Electrochemical Generation Research Articles

Electrogenerated chemiluminescence from luminol-labelled microbeads triggered by in situ generation of hydrogen peroxide.

We developed a sensing strategy that mimics the bead-based electrogenerated chemiluminescence immunoassay. However, instead of the most common metal complexes, such as Ru or Ir, the luminophore is luminol. The electrogenerated chemiluminescence of luminol was promoted by in situ electrochemical generation of hydrogen peroxide at a boron-doped diamond electrode. The electrochemical production of hydrogen peroxide was achieved in a carbonate solution by an oxidation reaction, while at the same time, microbeads labelled with luminol were deposited on the electrode surface. For the first time, we proved that was possible to obtain light emission from luminol without its direct oxidation at the electrode. This new emission mechanism is obtained at higher potentials than the usual luminol electrogenerated chemiluminescence at 0.3-0.5V, in conjunction with hydrogen peroxide production on boron-doped diamond at around 2-2.5V (vs Ag/AgCl).

Facile fabrication of SnO2/MnTe nanocomposite as an efficient electrocatalyst for OER in basic media

There is a strong demand for developing an extremely effective and robust electrocatalyst to facilitate oxygen evolution reaction in water electrolysis applications. Herein, we successfully produced SnO2/MnTe using an efficient ultrasonication technique that is cost-effective and readily accessible along with improved catalytic behavior. The physical properties of fabricated catalysts are examined to analyze textural, structural and morphological characteristics. The SnO2/MnTe nanocomposite exhibited the low overpotential (181 mV) at 10 mA cm−2 and smaller Tafel slope of 33 mV dec−1 in alkaline (1.0 M KOH) medium. Moreover, the material also showed prolonged and excellent stability over 50 h following 5000 stability cycles. Electrochemical impedance spectroscopy studies demonstrated that charge transfer kinetics at the catalyst-electrolyte interface could be achievable, with lower Rct values (0.8Ω) directing it to increase electrochemical behavior. The acquired outcomes obtained from electrochemical activity demonstrate the potential of SnO2/MnTe as a highly promising electrocatalyst for future electrochemical energy generation.

Hydrogen peroxide electrosynthesis using commercial carbon blacks as catalysts: the influence of surface properties and adsorption performance

AbstractBACKGROUNDSurface properties and adsorption performance of carbon materials play a crucial role in the electrochemical two‐electron oxygen reduction to produce H2O2. However, there is still a lack of in‐depth research on commercial carbon blacks in this area. Herein, four typical commercial carbon blacks (Acetylene black (AB), Ketjen black EC 600JD, Vulcan XC 72 and Black Pearls 2000) were used as cathode catalysts to generate H2O2. Surface chemistry and pore structure of electrodes of the four carbon blacks were systematically characterized, and their effects on H2O2 adsorption, electrochemical generation and degradation were investigated.RESULTSAmong the four carbon blacks, AB has the highest content of C–O–C/COOH and CO, which are active groups catalyzing the two‐electron oxygen reduction reaction to generate H2O2. AB has the lowest level of defects and highest degree of graphitization, and AB‐modified graphite felt electrode (AB‐Ele) has the largest average pore diameter, smallest specific surface area and smaller charge transfer resistance. H2O2 production using AB‐Ele is the largest and reaches 567.7 mg L−1 at 180 min under a current density of 5 mA cm−2, and only decreases by 17.6% after 10 repeated uses.CONCLUSIONOverall, rich oxygen‐containing functional groups such as C–O–C, COOH and CO, high degree of graphitization, suitable surface area and porosity as well as weak H2O2 adsorption performance are beneficial for the two‐electron oxygen reduction reaction to generate H2O2. AB‐modified graphite felt electrode exhibits good catalytic activity and reusability in H2O2 electrosynthesis, demonstrating promising application prospects. © 2024 Society of Chemical Industry (SCI).

Electrochemical Hydrogen Peroxide Generation and Removal of Moxifloxacin by Electro-Fenton Process

In this study, the removal of moxifloxacin, an antibiotic of the fluoroquinolone group, from aqueous solutions was investigated using the electro-Fenton process. As the efficiency of the electro-Fenton process is highly dependent on the amount of H2O2 produced during process, the formation of H2O2 under acidic conditions was also investigated. In this context, the effects of applied current, cathode type and O2 flow rate on H2O2 production were investigated using boron-doped diamond anode. The highest H2O2 production was achieved using the boron-doped diamond anode and the graphite felt cathode. In addition, the optimum conditions for the applied current and oxygen flow rate for H2O2 production were determined to be 0.25 A and 0.1 L min−1, respectively. The effects of applied current and Fe2+ concentration in the electro-Fenton process on the removal of moxifloxacin were investigated. It was found that the moxifloxacin removal rate increased with increasing applied current. The highest H2O2 accumulation was observed at 0.25 A applied current, and moxifloxacin removal also reached 93.6% after 60 min. The moxifloxacin removal rate reached the highest value at Fe2+ concentration of 0.01 mM. This study provides promising results for the efficient treatment of moxifloxacin-containing wastewater by the electro-Fenton process without the addition of H2O2 using boron-doped diamond anode anode and graphite felt cathode.

Design and synthesis of heteroleptic Ni(II) dipyrrin complexes for electrochemical proton reduction reactions: Cyclic voltammetric and theoretical studies

The effect of nuclearity on electrochemical hydrogen generation using new heteroleptic Ni(II) complexes containing redox-active dipyrrin and dithiocarbamate ligands has been described. Complexes 1–2 have been meticulously characterized by spectroscopic studies (ESI-MS, IR, 1H, 13C NMR, UV–vis) and their structures unambiguously confirmed by X-ray single crystal analyses. Electrocatalytic properties of the complexes toward hydrogen evolution reaction have been investigated by cyclic voltammetric studies in an organic medium in the presence of acetic acid as a weak proton source. Notably, complexes 1 and 2 produce H2 via doubly reduced Ni(II) species i.e. Ni(0) in the presence of acetic acid. Further, these complexes exhibited significant electrocatalytic activity (TOF: 264 (1) and 650 s−1 (2). Controlled potential electrolysis established a minimum Faradaic efficiency of 92 (1) and 96 % (2). Complex 2 exhibited higher turnover frequency relative to 1, while 1 showed lower overpotential (0.35 V) in comparison to 2 (0.45 V). The stability of the complexes and the amount of produced H2 has been investigated by bulk electrolysis study. A tentative mechanism (ECEC; E, electrons and C, chemical steps) and involved intermediate species for the proton reduction reaction for 1 has been established by theoretical studies.

Innovative carbon materials from lignocellulosic wastes for electrochemical hydrogen peroxide production: Bridging biomass conversion and material properties

This study aims to assess the electrochemical generation of hydrogen peroxide and hydroxyl radicals (*OH) using carbon cathodes synthesized from three different lignocellulosic residues, Phragmites australis (PA), Cladium mariscus (CM) and Typha domingensis (TD). These vegetal species are commonly used in natural wetlands and phytoremediation processes and can accumulate recalcitrant pollutants within these treatment processes, generating a waste that should be properly managed. To convert these residues into valuable carbon materials, they underwent hydrothermal carbonization (HTC) followed by either chemical activation with KOH or pyrolysis at 1000 ºC. The best results were obtained with chemically activated materials, yielding a maximum H2O2 concentration of 313 mg L−1 with the carbon cathode produced from PA. The specific surface area, oxygenated functional groups and presence of structural defects in carbonous structures, were key parameters related to a good performance as catalysts towards the 2e- Oxygen Reduction Reaction (ORR). It was also demonstrated, in comparison with previous studies, that the presence of heavy metals in the structure of the lignocellulosic residue enhanced the decomposition of H2O2 into *OH. However, in the study of the degradation of a model organic contaminant as methylene blue (MB), it was shown that these *OH were not the main contributors to degradation, as direct H2O2 chemical degradation and adsorption on the carbon materials played the most significant role. Therefore, the outstanding capacity of these lignocellulosic residues as catalysts for the electrogeneration of H2O2 was confirmed, suggesting their potential future application in advanced oxidation processes for water decontamination.

Electrocatalytic Poly(3,4-ethylenedioxythiophene) for Electrochemical Conversion of 5-Hydroxymethylfurfural.

This study investigates the utilization of the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) as a catalytic material for the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). PEDOT films doped with different counterions were electrodeposited on graphite foil. In particular, the mobile anion perchlorate and the polymeric ionomers polystyrenesulfonate, Nafion, and Aquivion were used. The electrocatalytic properties of PEDOT films were evaluated toward the TEMPO redox mediator in the absence and the presence of HMF as a substrate for oxidation reactions. The electrocatalytic HMF oxidation was confirmed to occur at PEDOT electrodes, and it was also found that the chemical nature of PEDOT counterions controls the electrocatalytic conversion of HMF by modulating the kinetics of the electrochemical generation of the oxoammonium cation TEMPO(+). Potentiostatic electrolysis experiments showed that both the reference graphite electrode and PEDOT substrates were able to convert HMF to FDCA with an 80% faradaic efficiency (FE) and a >90% yield (FDCA), but, compared to graphite, the complete conversion of HMF to FDCA required a ca. 30% shorter time when using PEDOT electrodes doped with perchlorate or Aquivion, thanks to their ability to sustain a higher current density in the initial phase of the electrolysis. In addition, while all PEDOT films were chemically stable under the electrochemical conditions herein described, only PEDOT films doped with Aquivion were also mechanically robust and stable against delamination. Thus, the new PEDOT/Aquivion composite may represent the best choice for the implementation of PEDOT-based electrodes in TEMPO-mediated electrocatalytic applications.

Rapid CO2 laser treatment of Pt–Fe MOF for efficient electrochemical hydrogen evolution reaction

The quest for efficient hydrogen production via electrochemical water splitting has led to extensive research on catalytic materials. This work focuses on enhancing the catalytic functionality of metal-organic frameworks (MOFs) by incorporating platinum (Pt) to improve the performance of the hydrogen evolution reaction (HER). Fe-based MOFs mixed with platinum precursors were altered through laser treatment, which caused considerable changes in their structure and catalytic activity in just 3 min. This was achieved without the need for vacuum or an inert atmosphere. Characterization techniques including X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and electrochemical measurements were used to characterize the synthesized materials. The laser-treated Pt–Fe MOF demonstrated outstanding HER performance with 3.5 wt% Pt content, outperforming commercial 20 wt% Pt/C catalysts, and exhibiting good stability even after prolonged cycling. These results highlight the potential of laser-treated MOFs for efficient and cost-effective electrochemical hydrogen generation.

Electrolyte-free electrochemical oxygen generator for providing sterile and medical-grade oxygen in household applications

Electrolyte-free electrochemical oxygen generator for providing sterile and medical-grade oxygen in household applications

Pathways for marine carbon dioxide removal using electrochemical acid-base generation

Research over the past decade has resulted in various methods for removing CO2 from the atmosphere using seawater and electrochemically generated acids and bases. This Perspective aims to present a unified framework for comparing these approaches. Specifically, these methods can all be seen as falling into one of two categories: those that result in a net increase in ocean alkalinity and use the “ocean as a sponge” for atmospheric CO2 (ocean alkalinity enhancement, or OAE) and those that cycle ocean alkalinity and use the “ocean as a pump” for atmospheric CO2 (ocean alkalinity cycling, or OAC). In this Perspective, approaches for marine carbon dioxide removal (mCDR) using electrochemistry are compared using this framework, and the similarities and differences of these two categories are explored.

Performance enhancement of electrochemical degradation of H-acid wastewater via novel membrane electrode assembly electrolyser

A membrane electrode assembly (MEA) based electrolyser is designed and fabricated for H-acid wastewater treatment and harmful chemical degradation. The electrochemical O3 and H2O2 generation performance has been greatly enhanced owing to the nano PbO2 catalyst on the anode and the PTFE/C catalyst on the cathode. Since the anode oxidation (AO) combined with oxygen reduction reaction (ORR) enhances ·OH radical generation, the in situ AO-ORR coupling system shows better mineralization efficiency and lower electrochemical energy consumption for organic degradation. Additionally, the nano PbO2 anode exhibited excellent stability and maintained high degradation efficiencies after 15 times of successive reuse of the in situ AO-ORR coupling system. Based on 16 identified intermediates categorized as primary, secondary, and downstream intermediates, a possible degradation pathway of the H-acid electrochemical oxidation was proposed and the toxicity was drastically reduced after the degradation.

On-site monitoring of dissolved Sb species in natural waters by an automatic system using flow injection coupled with hydride generation atomic fluorescence spectrometer

Antimony (Sb) is a toxic and potentially carcinogenic element in the environment. The toxicity of Sb(III) is ten times that of Sb(V). Therefore, on-site monitoring technique for dissolved Sb species is crucial for the study of Sb environmental processes. In this study, an automated, portable, and cost-effective system was developed for field simultaneous analysis of Sb(III) and Sb(III + V) in natural waters. The system comprised a portable atomic fluorescence spectrometer equipped with a built-in electrochemical H2 generator to reduce the consumption of acid/borohydride solution and make the atomizer more stable for on-site analysis. Flow injection technique was also used to achieve on-line pretreatment of water samples, including filtration, acidification, pre-reduction, and hydride generation procedures. Under the optimal conditions, the limits of detection (3σ, n = 11) of the developed method were 0.015 μg/L and the linear ranges were 0.05–5.0 μg/L for both Sb(III) and Sb(III + V). The relative standard deviations (n = 11) of the spiked samples of Sb(V) were 3.2% (0.05 μg/L), 3.3% (0.2 μg/L), and 1.7% (0.5 μg/L), respectively. The spiked recoveries of lake water, treated wastewater, and seawater ranged from 97.0% to 108.5%. The novel system of flow injection coupled with hydride generation atomic fluorescence spectrometer (FI-HG-AFS) was applied to carry out an 18-h fixed-point monitoring at a secondary settling tank of a wastewater treatment facility in Xiamen University, and a 6-h real-time underway analysis in the surface seawater of Dongshan Bay, China, proving that the system was capable of long-term monitoring in the field.

Remediation of groundwater polluted with lindane production wastes by conductive-diamond electrochemical oxidation

This work studies the remediation of groundwater saturated with dense non-aqueous phase liquid (DNAPL) from lindane production wastes by electrochemical oxidation. DNAPL-saturated groundwater contains up to 26 chlorinated organic compounds (COCs), including different isomers of hexachlorocyclohexane (HCH). To do this, polluted groundwater was electrolysed using boron-doped diamond (BDD) and stainless steel (SS) as anode and cathode, respectively, and the influence of the current density on COCs removal was evaluated in the range from 5 to 50 mA cm−2. Results show that current densities higher than 25 mA cm−2 lead to the complete removal and mineralisation of all COCs identified in groundwater. The higher the current density, the higher the COCs removal rate. At lower current densities (5 mA cm−2), chlorobenzenes were completely removed, and degradations above 90 % were reached for COCs with more than five chlorine atoms in their molecules. The use of BDD anodes promotes the electrochemical generation of powerful reactive species, such as persulfate, hypochlorite or hydroxyl radicals, that contribute to the degradation and mineralisation of COCs. The applied current density also influences the generation of these species. Finally, no acute toxicity towards Vibrio fischeri was observed for the treated groundwater after the electrochemical oxidation performed at 5 and 10 mA cm−2. These findings demonstrate that electrochemical oxidation with BDD anodes at moderate current densities is a promising alternative for the remediation of actual groundwater contaminated with DNAPLs.

Synthesis of bimetal-decorated N-doped carbon nanoparticles for enhanced oxygen evolution reaction

Electrochemical hydrogen generation from the most plausible splitting water is severely hindered by OER (oxygen evolution reaction). Hence, the Fe4Co6@NDC amorphous sheet-like lamellar potential electrocatalyst prepared through simple solvothermal synthesis towards OER with low overpotential 307 mV @ 10 mA cm−2, Tafel slope of −55 mV dec-1 and turnover frequency of 0.0396 s−1, compared to 393 mV, Tafel slope of −81 mV dec-1, and a turnover frequency of 0.0136 s−1 at an IrO2 on an inert glassy carbon electrode, under the same conditions in 1 M KOH. The iron: cobalt adjacent ratio (4:6) could give a cooperative synergistic effect for OER, further nitrogen-doped carbon substrate (NDC) offers even metal anchoring sites has provided higher ECSA of 10.202 cm2 and also provides low resistive (5.6 Ω) material. Full cell water splitting Fe4Co6@NDC/NF (anode)//PtC/NF (cathode) with cell potential 1.58 V and the same setup will be used with perennial solar energy source only consumes 1.57 V enhanced hydrogen generation. We anticipate that the developed Fe4Co6@NDC electrocatalyst will be used as a formidable OER catalyst for a clean electrochemical energy conversion process.

Producing p‐tolylmethanol derivatives through an eco‐friendly electro‐organic method: A highly efficient Grignard reaction utilizing a magnesium electrode

This research introduces an eco‐friendly and innovative technique for efficiently producing p‐tolylmethanol derivatives 4(a–k) using electro‐organic synthesis based on the Grignard reaction. By employing electrochemical methods, this approach offers several advantages, including enhanced reaction efficiency and reduced environmental impact. The process involves the electrochemical generation of the Grignard reagent, followed by its reaction with appropriate substrates to yield the desired p‐tolylmethanol derivatives. Our team optimized various reaction parameters like choice of solvent, electrode material, and reaction conditions to achieve high yields and selectivity. The developed electro‐organic method demonstrated outstanding efficiency and presents a fresh and environmentally conscious approach to synthesizing p‐tolylmethanol derivatives from benzaldehyde 1(a–e) and bromobenzene 2(a–h) via the Grignard reaction, yielding excellent results (85–93%). The resulting compounds were comprehensively characterized using melting point, 1H NMR spectroscopy, and CHN analysis to verify their structures. This electro‐organic approach holds significant potential as a sustainable strategy for synthesizing valuable organic compounds.

High-performance electrochemical power generation humidity sensor based on NaCl/sodium alginate humidity sensing electrolyte and Cu/Zn electrodes for visual humidity indication and respiratory patterns detection

Electrochemical power generation humidity sensors have received great attention recently, but it is challenging for achieving good humidity sensing and power generation performances simultaneously. Herein, we construct a high-performance power generation humidity sensor based on NaCl/sodium alginate (SA) humidity sensing electrolyte and Cu/Zn electrodes. Benefiting from the reasonable selection of humidity sensing electrolyte and electrode materials and the design of sensor structure, the optimized NaCl/SA humidity sensor exhibits wide humidity sensing detection range (10.9−91.5% relative humidity (RH)), short response time (5.6 s), and good repeatability (20 cycles) at 25°C. Importantly, the humidity sensor has high response voltage (∼0.7 V), large short circuit current (∼24 μA) and loading power (∼2.63 μW) at 91.5% RH. The NaCl/SA humidity sensor can be used for passive visual humidity indication by connecting it to a pointer microammeter. In addition, we designed signal processing circuit and software program to recognize respiratory patterns using NaCl/SA humidity sensor. This work not only achieves a high-performance electrochemical humidity sensor, but also provides a useful reference for its applications in passive visual humidity and respiratory patterns detections.

Enhanced electrochemical oxygen generation from sillenite phase of bismuth iron oxide (Bi24Fe2O39) ultrafine particles stabilised at room temperature

Recently, lot of research is going on in development of clean energy-based technology to address the issue of exponentially increasing energy demands. Electrochemical water splitting is a clean and efficient process for generation of H2 and O2. Water electrolysis produces hydrogen and oxygen on cathode and anode respectively as separate half-cell reactions is one of the most important clean alternative processes. This work reports synthesis of Bi24Fe2O39 ultrafine crystalline nanoparticles via facile room temperature chemical method for the first time. Bi24Fe2O39 shows a spherical morphology with an average size of 8 nm. As obtained Bi24Fe2O39 acts as an electrocatalyst for electrochemical oxygen evolution reaction (OER). Electrochemical oxygen generation studies confirm the overpotential of 420 mV in 1 M KOH solution at a current density of 10 mA/cm2. Tafel slope and EIS studies give further insight of oxygen generation process. The results show that Bi24Fe2O39 exhibits low Tafel slope of 63 mV dec−1 and a very low charge transfer resistance of ∼10 Ω. This study paves a new way for future research into bismuth based sillenite structure for various energy related applications.

Electrochemical Generation of Ketyl Radicals and Their Applications

AbstractKetyl radicals display new reactivities beyond the intrinsic electrophilicity of carbonyls. Recent progress in organic electrosynthesis has fueled the generation and utilization of ketyl radicals under ‘greener’ conditions. This graphical review summarizes these electrochemical advancements into three major categories: cross-pinacol couplings, coupling of carbonyls with alkyl radical precursors, and coupling of carbonyls with unsaturated systems (alkenes, alkynes, cyanoarenes, and N-heterocycles).

Synergistically S/N self-doped biochar as a green bifunctional cathode catalyst in electrochemical degradation of organic pollutant

Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes (EAOPs) due to its high performance and sustainable synthesis. Herein, we illustrated the morphological fates of waste leaf-derived graphitic carbon (WLGC) produced from waste ginkgo leaves via pyrolysis temperature regulation and used as bifunctional cathode catalyst for simultaneous H2O2 electrochemical generation and organic pollutant degradation, discovering S/N-self-doping shown to facilitate a synergistic effect on reactive oxygen species (ROS) generation. Under the optimum temperature of 800 °C, the WLGC exhibited a H2O2 selectivity of 94.2% and tetracycline removal of 99.3% within 60 min. Density functional theory calculations and in-situ Fourier transformed infrared spectroscopy verified that graphitic N was the critical site for H2O2 generation. While pyridinic N and thiophene S were the main active sites responsible for •OH generation, N vacancies were the active sites to produce 1O2 from O2. The performance of the novel cathode for tetracycline degradation remains well under a wide pH range (3–11), maintaining excellent stability in 10 cycles. It is also industrially applicable, achieving satisfactory performance treating in real water matrices. This system facilitates both radical and non-radical degradation, offering valuable advances in the preparation of cost-effective and sustainable electrocatalysts and hold strong potentials in metal-free EAOPs for organic pollutant degradation.

Electrochemical generation of phenothiazin-5-ium. A sustainable strategy for the synthesis of new bis(phenylsulfonyl)-10H-phenothiazine derivatives

In this work, the electrochemical generation of phenothiazin-5-ium (PTZox) from the direct oxidation of phenothiazine (PTZ) in a water/acetonitrile mixture using a commercial carbon anode and conventional stainless steel cathode is reported. PTZox is a reactive intermediate with high potential synthetic applications, which is used in this paper for the synthesis of new phenothiazine derivatives. In this work a novel and simple electrochemical methodology for the synthesis of some bis(phenylsulfonyl)-10H-phenothiazine derivatives was established. In this paper, a mechanism for PTZ oxidation in the presence of arylsulfinic acids has been proposed based on the results obtained from voltammetric and coulometric experiments as well as spectroscopic data of the products. These syntheses are performed in a simple cell by applying constant current under mild conditions and at room temperature with high atom economy.