Electrochemical Method for the Design of New Possible Gadolinium-Based Contrast Agents.

Magnetic resonance imaging (MRI) is a technique that employs strong magnetic fields and radio frequencies to generate detailed images of the body's interior. In oncology patients, gadolinium-based contrast agents (GBCAs) are frequently administered to enhance the visualization of tumors. Those contrast agents are gadolinium chelates, characterized by high stability that prevents the release of the toxic gadolinium ion into the body.

In Situ X-ray Absorption Spectroscopy Study of the Deactivation Mechanism of a Ni-SrTiO Photocatalyst Slurry Active in Water Splitting.

We used in situ X-ray absorption spectroscopy (XAS) to investigate the composition-performance correlation of Ni-SrTiO photocatalysts active for water splitting. After preparation and exposure to ambient conditions, the Ni particles on SrTiO consist of Ni(0) and Ni(II) phases, with a 4:1 at % ratio, in a metal/oxide core/shell configuration, as confirmed by XPS and TEM-EDX. In situ XAS experiments using an aqueous slurry of the Ni-SrTiO photocatalyst and simultaneous continuous exposure to 365 nm light with a power density of 100 mW cm and the X-rays do not reveal significant changes in oxidation state of the Ni particles.

Magnetron Sputtering Formation of Germanium Nanoparticles for Electrochemical Lithium Intercalation.

In the drive towards increased lithium based battery capacity, germanium is an attractive material due to its very high lithium storage capacity, second only to silicon. The persistent down-side is the considerable embrittlement accompanying its remarkable volume expansion of close to 300 %. A proven method to accommodate for this lattice expansion is the reduction of the size towards the nanoscale at which the fracturing is prevented by "breathing".

Metastable Ni(I)-TiO Photocatalysts: Self-Amplifying H Evolution from Plain Water without Noble Metal Co-Catalyst and Sacrificial Agent.

Decoration of semiconductor photocatalysts with cocatalysts is generally done by a step-by-step assembly process. Here, we describe the self-assembling and self-activating nature of a photocatalytic system that forms under illumination of reduced anatase TiO nanoparticles in an aqueous Ni solution. UV illumination creates a Ni/TiO/Ti photocatalyst that self-activates and, over time, produces H at a higher rate.

Electrochemical Iodination through the In Situ Generation of Iodinating Agents: A Promising Green Approach.

The synthesis of iodinated compounds using cheap, simple, and green strategies is of fundamental importance. Iodination reactions are mainly used to synthesize useful intermediates, especially in the pharmaceutical field, where they are employed for the production of contrast media or of iodinated active pharmaceutical ingredients. Traditional synthetic methods suffer from the use of erosive, toxic, or hazardous reactants.

Copper Oxide-Based Photocatalysts and Photocathodes: Fundamentals and Recent Advances.

This work aims at reviewing the most impactful results obtained on the development of Cu-based photocathodes. The need of a sustainable exploitation of renewable energy sources and the parallel request of reducing pollutant emissions in airborne streams and in waters call for new technologies based on the use of efficient, abundant, low-toxicity and low-cost materials. Photoelectrochemical devices that adopts abundant element-based photoelectrodes might respond to these requests being an enabling technology for the direct use of sunlight to the production of energy fuels form water electrolysis (H) and CO reduction (to alcohols, light hydrocarbons), as well as for the degradation of pollutants.

ORR in Non-Aqueous Solvent for Li-Air Batteries: The Influence of Doped MnO-Nanoelectrocatalyst.

One of the major drawbacks in Lithium-air batteries is the sluggish kinetics of the oxygen reduction reaction (ORR). In this context, better performances can be achieved by adopting a suitable electrocatalyst, such as MnO. Herein, we tried to design nano-MnO tuning the final ORR electroactivity by tailoring the doping agent (Co or Fe) and its content (2% or 5% molar ratios).

Role of Synthetic Parameters on the Structural and Optical Properties of N,Sn-Copromoted Nanostructured TiO: A Combined Ti K-Edge and Sn L-Edges X-ray Absorption Investigation.

Sn-modification of TiO photocatalysts has been recently proposed as a suitable strategy to improve pollutant degradation as well as hydrogen production. In particular, visible light activity could be promoted by doping with Sn species, which are, however, thermally unstable. Co-promotion with N and Sn has been shown to lead to synergistic effects in terms of visible light activity, but the underlying mechanism has, so far, been poorly understood due to the system complexity.

Chlorine Dioxide Degradation Issues on Metal and Plastic Water Pipes Tested in Parallel in a Semi-Closed System.

Chlorine dioxide (ClO) has been widely used as a disinfectant in drinking water in the past but its effects on water pipes have not been investigated deeply, mainly due to the difficult experimental set-up required to simulate real-life water pipe conditions. In the present paper, four different kinds of water pipes, two based on plastics, namely random polypropylene (PPR) and polyethylene of raised temperature (PERT/aluminum multilayer), and two made of metals, i.e.

Structure and Stability of a Copper(II) Lactate Complex in Alkaline Solution: a Case Study by Energy-Dispersive X-ray Absorption Spectroscopy.

Energy-dispersive X-ray absorption spectroscopy was applied, aimed at solving the problem of the structure and stability of a copper(II) lactate complex in alkaline solution, used as a precursor for the electrodeposition of CuO. The application of multiple scattering calculations to the simulation of the X-ray absorption near-edge structure part of the spectra allowed an accurate resolution of the structure: the copper(II) cation is surrounded by four lactate ions in a distorted tetrahedral environment, with the lactate anions acting as monodentate ligands. This results in an atomic arrangement where copper is surrounded by four oxygen atoms located at quite a short distance (ca.

Observation of charge transfer cascades in α-FeO/IrO photoanodes by operando X-ray absorption spectroscopy.

Electrochemical devices for energy conversion and storage are central for a sustainable economy. The performance of electrodes is driven by charge transfer across different layer materials and an understanding of the mechanistics is pivotal to gain improved efficiency. Here, we directly observe the transfer of photogenerated charge carriers in a photoanode made of hematite (α-FeO) and a hydrous iridium oxide (IrO) overlayer, which plays a key role in photoelectrochemical water oxidation.

An Efficient CuxO Photocathode for Hydrogen Production at Neutral pH: New Insights from Combined Spectroscopy and Electrochemistry.

Light-driven water splitting is one of the most promising approaches for using solar energy in light of more sustainable development. In this paper, a highly efficient p-type copper(II) oxide photocathode is studied. The material, prepared by thermal treatment of CuI nanoparticles, is initially partially reduced upon working conditions and soon reaches a stable form.

3D-printed photo-spectroelectrochemical devices for in situ and in operando X-ray absorption spectroscopy investigation.

Three-dimensional printed multi-purpose electrochemical devices for X-ray absorption spectroscopy are presented in this paper. The aim of this work is to show how three-dimensional printing can be a strategy for the creation of electrochemical cells for in situ and in operando experiments by means of synchrotron radiation. As a case study, the description of two cells which have been employed in experiments on photoanodes for photoelectrochemical water splitting are presented.

The Influence of Carbonaceous Matrices and Electrocatalytic MnO₂ Nanopowders on Lithium-Air Battery Performances.

Here, we report new gas diffusion electrodes (GDEs) prepared by mixing two different pore size carbonaceous matrices and pure and silver-doped manganese dioxide nanopowders, used as electrode supports and electrocatalytic materials, respectively. MnO₂ nanoparticles are finely characterized in terms of structural (X-ray powder diffraction (XRPD), energy dispersive X-ray (EDX)), morphological (SEM, high-angle annular dark field (HAADF)-scanning transmission electron microscopy (STEM)/TEM), surface (Brunauer Emmet Teller (BET)-Barrett Joyner Halenda (BJH) method) and electrochemical properties. Two mesoporous carbons, showing diverse surface areas and pore volume distributions, have been employed.

IrO2-based disperse-phase electrocatalysts: a complementary study by means of the cavity-microelectrode and ex-situ X-ray absorption spectroscopy.

In this work, IrO(2)-based powders are screened by cyclic voltammetry for the determination of the electrochemical active sites and for the qualitative evaluation of the iridium atoms speciation. All results are obtained using a cavity-microelectrode as powder holder, thus exploiting the features of this innovative tool, whose best potentialities have been recently introduced by our group. All the studied materials have been prepared by the sol-gel technique and differ in calcination temperature and method of mixing the metal oxide precursors.

Quantitative studies on electrode material properties by means of the cavity microelectrode.

The determination of the number of active sites is a key issue in the evaluation of electrode materials for any electrochemical application. Nonetheless, and particularly in the case of powder materials, a commonly accepted method to determine the actual density of active sites is not yet available, mainly because a method to quantify the amount of material under investigation is missing. In this study, we propose the use of the cavity microelectrode (C-ME, i.

Impact of self-assembly composition on the alternate interfacial electron transfer for electrostatically immobilized cytochrome c.

We report on the effects of self-assembled monolayer (SAM) dilution and thickness on the electron transfer (ET) event for cytochrome c (CytC) electrostatically immobilized on carboxyl terminated groups. We observed biphasic kinetic behavior for a logarithmic dependence of the rate constant on the SAM carbon number (ET distance) within the series of mixed SAMs of C(5)COOH/C(2)OH, C(10)COOH/C(6)OH, and C(15)COOH/C(11)OH that is in overall similar to that found earlier for the undiluted SAM assemblies. However, in the case of C(15)COOH/C(11)OH and C(10)COOH/C(6)OH mixed SAMs a notable increase of the ET standard rate constant was observed, in comparison with the corresponding unicomponent (omega-COOH) SAMs.

Ion-channel sensors based on ETH 1001 ionophore embedded in charged-alkanethiol self-assembled monolayers on gold electrode surfaces.

An ion-channel sensor was demonstrated by immobilizing ETH 1001, an ionophore for ion-selective electrodes, on a gold electrode surface. The approach for preparing the sensor was to incorporate the ionophore into a mixed self-assembled monolayer of 10-mercaptodecanesulfonate and 11-hydroxy-1-undecanethiol formed on the surface. The voltammetric responses for the thus prepared sensor to the primary cation Ca(2+) were observed by using [Fe(CN)(6)](3-/4-) as an electroactive marker.

Selective electrodehalogenation of bromophenols on Ag electrocatalyst.

Among the innovative technologies for the detoxification and disposal of industrial effluents, our recently described electroreductive dehalogenation of organic halides on silver electrocatalyst provides a promising route, to be easily "plugged-in" into integrated waste treatments. Although electroreductions do not lead to total substrate mineralization, complete and selective dehalogenation may be achieved by the appropriate choice of the cathode material, thus decreasing the biotoxicity of the waste. In particular the use of silver as electrocatalyst greatly reduces the energy demand, and ensures higher yields and no by-products also when treating highly toxic aromatic halides.