Synergetic effect in water treatment with mesoporous TiO2/BDD hybrid electrode

Boron-doped diamond (BDD) electrodes have a wide potential window and can produce ozone by water electrolysis at high voltage. Though ozone has strong oxidative power (standard oxidation potential: 2.07 V vs. NHE), it cannot decompose certain types of recalcitrant organic matter completely. We developed an advanced oxidation process (AOP), in which hydroxy radicals with stronger oxidative power (standard oxidation potential: 2.85 V vs. NHE) are formed using a combination of ozone, photocatalyst, and UV. In this study, we fabricated a mesoporous TiO₂/BDD hybrid electrode and examined its potential for AOPs. A synergetic effect between electrochemical water treatment and photocatalytic water treatment was observed with the hybrid electrode that did not occur with the BDD electrode.

A mesoporous TiO₂/BDD hybrid electrode showed a synergetic effect between electrochemical water treatment and photocatalytic water treatment.     

Boron-doped diamond nanowire array electrode with high mass transfer rates in flow-by operation

We fabricated a boron-doped diamond nanowire (BDDNW) array electrode via soft lithography and metal-assisted chemical etching (MACE) of Si to provide a highly promoted effective surface area and increased mass transport during the electrochemical oxidation process. The effects of aligning the BDDNW on the electrochemical oxidation performance and the current efficiency of the electrode in phenol oxidation were examined. Although the effective surface area of the BDDNW array with an aligned nanowire configuration was smaller than that of the BDDNW with a random nanowire configuration, the BDDNW array electrode exhibited a higher mass transfer coefficient, resulting in a better performance in the removal of phenol. The enhanced mass transport exhibited by the BDDNW array electrode also greatly enhanced the chemical oxygen demand (COD) and current efficiency. Furthermore, because of its excellent oxidation performance, the BDDNW array electrode also exhibited much lower energy consumption during the phenol oxidation process.

We fabricated a boron-doped diamond nanowire (BDDNW) array electrode via lithography and metal-assisted chemical etching (MACE) to provide a highly promoted surface area and increased mass transport during the electrochemical oxidation process.     

Electrochemical study of 4-chloroaniline in a water/acetonitrile mixture. A new method for the synthesis of 4-chloro-2-(phenylsulfonyl)aniline and N-(4-chlorophenyl)benzenesulfonamide

The electrochemical oxidation of 4-chloroaniline as a model compound in a water/acetonitrile mixture was investigated by cyclic voltammetry and differential pulse voltammetry. It was established that one-electron oxidation of 4-chloroaniline followed by disproportionation reaction affords unstable (4-iminocyclohexa-2,5-dien-1-ylidene)chloronium. In water/acetonitrile mixtures and in the absence of nucleophiles, the most likely reaction on produced chloronium is hydrolysis and p-quinoneimine formation. The electrochemical oxidation of 4-chloroaniline in the presence of arylsulfinic acids was also investigated in a water/acetonitrile mixture at a glassy carbon electrode. It was established that under these conditions, the anodically generated chloronium reacts with benzenesulfinic acid to produce the corresponding diaryl sulfone and N-phenylbenzenesulfonamide derivatives. In addition, Gaussian 09W was applied for prediction of the possible product by the calculation of natural charge, LUMO orbital energies and thermodynamic stability of intermediates and products.

Electrochemical oxidation pathway of p-chloroaniline (PCA) in the presence of benzenesulfinic acid (BSA).     

Influence of electrochemical co-deposition of bimetallic Pt–Pd nanoclusters on polypyrrole modified ITO for enhanced oxidation of 4-(hydroxymethyl) pyridine

Bimetallic Pt–Pd nanoparticles were dispersed on polypyrrole coated indium-tin oxide coated polyethylene terephthalate sheets (ITO-PET sheets). The excellent filming property of pyrrole gives a high porous uniform active area for the proper adsorption of bimetallic transition metal nanoparticles. Electrochemical behavior of the modified electrodes was determined using cyclic voltammetry and impedance studies. The physicochemical properties of the modified electrodes were analyzed by scanning electron microscopy, X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. To study the electrochemical oxidation of 4-(hydroxymethyl) pyridine in the presence of sodium nitrate in aqueous acidic medium, the modified electrode was used. It is evident from the study that the modified electrode shows better electrochemical activity towards the oxidation of 4-(hydroxymethyl) pyridine.

Bimetallic Pt–Pd nanoparticles were dispersed on polypyrrole coated indium–tin oxide coated polyethylene terephthalate sheets (ITO-PET sheets).     

Electrochemical bubble generation via hydrazine oxidation for the in situ control of an electrodeposited conducting polymer micro/-nanostructure

Herein, a simple, in situ, on step and highly repeatable electrochemical method that allows controlling the nanostructure of electrodeposited polymer films is reported. As an example, the tuning of the electrodeposited polypyrrole nanostructures using inert gas bubbles as the template at the electrode surface generated by the electrochemical oxidation of hydrazine is shown. The hydrazine discharge occurs at a lower potential regarding the beginning of pyrrole electropolymerization process, which allows the modulation of the density and size of the bubbles on the surface electrode controlling electrochemical parameters (applied potential, concentration, time, etc.). Subsequently, the applied potential is moved to where the pyrrole polymerization begins, which induces the material discharges around the bubble template producing polypyrrole hollow structures with definite patterns on the electrode surface. This methodology is proposed as a simple model for the electrodeposition with the morphological control of a wide range of conductive polymers.

An electrochemical method to manipulate the size and density of electrodeposited polypyrrole structures at the micro-nanoscale by the discharge of hydrazine.     

In situ autologous growth of self-supporting NiFe-based nanosheets on nickel foam as an efficient electrocatalyst for the oxygen evolution reaction

A highly efficient and low-cost oxygen evolution reaction electrocatalyst is essential for water splitting. Herein, a simple and cost-effective autologous growth method is developed to prepare NiFe-based integrated electrodes for water oxidation. In this method, a Ni(OH)₂ nanosheet film is first developed on nickel foam by oxidative deposition in a chemical bath solution. The as-prepared nanosheet electrode is then immersed into a solution containing Fe(iii) cations to form an Fe-doped Ni(OH)₂ electrode by utilization of the different solubility of metal cations. Benefiting from its unique and integrated nanostructure, this hierarchically structured electrode displays extremely high catalytic activity toward water oxidation. In 1 M KOH, the electrode can deliver a current density of 1000 mA cm⁻² at an overpotential of only 330 mV. This work provides a facile way to produce an efficient, durable, and Earth-abundant OER electrocatalyst with no energy input, which is attractive for large-scale water splitting.

We report here a simple and cost-effective autologous growth method to prepare a NiFe-based integrated electrode for efficient electrocatalytic water oxidation.     

A voltammetric sensor based on reduced graphene oxide-hemin-Ag nanocomposites for sensitive determination of tyrosine

A novel voltammetric sensor was designed and used for the determination of l-tyrosine (l-Tyr) by surface modification of a glassy carbon electrode with reduced graphene oxide-hemin-Ag (rGO-H-Ag) nanocomposites. The nanocomposites were synthesized by a facile one-pot hydrothermal method and characterized by means of transmission electron microscopy and Raman spectroscopy. The determination of l-Tyr was investigated by cyclic voltammetry and further quantified using differential pulse voltammetry. The results revealed a significant enhanced electrochemical oxidation effect for l-Tyr at the nanocomposites modified electrode. Two linear ranges from 0.1 to 100 μM and 100 to 1000 μM as well as a low detection limit of 30 nM (S/N = 3) were obtained. In addition, the sensor also demonstrated good selectivity, reproducibility and stability.

A novel electrochemical sensor for the sensitive determination of l-Tyr was designed with a rGO-H-Ag nanocomposite modified electrode.     

Electrochemical preparation of monodisperse Pt nanoparticles on a grafted 4-aminothiophenol supporting layer for improving the MOR reaction

The methanol oxidation reaction (MOR) has recently gained a lot of attention due to its application in fuel cells and electrochemical sensors. To enhance the MOR, noble metal nanoparticles should be homogeneously dispersed on the electrode surface with the aid of one suitable support. In this work, 4-aminothiophenol (4-ATP) molecules which contain simultaneously amine and thiol groups were electro-grafted onto the electrode surface to provide anchoring sites, limit aggregation and ensure good dispersion of metal nanoparticles. The results showed a high density of platinum nanoparticles (PtNPs) with an average size of 25 nm on the glassy electrode modified with a 4-ATP supporting layer. Consequently, the MOR was improved by 2.1 times with the aid of the grafted 4-ATP layer. The electrochemical sensor based on PtNPs/4-ATP/GCE is able to detect MeOH in a linear range from 1.26 to 21.42 mM with a detection limit of 1.21 mM.

Well-dispersed Pt nanoparticles for MOR reaction.     

Iodine/water-mediated deprotective oxidation of allylic ethers to access α,β-unsaturated ketones and aldehydes

The first iodine/water-mediated deprotective oxidation of allylic ethers to access α,β-unsaturated ketones and aldehydes was achieved. The reaction tolerates a wide range of functionalities. Furthermore, this protocol was found to be applicable to the oxidative transformation of allylic acetates. The proposed mechanism involves an oxygen transfer from solvent water to the carbonyl products.

The first iodine/water-mediated deprotective oxidation of allylic ethers to access α,β-unsaturated ketones and aldehydes was effectively achieved.     

Mechanism of N,N-dimethylformamide electrochemical oxidation using a Ti/RuO2–IrO2 electrode

The compound N,N-dimethylformamide (DMF) is a widely used industrial chemical and a common environmental contaminant that has been found to be harmful to human health. In this study, electrochemical oxidation was adopted for the degradation of DMF. The effects of four kinds of electrodes on the removal rates of DMF and total organic carbon were compared, and based on the result, the Ti/RuO₂–IrO₂ electrode was selected as the operating electrode. The effects of three independent factors (current density, pH, and NaCl proportion) on the DMF degradation were investigated through single-factor experiments, and the experimental results were optimized by response surface methodology. The optimal experimental conditions were obtained as follows: current density = 47 mA cm⁻², pH = 5.5, and NaCl proportion = 15%. The electrochemical oxidation of 50 mg L⁻¹ DMF was performed under the optimal conditions; the degradation rate was 97.2% after 7 h, and the reaction followed the pseudo-first-order kinetic model. The degradation products under optimal conditions and chlorine-free conditions were analyzed, and four degradation pathways were proposed. The DMF degradation was more thorough under optimal conditions.

DEMS as an emerging technology was used to investigate the degradation mechanism of DMF.     

Polyphenol oxidase/gold nanoparticles/mesoporous carbon-modified electrode as an electrochemical sensing platform for rutin in dark teas

In the communication, by virtue of the excellent conductivity and great surface area of mesoporous carbon (FDU-15), the enhanced conductivity of Au NPs, and the good electrochemical response of polyphenol oxidase (PPO) to rutin, a PPO/AuNPs/FDU-15-modified electrode was used as a candidate for the determination of rutin in dark teas with satisfactory results.

By virtue of great surface area of mesoporous carbon, enhanced conductivity of AuNPs, and good electrochemical response of polyphenol oxidase to rutin, a PPO/AuNPs/FDU-15-modified electrode was used for the determination of rutin in dark teas.     

Experimental and theoretical research on a new corrosion inhibitor for effective oil and gas acidification

A new dibenzylamine-quinoline derivative (DEEQ) was synthesized and investigated as a corrosion inhibitor for mild steel in 15% HCl solution in various ways, including via weight loss measurements, contact angle measurements, electrochemical measurements (EIS), scanning electron microscopy (SEM), scanning Kelvin probe (SKP) and theoretical calculations. The experimental results revealed that DEEQ is an effective corrosion inhibitor for oil and gas acidification. In an oil–water two-phase system, the wettability of mild steel can be changed by adsorption, while obeying the Langmuir adsorption isotherm. Finally, quantum chemical calculations and molecular dynamic simulation parameters further show a definite correlation between the theoretical and experimental results.

A new dibenzylamine-quinoline derivative (DEEQ) was synthesized and shown to be an effective corrosion inhibitor for mild steel in 15% HCl solution for oil and gas acidification.     

Electrochemical synthesis of copper(i) acetylides via simultaneous copper ion and catalytic base electrogeneration for use in click chemistry

We report an efficient and sustainable electrochemical synthesis of copper(i) acetylides using simultaneous copper oxidation and Hofmann elimination of quaternary ammonium salts. The electrochemically-generated base was also regenerated electrochemically, making it catalytic. A ‘Click test’ (CuAAC reaction) was performed to assess product purity and an electrochemically-promoted, one-pot CuAAC reaction was performed, which serves as a promising initial demonstration of this approach in a pharmaceutically-relevant reaction.

We report an efficient and sustainable electrochemical synthesis of copper(i) acetylides using simultaneous copper oxidation and Hofmann elimination of quaternary ammonium salts.     

Sensitive detection of ascorbic acid using screen-printed electrodes modified by electroactive melanin-like nanoparticles

In this work, we report on the design of an enzyme-less sensitive and selective electrochemical electrode for ascorbic acid (AA) detection using a modified screen-printed electrode of melanin-like nanoparticles (Mel-NPs). Cyclic voltammetry shows that the melanin-modified electrode exhibits high electrocatalytic activity for ascorbic acid. The melanin-like nanoparticles serve as a shuttle to transport electrons from ascorbic acid to the electrode surface. The modified electrode is endowed with a large dynamic window ranging from 5 to 500 ppb. The detection and quantification limits were estimated to be 0.07 and 0.23 ppb, respectively. The modified electrode was successfully used to determine AA in human blood serum, urine and saliva with satisfactory recovery levels.

A melanin-like nanoparticle modified screen-printed electrode for enzyme-less detection of ascorbic acid.     

A dopamine electrochemical sensor based on a platinum–silver graphene nanocomposite modified electrode

A platinum–silver graphene (Pt–Ag/Gr) nanocomposite modified electrode was fabricated for the electrochemical detection of dopamine (DA). Electrochemical studies of the Pt–Ag/Gr nanocomposite towards DA detection were performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The CV analysis showed that Pt–Ag/Gr/GCE had enhanced electrocatalytic activity towards DA oxidation due to the synergistic effects between the platinum–silver nanoparticles and graphene. The DPV results showed that the modified sensor demonstrated a linear concentration range between 0.1 and 60 μM with a limit of detection of 0.012 μM. The Pt–Ag/Gr/GCE presented satisfactory results for reproducibility, stability and selectivity. The prepared sensor also showed acceptable recoveries for a real sample study.

A platinum–silver graphene nanocomposite was synthesized and characterized. A nanocomposite modified electrode was fabricated in order to investigate the electrochemical detection of dopamine.     

A study on the electrochemical behavior of hydroquinone at a nanometer cobalt/l-glutamate-modified electrode

A new electrochemical sensor for hydroquinone (HQ) was prepared. The electrochemical sensor was modified by electrodeposition and electrochemical polymerization to modify nanometer cobalt (nano-Co) and poly-l-glutamic acid (poly-l-glu) on the surface of a glassy carbon electrode (GCE). Then, the electrochemical behavior of hydroquinone on the electrochemical sensor was investigated by cyclic voltammetry (CV). The experimental conditions were optimized from the aspects of electrolyte type, concentration, acidity, enrichment time and scanning speed. The experimental results showed that under optimized conditions the oxidation peak current has a good linear relationship with the concentration of hydroquinone in the range of 3.85 × 10⁻⁶ to 1.30 × 10⁻³ mol L⁻¹ (R² = 0.9998). Moreover, there was a low detection limit of 4.97 × 10⁻⁷ mol L⁻¹. When the sensor was used for the analysis of hydroquinone in water samples, the recoveries with satisfactory results were in the range of 97.2–102.6%.

A new electrochemical sensor for hydroquinone (HQ) was prepared.     

Investigating electrochemical deposition of gold on commercial off-the-shelf 3-D printing materials towards developing sensing applications

The COVID-19 pandemic highlighted the inaccessibility of quick and affordable clinical diagnostics. This led to increased interest in creating low-cost portable electrochemical (EC) devices for environmental monitoring and clinical diagnostics. One important perspective is to develop new fabrication methods for functional and low-cost electrode chips. Techniques, such as electron beam and photolithography, allow precise and high-resolution electrode fabrication; however, they are costly and can be time-consuming. More recently, fused deposition modeling three-dimensional (3-D) printing is being used as an alternative fabrication technique due to the low-cost of the printer and rapid prototyping capability. In this study, we explore enhancing the conductivity of 3-D printed working electrodes with EC gold deposition. Two commercial conductive filament brands were used and investigated to fabricate electrode chips. Furthermore, strategies to apply epoxy glue and conductive silver paint were investigated to control the electrode surface area and ensure good electrical connection. This device enables detection at drinking water concentration thresholds. The practical application of the fabricated electrodes is demonstrated by detecting Cu²⁺ using anodic stripping voltammetry.

Customized electrodes were made with 3-D printing and gold electrochemical reduction towards analytical applications.     

Enhanced electrochemical response of a modified glassy carbon electrode by poly(2-vinlypyridine-b-methyl methacrylate) conjugated gold nanoparticles for detection of nicotine

Poly(2-vinylpyridine-b-methylmethacrylate) coated gold nanoparticles [P(2VP-MMA)-AuNPs] were prepared and characterized by UV-Vis, FTIR, AFM, and zetasizer analysis. Investigation of the potential of the synthesized poly(2-vinylpyridine-b-methylmethacrylate) coated gold nanoparticles [P(2VP-MMA)-AuNPs] for detection of nicotine is the main focus of the current study. P(2VP-MMA)-AuNPs were coated on a glassy carbon electrode (GCE) for electrochemical detection of nicotine by cyclic voltammetry. The effect of molar mass of individual P2VP blocks and total molar mass of the block copolymer is evaluated in the context of an enhanced electrochemical response of the modified GCE for its sensing ability of nicotine in both aqueous and organic media. The electrochemical detection of nicotine is significantly enhanced by modification of the GCE with P(2VP-MMA)-AuNPs.

Poly(2-vinylpyridine-b-methylmethacrylate) coated gold nanoparticles [P(2VP-MMA)-AuNPs] are employed for enhancement of electrochemical response of glassy carbon electrode for nicotine.     

4-Pentenoyl-isoleucyl-chitosan oligosaccharide and acrylamide functional monomer-dependent hybrid bilayer molecularly imprinted membrane for sensitive electrochemical sensing of bisphenol A

In this work, an electrochemical sensor was designed for trace monitoring of bisphenol A (BPA) by decorating a hybrid bilayer molecularly imprinted membrane (MIM) on a multi-walled carbon nanotube-modified glassy carbon electrode. When BPA in the MIM was eluted, a composite molecularly imprinted electrochemical sensor was constructed. Under optimal conditions, the developed sensor showed two linear relationships between ΔI_p and BPA concentration in the range of 0.04 μM to 8 μM, as well as good selectivity and stability, and was also applied to detect BPA in water samples with desirable recoveries ranging from 92.0% to 107.0%.

A hybrid bilayer molecularly imprinted membrane-dependent electrochemical sensor was developed for bisphenol A assay based on 4-pentenoyl-isoleucyl-chitosan oligosaccharide and acrylamide functional monomers.     

Properties of amorphous iron phosphate in pseudocapacitive sodium ion removal for water desalination

Capacitive deionization (CDI) is an energy saving and environmentally friendly technology for water desalination. However, classical CDI is challenged by a low salt removal capacity. To improve the desalination capacity, electrode materials utilizing the battery mechanism for salt ion removal have emerged as a new direction more recently. In this work, we report a study of amorphous iron phosphate (FePO₄) as a promising electrode material for pseudocapacitive sodium ion removal. Sodium ions can be effectively, reversibly intercalated and de-intercalated upon its electrochemical reduction and oxidation, with an excellent sodium ion capacity under half-cell testing conditions. By assembling a hybrid CDI (HCDI) system utilizing the FePO₄ electrode for pseudocapacitive sodium ion removal and active carbon electrode for capacitive chloride ion removal, the cell exhibited a high salt removal capacity and good reversibility and durability, which was attributed to the advantageous features of amorphous FePO₄. The HCDI system achieved a high deionization capacity (82 mg g⁻¹) in 10 mM NaCl, a fast deionization rate (0.046 mg g⁻¹ s⁻¹), and good stability and cyclability.

Amorphous iron phosphate (FePO₄) exhibits excellent capacity, reversibility and stability in pseudocapacitive sodium ion removal for water desalination.