On the Electrochemical Growth of a Crystalline p-n Junction From Aqueous Solutions.

Our society largely relies on inorganic semiconductor devices which are, so far, fabricated using expensive and complex processes requiring ultra-high vacuum equipment. Here we report on the possibility of growing a p-n junction taking advantage of electrochemical processes based on the use of aqueous solutions. The growth of the junction has been carried out using the Electrochemical Atomic Layer Deposition (E-ALD) technique, which allowed to sequentially deposit two different semiconductors, CdS and Cu2S, on an Ag(111) substrate, in a single procedure. The growth process was monitored in situ by Surface X-Ray Diffraction (SXRD) and resulted in the fabrication of a thin double-layer structure with a high degree of crystallographic order and a well-defined interface. The high-performance electrical characteristics of the device were analysed ex-situ and show the characteristic feature of a diode.

Spin-dependent charge transmission through chiral 2T3N self-assembled monolayer on Au.

A gold surface is functionalized by chemisorption of the enantiopure N,N'-bis-[2,2';5',2″]tert-thiophene-5-yl methylcyclohexane-1,2-diamine (2T3N), a chiral oligothiophene derivative, via overnight incubation in a 2T3N ethanol solution. The Au|2T3N interface is characterized by x-ray photoelectron circular dichroism and comparing x-ray photoemission spectroscopy and electro-desorption results. Charge transmission at the Au|2T3N| solution interface is characterized by recording the cyclic voltammetry of the Fe(III)/Fe(II) reversible redox couple, finding a charge transfer rate constant, k°, variation from 1 × 10-1 to 3.3 × 10-2 cm s-1, when comparing the bare Au and the Au|2T3N interfaces, respectively. The "anomalous" high value of k° found for the chiral Au|2T3N interface can be rationalized on the basis of the chiral-induced spin selectivity effect, as further proved by magnetic-conductive atomic force microscopy measurements at room temperature. A spin polarization of about 30% is found.

Ethanol electro-oxidation reaction on the Pd(111) surface in alkaline media: insights from quantum and molecular mechanics.

The ethanol electro-oxidation catalyzed by Pd in an alkaline environment involves several intermediate reaction steps promoted by the hydroxyl radical, OH. In this work, we report on the dynamical paths of the first step of this oxidation reaction, namely the hydrogen atom abstraction CH3CH2OH + OH → CH3CHOH + H2O, occurring at the Pd(111) surface and address the thermodynamic stability of the adsorbed reactants by means of quantum and molecular mechanics calculations, with special focus on the effect of the solvent. We have found that the impact of the solvent is significant for both ethanol and OH, contributing to a decrease in their adsorption free energies by a few dozen kcal mol-1 with respect to the adsorption energy under vacuum. Furthermore, we observe that hydrogen atom abstraction is enhanced for those simulation paths featuring large surface-reactant distances, namely, when the reactants weakly interact with the catalyst. The picture emerging from our study is therefore that of a catalyst whose coverage in an aqueous environment is largely dominated by OH with respect to ethanol. Nevertheless, only a small amount of them, specifically those weakly bound to the catalyst, is really active in the ethanol electro-oxidation reaction. These results open the idea of a rational design of co-catalysts based on the tuning of surface chemical properties to eventually enhance exchange current density.

On the Dynamics of the Carbon-Bromine Bond Dissociation in the 1-Bromo-2-Methylnaphthalene Radical Anion.

This paper studies the mechanism of electrochemically induced carbon-bromine dissociation in 1-Br-2-methylnaphalene in the reduction regime. In particular, the bond dissociation of the relevant radical anion is disassembled at a molecular level, exploiting quantum mechanical calculations including steady-state, equilibrium and dissociation dynamics via dynamic reaction coordinate (DRC) calculations. DRC is a molecular-dynamic-based calculation relying on an ab initio potential surface. This is to achieve a detailed picture of the dissociation process in an elementary molecular detail. From a thermodynamic point of view, all the reaction paths examined are energetically feasible. The obtained results suggest that the carbon halogen bond dissociates following the first electron uptake follow a stepwise mechanism. Indeed, the formation of the bromide anion and an organic radical occurs. The latter reacts to form a binaphthalene intrinsically chiral dimer. This paper is respectfully dedicated to Professors Anny Jutand and Christian Amatore for their outstanding contribution in the field of electrochemical catalysis and electrosynthesis.

Low-Cost Potentiometric Sensor for Chloride Measurement in Continuous Industrial Process Control.

Recently, the new updates in legislation about drinking water control and human health have increased the demand for novel electrochemical low-cost sensors, such as potentiometric ones. Nowadays, the determination of chloride ion in aqueous solutions has attracted great attention in several fields, from industrial processes to drinking water control. Indeed, chloride plays a crucial role in corrosion, also influencing the final taste of beverages, especially coffee. The main goal is to obtain devices suitable for continuous and real-time analysis. For these reasons, we investigated the possibility to develop an easy, low-cost potentiometric chloride sensor, able to perform analysis in aqueous mediums for long immersion time and reducing the need of periodic calibration. We realized a chloride ion selective electrode made of Ag/AgCl sintered pellet and we tested its response in model solutions compatible with drinking water. The sensor was able to produce a stable, reproducible, and accurate quantification of chloride in 900 s, without the need for a preliminary calibration test. This opens the route to potential applications of this sensor in continuous, in situ, and real time measurement of chloride ions in industrial processes, with a reduced need for periodic maintenance.

Electrodeposition of Molybdenum Disulfide (MoS2) Nanoparticles on Monocrystalline Silicon.

Molybdenum disulfide (MoS2) has attracted great attention for its unique chemical and physical properties. The applications of this transition metal dichalcogenide (TMDC) range from supercapacitors to dye-sensitized solar cells, Li-ion batteries and catalysis. This work opens new routes toward the use of electrodeposition as an easy, scalable and cost-effective technique to perform the coupling of Si with molybdenum disulfide. MoS2 deposits were obtained on n-Si (100) electrodes by electrochemical deposition protocols working at room temperature and pressure, as opposed to the traditional vacuum-based techniques. The samples were characterized by X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and Rutherford Back Scattering (RBS).

Influence of Chiral Compounds on the Oxygen Evolution Reaction (OER) in the Water Splitting Process.

Results are presented concerning the influence on the water splitting process of enantiopure tartaric acid present in bulk solution. Stainless steel and electrodeposited nickel are used as working electrode (WE) surface. The latter is obtained by electrodeposition on the two poles of a magnet. The influence and role played by the chiral compound in solution has been assessed by comparing the current values, in cyclic voltammetry (CV) experiments, recorded in the potential range at which oxygen evolution reaction (OER) occurs. In the case of tartaric acid and nickel WE a spin polarization of about 4% is found. The use of the chiral environment (bulk solution) and ferromagnetic chiral Ni electrode allows for observing the OER at a more favorable potential: About 50 mV (i.e., a cathodic, less positive, shift of the potential at which the oxygen evolution is observed).

Sustainable and effective reconditioning of SPR gold chips functionalized with molecularly imprinted polynorepinephrine.

Surface Plasmon Resonance (SPR) technology has revolutionized the study of affinity-based biomolecular interactions, offering label-free and real-time analysis capabilities. However, traditional SPR gold chips have been viewed as disposable due to challenges in post-use reconditioning, leading to significant resource wastage and increased costs. To address this issue, we propose a novel approach utilizing polynorepinephrine-based (PNE) Molecularly Imprinted Bio-Polymers (MIBPs) as alternative receptors to conventional antibodies. Self-adhesive MIBPs do not require covalent immobilization. This enables efficient and rapid chip functionalization and post-use removal, facilitating multiple reuses of the plasmon source without compromising analytical performance. We conducted a thorough characterization and data analysis, confirming the robustness and repeatability of a single MIBP-functionalized chip for human IgG detection. 10 cycles of reconditioning and reuse, assayed by 60 kinetic calibrations, were performed. Our findings demonstrate the potential indefinite reuse of SPR chips facilitated by PNE MIBPs, with implications for streamlining test development and routine implementation in SPR biosensing applications. Therefore, they represent a sustainable solution to the longstanding challenge of disposable SPR gold chips also by reducing the reliance on animal-derived Abs for bioanalytic testing. Being also extremely low-cost and green, PNE-based MIBPs minimize the ecological footprint associated with traditional SPR assays. Overall, our work represents a significant advancement towards the development of reusable SPR biosensors. It promises a more sustainable and cost-effective future for biomedical research and diagnostic applications, with application on other transducers and bioanalytical platforms.

Biochar from co-pyrolysis of biological sludge and woody waste followed by chemical and thermal activation: end-of-waste procedure for sludge management and biochar sorption efficiency for anionic and cationic dyes.

Nine biochars were produced by co-pyrolysis of sawdust and biological sludge following the "design of experiment" approach. Two kinds of sludge (both deriving from the treatment of mixed industrial-municipal wastewater) and two types of woody waste were selected as categorical predicting variables, while contact time, pyrolysis temperature, and sludge percentage were used as quantitative variables. Biochars were analysed for their product characteristics and environmental compatibility based on the European Standards (EN 12915-1:2009) for materials intended for water treatment (i.e. ash content, water leachable polycyclic aromatic hydrocarbons (PAHs) and elements), as well as for specific surface area (SSA), using them as response variables of a multivariate partial least square multiple regression, whose results provided interesting insights on the relationships between pyrolysis conditions and biochar characteristics. Biochars produced with sludge and/or providing the highest SSA values (258-370 m2 g-1) were selected to undergo a sustainable chemical treatment using a by-product of the gasification of woody biomass, complying in all cases with European Standards and achieving therefore the end-of-waste status for sewage sludge. The biochar deriving from the highest percentage of sludge (30% by weight) and with the highest SSA (390 m2 g-1) was thermally activated achieving SSA of 460 m2 g-1 and then tested for the sorption of direct yellow 50 and methylene blue in ultrapure water and real wastewater, compared to a commercial activated carbon (AC). The biochar showed Langmuir sorption maxima (Qm) 2-9 times lower than AC, thus highlighting promising sorption performances. Qm for methylene blue in wastewater (28 mg‧g-1) was confirmed by column breakthrough experiments.

Tailoring barrier layers design for haute couture through X-ray microanalysis: Insights and guidelines.

Barrier layers against intermetallic diffusion are a fundamental part on engineering electroplated coatings as they improve the lifetime of goods reducing wastes and improving the sustainability of the production chain. This study aims to set a cost-effective methodology to characterize barrier systems by evaluating the effectiveness with a recent approach based on XRF and EDS and characterize the kinetic of diffusion processes with X-ray diffractometry. Several high fashion barrier systems were tested highlighting that anticorrosion systems are not automatically suited as barrier layers for intermetallic diffusion, as opposed to industrial practice. Investigations on gold coatings obtained varying the current density revealed a correlation between the activation energy of the diffusion process, roughness, and crystallite size.

Oxygen reduction reaction (ORR) in alkaline solution catalysed by an atomically precise catalyst based on a Pd(II) complex supported on multi-walled carbon nanotubes (MWCNTs). Electrochemical and structural considerations.

A new atomically precise, single-ion catalyst (MWCNT-LPd) for ORR (oxygen reduction reaction), consisting of a Pd(II) complex of a tetraazacycloalkane anchored on multiwalled carbon nanotubes, has been prepared through a supramolecular approach ensuring a uniform distribution of catalytic centres on the support surface. A tetraazacycloalkane was chosen to saturate the four coordination sites of the typical square planar coordination geometry of Pd(II) with the aim of ascertaining whether the metal ion must have free coordination sites to function effectively in the ORR or whether, as predicted by quantum mechanical calculations, the catalytic effect can be originated from an interaction of O2 in the fifth coordinative position. The results clearly demonstrated that tetracoordination of Pd(II) does not influence its catalytic capacity in the ORR. Electrodes based on this catalyst show ORR performance very close to that of commercial Pt electrodes, despite the low Pd(II) content (1.72% by weight) in the catalyst. The onset potential (Eon) value and the half-wave potential (E1/2) of the catalyst are, respectively, only 53 mV and 24 mV less positive than those observed for the Pt electrode and direct conversion of O2 to H2O reaches 85.0%, compared to 89% of the Pt electrode. Furthermore, a preliminary galvanostatic test (simulating a working fuel cell at a fixed potential) showed that the catalyst maintains its efficiency continuing to produce water throughout the process (the average number of electrons exchanged over time per O2 molecule remains close to 4).

PVD for Decorative Applications: A Review.

Physical Vapor Deposition (PVD) is a widely utilized process in various industrial applications, serving as a protective and hard coating. However, its presence in fields like fashion has only recently emerged, as electroplating processes had previously dominated this reality. The future looks toward the replacement of the most hazardous and toxic electrochemical processes, especially those involving Cr(VI) and cyanide galvanic baths, which have been restricted by the European Union. Unfortunately, a complete substitution with PVD coatings is not feasible. Currently, the combination of both techniques is employed to achieve new aesthetic features, including a broader color range and diverse textures, rendering de facto PVD of primary interest for the decorative field and the fashion industry. This review aims to outline the guidelines for decorative industries regarding PVD processes and emphasize the recent advancements, quality control procedures, and limitations.

Analytic procedure for the evaluation of copper intermetallic diffusion in electroplated gold coatings with energy dispersive X-ray microanalysis.

A method for the determination of the intermetallic diffusion coefficient in the Cu-Au system is described based on energy dispersive X-ray techniques. XRF and EDS analysis were used to measure the thickness of the electroplated gold coating and the copper diffused through it, respectively. This information was used to obtain the diffusion coefficient through an equation based on Fick's law. Colour measurements and metallographic section analysis of the samples were also performed to evaluate alternative methods for a qualitative determination of diffusion rate. The thickness of the gold layer was chosen in agreement with what is used in decorative and functional applications (<1 µm). The measurements were performed on samples heated in a range of temperatures between 100 °C and 200 °C from 12 to 96 h. The results obtained follow a linear trend between the logarithm of the diffusion coefficient and the inverse of the temperature and are in line with the values found in the literature.

Chiral "doped" MOFs: an electrochemical and theoretical integrated study.

This work reports on the electrochemical behaviour of Fe and Zn based metal-organic framework (MOF) compounds, which are "doped" with chiral molecules, namely: cysteine and camphor sulfonic acid. Their electrochemical behaviour was thoroughly investigated via "solid-state" electrochemical measurements, exploiting an "ad hoc" tailored experimental set-up: a paste obtained by carefully mixing the MOF with graphite powder is deposited on a glassy carbon (GC) surface. The latter serves as the working electrode (WE) in cyclic voltammetry (CV) measurements. Infrared (IR), X-ray diffraction (XRD) and absorbance (UV-Vis) techniques are exploited for a further characterization of the MOFs' structural and electronic properties. The experimental results are then compared with DFT based quantum mechanical calculations. The electronic and structural properties of the MOFs synthesized in this study depend mainly on the type of metal center, and to a minor extent on the chemical nature of the dopant.

Specific ion effects on copper electroplating.

The main goal of this work is to open new perspectives in the field of electrodeposition and provide green alternatives to the electroplating industry. The effect of different anions (SO42-, ClO3-, NO3-, ClO4-, BF4-, PF6-) in solution on the electrodeposition of copper was investigated. The solutions, containing only the copper precursor and the background electrolyte, were tailored to minimize the environmental impact and reduce the use of organic additives and surfactants. The study is based on electrochemical measurements carried out to verify that no metal complexation takes place. We assessed the nucleation and growth mechanism, we performed a morphological characterization through scanning electron microscopy and deposition efficiency by measuring the film thickness through X-ray fluorescence spectroscopy. Significant differences in the growth mechanism and in the morphology of the electrodeposited films, were observed as a function of the background electrolyte.

A systematic study of pulse and pulse reverse plating on acid copper bath for decorative and functional applications.

Today industrial electroplating is mainly carried out using direct current even if the use of modulated currents could offer greats opportunities. Adjusting the amplitude and length of the current's pulses it is possible to control grain size, porosity and homogeneity of the deposits; the use of modulated currents could also decrease the environmental impact of deposition processes as they require a much lower percentage of organic additives. The aim of this work is to assess, through both theoretical and experimental investigation, how the deposition parameters affect the various characteristics of the deposit. We used a commercial acid copper bath for the depositions performing both pulse and reverse pulse sequences. The coatings have been characterised by estimating the deposition yield, homogeneity, hardness and reflectivity. Using pulsed currents, we obtained shinier and brighter films respect to those produced with stationary currents; the deposition efficiency was also improved. Bipolar currents, on the other hand, favour more homogeneous deposits over the entire deposition area, and are less affected by the edge effect.

Optimization and Characterization of Electrodeposited Cadmium Selenide on Monocrystalline Silicon.

In this work, the optimal conditions for the electrodeposition of a CdSe film on n-Si were demonstrated. The structural and optical properties of the bare films and after annealing were studied. In particular, the crystallinity and photoluminescence of the samples were evaluated, and after annealing at 400 °C under a nitrogen atmosphere, a PL increase by almost an order of magnitude was observed. This paper opens the route towards the use of electrochemical deposition as a cost-effective and easy fabrication approach that can be used to integrate other interesting materials in the silicon-manufacturing processes for the realization of optoelectronic devices.

Graphene-based nanomaterials in the electroplating industry: A suitable choice for heavy metal removal from wastewater.

The presence of various heavy metal ions in the industrial waste waters has recently been a challenging issue for human health. Since heavy metals are highly soluble in the aquatic environments and they can be absorbed easily by living organisms, their removal is essential from the environmental point of view. Many studies have been devoted to investigating the environmental behaviour of graphene-based nanomaterials as sorbent agents to remove metals from wastewaters arising by galvanic industries. Among the graphene derivates, especially graphene oxide (GO), due to its abundant oxygen functional groups, high specific area and hydrophilicity, is a high-efficient adsorbent for the removal of heavy and precious metals in aquatic environment. This paper reviews the main graphene, GO, functionalized GO and their composites and its applications in the metals removal process. The influencing factors, adsorption capacities and reuse capability are highlighted for the most extensively used heavy metals, including copper, zinc, nickel, chromium, cobalt and precious metals (i.e., gold, silver, platinum, palladium, rhodium, and ruthenium) in the electroplating process.

Thickness determination of metal multilayers by ED-XRF multivariate analysis using Monte Carlo simulated standards.

We present the thickness measurement of multilayer samples by X-ray fluorescence (XRF) using calibration curves obtained from simulated spectra through Monte Carlo (MC) algorithm. The XRF is a widespread technique for the analysis of single and multilayer films but the accuracy of quantitative analysis must be increased. Moreover, the use certified standards is not easy to implement due to the high variability of combination and/or concentration in layered samples. The results of this work were compared with fundamental parameter (FP) method and focussed ion beam scanning electron microscopy (FIB-SEM) analysis. The results show good quantitative values even without the use of any standard with known thickness. In addition to having built the calibration curves with a simple univariate approach, also multivariate data analysis was performed to consider multiple variables simultaneously. From the comparison of the obtained results, it can be inferred that the univariate analysis worked well in the case of single layer samples and in the determination of the upper layer in multilayer samples but only multivariate analysis, taking into account the matrix effect of each layer, provided maximum accuracy on each layer of multilayer samples.

Redox-Active Ferrocene grafted on H-Terminated Si(111): Electrochemical Characterization of the Charge Transport Mechanism and Dynamics.

Electroactive self-assembled monolayers (SAMs) bearing a ferrocene (Fc) redox couple were chemically assembled on H-terminated semiconducting degenerate-doped n-type Si(111) substrate. This allows to create a Si(111)|organic-spacer|Fc hybrid interface, where the ferrocene moiety is covalently immobilized on the silicon, via two alkyl molecular spacers of different length. Organic monolayer formation was probed by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) and X-ray photoelectron spectroscopy (XPS) measurements, which were also used to estimate thickness and surface assembled monolayer (SAM) surface coverage. Atomic force microscopy (AFM) measurements allowed to ascertain surface morphology and roughness. The single electron transfer process, between the ferrocene redox probe and the Si electrode surface, was probed by cyclic voltammetry (CV) measurements. CVs recorded at different scan rates, in the 10 to 500 mV s-1 range, allowed to determine peak-to-peak separation, half-wave potential, and charge-transfer rate constant (KET). The experimental findings suggest that the electron transfer is a one electron quasi-reversible process. The present demonstration of surface engineering of functional redox-active organometallic molecule can be efficient in the field of molecular electronics, surface-base redox chemistry, opto-electronic applications.