to natural ones. The effects that these trace metals have on Sb(iii) oxidation by hydrogen peroxide vary. Zn(II) had no catalytic effect at all, but Cu(II), Mn(II) and Pb(II) did, though their effects were not uniform. Cu(II) significantly accelerated the reaction, which remained first-order with respect to Sb(III) at any Cu(II) concentration tested. Pb(II) and Mn(II) also enhanced the reaction rates, but the apparent order of the reaction with respect to Sb(III) changed to two. The trace metal effect observed was concentration dependent for Pb(II). The addition of the hydroxyl radical scavenger 2-propanol suggests that the trace metal catalytic effect observed involves the action of hydroxyl radicals, but that they are not responsible for the oxidation of Sb(III) by H2O2 in the absence of trace metals. The fact that Sb(III) can be oxidized by hydroxyl radicals present in water, even if it is not capable of producing them, has important environmental implications because hydroxyl radicals are known to be abundant in many natural waters such as seawater, humic-rich surface waters or rainwater.