Charge Transfer Rate Constant Research Articles

The Influence of Spirodi(Iminohydantoin) on Charge Transfer through ds-DNA Containing 8-OXO-dG: A Theoretical Approach.

Genetic information stored in a DNA base sequence is continuously exposed to harmful factors. It has been determined that 9 × 104 different DNA damage events occur in a single human cell every 24 h. Of these, 7,8-dihydro-8-oxo-guanosine (OXOG) is one of the most abundant and can undergo further transformations towards spirodi(iminohydantoin) (Sp). Sp is highly mutagenic in comparison to its precursor if not repaired. In this paper, the influence of both Sp diastereomers 4R and 4S as well as their anti and syn conformers on charge transfer through the double helix was taken into theoretical consideration. In addition, the electronic properties of four modelled double-stranded oligonucleotides (ds-oligos) were also discussed, i.e., d[A1Sp2A3oxoG4A5] * [T5C4T3C2T1]. Throughout the study, the M06-2X/6-31++G** level theory was used. Solvent-solute non-equilibrated and equilibrated interactions were also considered. The subsequent results elucidated that the 7,8-dihydro-8-oxo-guanosine:cytidine (OXOGC) base pair is the settled point of a migrated radical cation in each of the discussed cases, due to its low adiabatic ionization potential, i.e., ~5.55 [eV]. The opposite was noted for excess electron transfer through ds-oligos containing anti (R)-Sp or anti (S)-Sp. The radical anion was found on the OXOGC moiety, whereas in the presence of syn (S)-Sp or syn (R)-Sp, an excess electron was found on the distal A1T5 or A5T1 base pair, respectively. Furthermore, a spatial geometry analysis of the discussed ds-oligos revealed that the presence of syn (R)-Sp in the ds-oligo caused only a slight deformation to the double helix, while syn (S)-Sp formed an almost ideal base pair with a complementary dC. The above results are in strong agreement with the final charge transfer rate constant, as calculated according to Marcus' theory. In conclusion, DNA damage such as spirodi(iminohydantoin), especially when becoming part of clustered DNA damage, can affect the effectiveness of other lesion recognition and repair processes. This can lead to the acceleration of undesired and deleterious processes such as carcinogenesis or aging. However, in terms of anticancer radio-/chemo- or combined therapy, the slowing down of the repair machinery can result in increased effectiveness. With this in mind, the influence of clustered damage on charge transfer and its subsequent effect on single-damage recognition by glycosylases justifies future investigation.

Dark Current Water Splitting Employing Ni3TeO6 as a Photocharged Photoelectrocatalyst

Herein, the photoelectrocatalytic and photocharging activity of a Ni3TeO6 (NTO‐700) photoelectrocatalyst for water oxidation in alkaline medium is demonstrated and calcined at 700 °C. The photoelectrocatalytic (PEC) activity of the sample is increased upon an increase in the illumination time. With a twofold increase in photocurrent density at 1.8 V, the PEC 150 sample (having been illuminated for 150 min) attained the highest PEC activity. The synthesized material has displayed an excellent charge storage capacity in KOH and Na2SO4 electrolyte solutions (both 0.1 m). The chrono‐amperometry measurement, subsequent to light interruption, has sustained almost 44% higher current density (even after 200 min) compared to the pure electrocatalytic baseline in a Na2SO4 electrolyte. The charge transfer resistance, Rct, decreases from 633.40 to 170.40 Ω, while the charge transfer rate constant, kct, increases from 7.93 to 27.03 s−1, as a function of illumination time. This points to fast separation of electron–hole (e−–h+) pairs and a slower recombination rate. The lower values of the charge transfer resistance and the time constant recorded for the light interrupted samples, as compared to the electrochemical sample, are attributed to the stored charge that drives water oxidation at a higher rate.

ЭЛЕКТРОХИМИЧЕСКОЕ ПОВЕДЕНИЕ ТИТАНА В ХЛОРИДНО-ФТОРИДНЫХ РАСПЛАВАХ РАЗЛИЧНОГО СОСТАВА В ПРИСУТСТВИИ КАТИОНОВ ЩЕЛОЧНОЗЕМЕЛЬНЫХ МЕТАЛЛОВ

The electrochemical behavior of titanium and the influence of alkali earth metal cations (Mg2+, Ca2+, Sr2+ and Ва2+) on the charge transfer kinetics of the Ti(IV)/Ti(III) redox couple were studied by cyclic voltammetry method in chloride-fluoride melts of different composition. Standard rate constants of charge transfer and the activation energies of the charge transfer process were calculated.

The Influence of 5',8-Cyclo-2'-Deoxyguanosine on ds-DNA Charge Transfer Depends on Its Diastereomeric Form: A Theoretical Study.

The genetic information stored in the nucleobase sequence is continuously exposed to harmful extra- and intra-cellular factors, which can lead to different types of DNA damage, with more than 70 lesion types identified so far. In this article, the influence of a multi-damage site containing (5'R/S) 5',8-cyclo-2'-deoxyguanosine (cdG) and 7,8-dihydro-8-oxo-2'-deoxyguanosine (OXOdG) on charge transfer through ds-DNA was taken into consideration. The spatial geometries of oligo-RcdG: d[A1(5'R)cG2A3OXOG4A5]*d[T5C4T3C2T1] and oligo-ScdG: d[A1(5'S)cG2A3OXOG4A5]*d[T5C4T3C2T1] were optimized at the M06-2X/6-D95**//M06-2X/sto-3G level of theory in the aqueous phase using ONIOM methodology. For all the electronic property energies under discussion, the M06-2X/6-31++G** level of theory was used. Additionally, the non-equilibrated and equilibrated solvent-solute interactions were into consideration. The obtained results confirm the predisposition of OXOdG to radical cation formation regardless of the presence of other lesions in a ds-DNA structure. In the case of electron transfer, however, the situation is different. An excess electron migration towards (5'S)cdG was found to be preferred in the case of oligo-ScdG, while in the case of oligo-RcdG, OXOdG was favored. The above observation was confirmed by the charge transfer rate constant, vertical/adiabatic ionization potential, and electron affinity energy values, as well as the charge and spin distribution analysis. The obtained results indicate that 5',8-cyclo-2'-deoxyguanosine, depending on the C5' atom chirality, can significantly influence the charge migration process through the double helix. The above can be manifested by the slowdown of DNA lesion recognition and removal processes, which can increase the probability of mutagenesis and subsequent pathological processes. With regard to anticancer therapy (radio/chemo), the presence of (5'S)cdG in the structure of formed clustered DNA damage can lead to improvements in cancer treatment.

Revealing the enhanced photoelectrochemical water oxidation activity of Fe-based metal-organic polymer-modified BiVO4 photoanode

Metal-organic polymers (MOPs) can enhance the photoelectrochemical (PEC) water oxidation performance of BiVO4 photoanodes, but their PEC mechanisms have yet to be comprehended. In this work, we constructed an active and stable composite photoelectrode by overlaying a uniform MOP on the BiVO4 surface using Fe2+ as the metal ions and 2,5-dihydroxyterephthalic acid (DHTA) as ligand. Such modification on the BiVO4 surface yielded a core-shell structure that could effectively enhance the PEC water oxidation activity of the BiVO4 photoanode. Our intensity-modulated photocurrent spectroscopy analysis revealed that the MOP overlayer could concurrently reduce the surface charge recombination rate constant (ksr) and enhance the charge transfer rate constant (ktr), thus accelerating water oxidation activity. These phenomena can be ascribed to the passivation of the surface that inhibits the recombination of the charge carrier and the MOP catalytic layer that improves the hole transfer. Our rate law analysis also demonstrated that the MOP coverage shifted the reaction order of the BiVO4 photoanode from the third-order to the first-order, resulting in a more favorable rate-determining step where only one hole accumulation is required to overcome water oxidation. This work provides new insights into the reaction mechanism of MOP-modified semiconductor photoanodes.

Probability of charge transport through al/GaAs interfaces system using quantum model

The focus of this paper is on the investigation and the understanding of transition probability of charge at the metal/semiconductor interface depending on the calculation of the rate constant. For this system we can suppose two localized quantum vector states system with a conduction electron state vector l 〉 interacting with an acceptor state vector l 〉 of electron in band of metal with the interacting described by the coupling matrix element. Expression of rate constant of charge transfer for metal/semiconductor system derived upon the quantum model and perturbation theory for transition between l 〉 and I state when the coupling matrix element coefficient smaller than . The probability of the charge transfer rate constant for the metal/semiconductor interface in this context, is basically defined as a relatively to potential barrier between a metal and a semiconductor The probability of charge transfer rate constant evaluated with reorganization energy using a matlap program. Theoretical results obtained for our mode show that the probability of charge transfer is more probable with decreasing the reorganization energy.

Enhancement in Photoelectrochemical Efficiency and Modulation of Surface States in BiVO4 through the TiO2 Outer Layer Using the Atomic Layer Deposition Technique

Owing to several important properties, BiVO4 is the promising photoanode material for the photoelectrochemical (PEC) water oxidation reaction; however, the poor charge transfer and transport and slow surface catalytic activity limit to achieve the expected high theoretical efficiency. In the present investigation, thin films of TiO2 have been formed over the BiVO4 photoanode surface using the atomic layer deposition technique (ALD). Films are formed at 5, 50, and 150 nm thicknesses, and the PEC performances have been evaluated. Enhancement in the performance has been observed upon inclusion of the ALD/TiO2 films over BiVO4. The performance has been observed to be higher in the case of 50 nm ALD/TiO2 films. The ALD/TiO2 films have several important roles in the enhancement in the PEC efficiency other than only the enhancement of stability through retardation of the photocorrosion process. The intensity modulated photocurrent spectroscopy measurements have been carried out for the selective evaluation of the different modes of charge transfer processes upon excitation of the photoanode materials on photoexcitation. The enhancement in the charge transfer rate constant (kt) over the relative retardation of the charge recombination rate constant (kr) indicated the specific roles of modulation of the surface states. The investigation revealed the significant scopes of the modifications of surfaces using ALD techniques to selectively modulate the surface electronic states of materials in enhancing catalytic efficiency.

Morphological peculiarities of the lithium electrode from the perspective of the Marcus-Hush-Chidsey model

This study employs the kinetics framework of Marcus-Hush-Chidsey (MHC) to investigate the charge transfer at the interface of lithium electrode and electrolyte in lithium(ion)-batteries. The charge-transfer rate constant is evaluated for different facets of lithium, namely (1 0 0), (1 1 0), (1 0 1), and (1 1 1) as a function of surface charge density with the aid of density functional theory (DFT) calculations. The results highlight and quantify the sensitivity of the rate of lithium plating and stripping to the surface orientation, surface charge density, and charge-transfer over-potential. An intrinsic kinetics competition among the different surface orientations is identified together with an asymmetry between the lithium plating and stripping and showcased to influence the deposit morphology and surface protrusions and indentations.

Photo-induced carrier dynamics in nano-porous TiO2 electrochemically doped with cuprous oxide

In the present paper, photo-induced carrier dynamics and charge transfer processes on porous anodic TiO2, modified with Cu2O via pulse electrodeposition, are studied with steady-state and modulated photocurrent measurements in a wide range of experimental conditions. Surface composition was estimated using XPS. The obtained oxides are p-type semiconductors that effectively absorb visible light, and rates of charge transfer and recombination are strongly dependent on synthesis conditions. A tentative mechanism of photo-induced hydrogen evolution on such materials is proposed using recent simulation results from the literature and the dependence of formal charge transfer rate constant on potential.

Carbon Inks-Based Screen-Printed Electrodes for Qualitative Analysis of Amino Acids.

Due to the great significance of amino acids, a substantial number of research studies has been directed toward the development of effective and reliable platforms for their evaluation, detection, and identification. In order to support these studies, a new electrochemical platform based on PANI/ZnO nanowires' modified carbon inks screen-printed electrodes was developed for qualitative analysis of electroactive amino acids, with emphasis on tyrosine (Tyr) and tryptophan (Trp). A comparative investigation of the carbon ink before and after modification with the PANI/ZnO was performed by scanning electron microscopy and by Raman spectroscopy, confirming the presence of PANI and ZnO nanowires. Electrochemical investigations by cyclic voltammetry and electrochemical impedance spectroscopy have shown a higher charge-transfer rate constant, which is reflected into lower charge-transfer resistance and higher capacitance values for the PANI/ZnO modified ink when compared to the simple carbon screen-printed electrode. In order to demonstrate the electrochemical performances of the PANI/ZnO nanowires' modified carbon inks screen-printed electrodes for amino acids analysis, differential pulse voltammograms were obtained in individual and mixed solutions of electroactive amino acids. It has been shown that the PANI/ZnO nanowires' modified carbon inks screen-printed electrodes allowed for tyrosine and tryptophan a peak separation of more than 100 mV, enabling their screening and identification in mixed solutions, which is essential for the electrochemical analysis of proteins within the proteomics research field.

Исследование влияния катионов щелочноземельных металлов на электрохимическое поведение редокс-пары Ti (IV) / Ti (III) в расплаве CsCl — CsF

The influence of the alkaline earth metal cations (Mg2+, Ca2+, Sr2+ и Ва2+) on the charge transfer kinetics of the Ti (IV) / Ti (III) redox couple in melts of alkali metal halides was studied by cyclic voltammetry method. Standard rate constants of charge transfer have been determined by the Nicholson method. The activation energies of the charge transfer process in the CsCl — CsF (10 wt. %) — K2TiF6 melt with the addition of alkaline earth metal cations were calculated.

Reaction kinetics on facet-engineered bismuth tungstate photoanodes for water oxidation

Charge separation and transfer kinetics play a significant role in photocatalytic water oxidation, which is sensitive to the crystal facets. Herein, the bismuth tungstate (Bi2WO6) films were used as a model photoanode to investigate how the photogenerated charges react on {131} and {200} facets under constantly applied bias in a photoelectrochemical (PEC) cell. On the WO3 electron transport layer, the Bi2WO6 films have a {200} orientation while possessing a {131} orientation on the fluorine-doped tin oxide substrate. It is discovered that {200} facets on the WO3/Bi2WO6 heterojunction display a low overpotential of PEC water oxidation, showing a 1st-order reaction behavior and faster charge transfer rate constant. Differently, water oxidation on the {131} facet on Bi2WO6 displays a 2nd-order reaction behavior. Further, density functional theory calculations were applied to demonstrate how the rate-determining step and the major formed intermediate correlate with the charge accumulation and reaction orders. The findings of this work shed fundamental light on how to rationally design and precisely modulate surface charge density and reaction kinetics for efficient (photo)electrocatalysts.

Stimulation of ethylene glycol electrooxidation on electrodeposited Ni–PbO2–GN nanocomposite in alkaline medium

In this work, a novel system composed of non-precious nickel-based metal oxide/reduced graphene oxide nanocomposite (Ni–PbO2–GN) is used for electrooxidation of ethylene glycol (EG) in 1.0 M NaOH solution and compares its activity with that of Ni, Ni–GN, and Ni–PbO2. The facile electrodeposition technique is used to prepare the catalysts on glassy carbon (GC) substrates. The outcomes of electrochemical measurements show a high performance towards EG oxidation is obtained for Ni-nanocomposite electrodes compared to that of Ni mainly due to their higher surface areas. The excellent electrocatalytic properties of the Ni-nanocomposite could be ascribed to the synergistic contributions of PbO2 and graphene (GN) nano-sheets that help the reduction of Ni grains. A smaller charge transfer resistance value of 34.5 Ω cm2 for EG oxidation reaction at + 360 mV is recorded for GC/Ni–PbO2–GN compared to the other prepared electrodes. Moreover, it exhibits higher kinetic parameters of EG such as diffusion coefficient (D = 3.9 × 10–10 cm2 s−1) and charge transfer rate constant (ks = 32.5 mol−1 cm3 s−1). The overall performance and stability of the prepared catalysts towards EG electrooxidation have been estimated to be in the order of GC/Ni–PbO2–GN > GC/Ni–GN > GC/Ni–PbO2 > GC/Ni.Graphical abstract

Impedance analysis of electrodes made of continuous carbon filaments in a 20 cm2 redox flow cell

• Continuous filament electrodes permit studies on electrode filament arrangements. • Continuous filament electrodes allow for side electrical contact without compression. • A common charge-transfer rate constant, k 0 of 2.2·10 -4 cm s -1 , was estimated. • Mass-transfer resistance improved with non-uniform filament spatial density. The most commonly used electrodes in redox flow batteries are carbon fiber felts, which are assemblies of randomly oriented short fibers. The avenues to improve cell performance are usually pre-treatment to enhance their catalytic activity, modifications of their porosity, and reducing resistivity by increasing compression. Our investigations focus on carbon electrodes made of continuous carbon filaments, where filaments were arranged in specific geometric patterns in order to investigate the effect of the fiber density and spatial distribution across direction of flow on the cell performance. To identify the source of cell voltage losses, electrochemical evaluations were performed with electrochemical impedance spectroscopy (EIS), and compared with commonly used felt electrodes. The electrochemically reversible ferri/ferrocyanide system at 50% state-of-charge (SOC) was used as redox probe for both anolyte and catholyte to avoid varying electrode activities of anode/cathode due to differences in redox species. The findings generate electrode design considerations to reduce voltage losses in redox flow batteries.

Base-metal oxide semiconductor electrodes for PPCP degradation: Ti-doped α-Fe2O3 for sulfosalicylic acid oxidation as an example

Sulfosalicylic acid is a typical pharmaceutical and personal care product with high toxicity, environmental persistence, and low biodegradability. Electrochemical oxidation has been demonstrated to be a promising way for hazardous organics treatment, but it is severely limited by the high cost and resource shortage of electrode materials. Base-metal oxide semiconductor anodes have the merits of low cost, diversity, and tunable energy levels for charge transfer, and thus may be alternatives to the electrodes for wastewater treatment. Herein, we found that Ti-doped α-Fe2O3, as an example, could be efficient for sulfosalicylic acid oxidation, reaching comparable faraday efficiency of sulfosalicylic acid to that of the boron-doped diamond electrode. Ti-doped electrodes exhibited both higher removal rates and current efficiency compared to the undoped. This could be mainly ascribed to the enhanced charge transfer rate constant. Kinetic analysis shows that the apparent reaction order, in terms of sulfosalicylic acid in bulk solution, depended on applied potential and pollutant concentration. Mechanism study shows that the oxidation of sulfosalicylic acid was mainly through indirect pathway. Moreover, the oxidation products were determined and the oxidation mechanism was proposed. This study may open a door to employ base-metal oxide semiconductor anodes for the efficient treatment of organic wastewater.

Comprehension of the Synergistic Effect between m&t-BiVO4/TiO2-NTAs Nano-Heterostructures and Oxygen Vacancy for Elevated Charge Transfer and Enhanced Photoelectrochemical Performances.

Through the utilization of a facile procedure combined with anodization and hydrothermal synthesis, highly ordered alignment TiO2 nanotube arrays (TiO2-NTAs) were decorated with BiVO4 with distinctive crystallization phases of monoclinic scheelite (m-BiVO4) and tetragonal zircon (t-BiVO4), favorably constructing different molar ratios and concentrations of oxygen vacancies (Vo) for m&t-BiVO4/TiO2-NTAs heterostructured nanohybrids. Simultaneously, the m&t-BiVO4/TiO2-NTAs nanocomposites significantly promoted photoelectrochemical (PEC) activity, tested under UV-visible light irradiation, through photocurrent density testing and electrochemical impedance spectra, which were derived from the positive synergistic effect between nanohetero-interfaces and Vo defects induced energetic charge transfer (CT). In addition, a proposed self-consistent interfacial CT mechanism and a convincing quantitative dynamic process (i.e., rate constant of CT) for m&t-BiVO4/TiO2-NTAs nanoheterojunctions are supported by time-resolved photoluminescence and nanosecond time-resolved transient photoluminescence spectra, respectively. Based on the scheme, the m&t-BiVO4/TiO2-NTAs-10 nanohybrids exhibited a photodegradation rate of 97% toward degradation of methyl orange irradiated by UV-visible light, 1.14- and 1.04-fold that of m&t-BiVO4/TiO2-NTAs-5 and m&t-BiVO4/TiO2-NTAs-20, respectively. Furthermore, the m&t-BiVO4/TiO2-NTAs-10 nanohybrids showed excellent PEC biosensing performance with a detection limit of 2.6 μM and a sensitivity of 960 mA cm-2 M-1 for the detection of glutathione. Additionally, the gas-sensing performance of m&t-BiVO4/TiO2-NTAs-10 is distinctly superior to that of m&t-BiVO4/TiO2-NTAs-5 and m&t-BiVO4/TiO2-NTAs-20 in terms of sensitivity and response speed.

Low temperature growth of CuS nanosheets on hollow Co9S8 nanotubes: Synthesis and analytical application

Transition metal sulfides have found wide applications as promising catalysts and electrocatalysts. Herein, hollow Co9S8 nanotubes were prepared through hydrothermal method, on which CuS nanosheets were grown at low temperature, and hollow Co9S8@CuS heterostructure nanocomposite was synthesized. The prepared hollow Co9S8 nanotubes possess high specific surface area and efficient charge transfer ability, offering an ideal substrate for the growth of CuS nanosheets. Furthermore, the hollow structure of the synthesized Co9S8@CuS can accelerate mass transfer and provide more reaction sites with the specific area of 36.79 m2/g, and the heterostructure between Co9S8 and CuS enhanced their synergistic effect on the conductivity and electrocatalytic activities. For analytical application, the synthesized Co9S8@CuS nanocomposite was applied for the determination of glucose and H2O2, with the charge transfer rate constants of 3.89 and 1.94 s−1, respectively. Under optimal conditions, the Co9S8@CuS-modified glassy carbon electrode exhibits wide linear ranges of 0.03–13 mM and 0.05–14 mM with detection limits of 5.64 μM and 6.06 μM for the oxidation of glucose and the reduction of H2O2, respectively. Additionally, real sample analyses demonstrate satisfying recoveries of 96.43 % and 101.65 % to glucose and H2O2, respectively, indicating its potential to quantitatively analyze the real samples.

Kinetic and Thermodynamic Properties of Ytterbium Chloride and Fluoride Complexes in Chloride Melts

An important problem concerning rare earth metals and molten salts is the reprocessing of nuclear fuel, since lanthanides are always present in spent nuclear fuel. According to the technology being developed for pyroelectrochemical processing of nuclear waste spent fuel is converted into molten salts by anodic dissolution, followed by electrochemical extraction of actinides from lanthanides.Thus a knowledge of the electrochemistry and thermodynamics of lanthanide compounds in molten salt systems is very useful for the understanding the recycling of spent nuclear fuel.The electroreduction of YbCl3 in alkali chloride melts (NaCl-KCl, KCl, CsCl) was studied in the temperature range 973-1173 K by different electrochemical methods. The diffusion coefficients (D) for Yb(III) and Yb(II) were determined by linear sweep voltammetry, chronopotentiometry and chronoamperometry methods. Decreasing values of D were obtained when the cation in the second coordination sphere changed from Na to Cs. It was shown that such changes are due to the decreasing of counter polarizing effect of cations with increasing cationic radius.The standard rate constants of charge transfer (k s) for the Yb(III)/Yb(II) redox couple were calculated on the basis of cyclic voltammetry data using Nicholson’s approach. The following row of the standard rate constants of charge transfer has been experimentally determined: k s (KCl) < k s (CsCl) < k s (NaCl-KCl).The formal redox potentials E* Yb(III)/Yb(II were obtained in alkali chlorides melts from the linear sweep voltammetry data. From the values of the formal redox potentials were calculated the Gibbs energies and equilibrium constants for the reaction:YbCl2(sol.) +1/2 Cl2(g.) « YbCl3(sol.) (1)It was determined the increasing of the formal entropy for the reaction (1) in transition from NaCl-KCl to CsCl melt that associated with a greater degree of ordering of the reaction products due to the complex formation.Influence of fluoride ions (NaF) on the electrochemical behavior of the Yb(III)/Yb(II) redox couple in an equimolar NaCl-KCl melt was studied. It was determined а decrease of diffusion coefficients and standard rate constants, as well as a shift of the formal redox potentials to the negative region.

Electrochemistry of Neodymium in an Equimolar NaCl-KCl Melt without and with Addition of Fluoride Ions

An investigation of compounds of those few elements in the oxidation state (II), by opposition to the general trivalent lanthanides is of special interest. The present work follows our previous investigations on samarium, europium ytterbium chloride systems and, in particular, the electrochemical behavior of the Sm(III)/Sm(II), Eu(III)/Eu(II) Yb(III)/Yb(II) redox couples. It deals with neodimium compounds.The electrochemical behavior of NdCl3 in molten salts was studied in few works, but only melts with a low melting point LiCl-KCl and LiCl-KCl-CsCl were investigated.The electroreduction of NdCl3 in an equimolar NaCl-KCl mixture was studied in the temperature range 973-1123 K by different electrochemical methods. It was shown that the discharge of Nd(III) to Nd(II) is complicated by the disproportionation reaction (DPP):3Nd(II) ↔ 2Nd(III) + Nd (1)Ignoring of reaction DPP can lead to incorrect determination of values diffusion coefficients and formal standard redox potentials of the Nd(III)/Nd(II) redox couple. The relatively narrow interval of polarization rate was found when the recharge process was reversible and not accompanied by the DPP reaction. At these scan rates the diffusion coefficients and formal standard redox potentials of the Nd(III)/Nd(II) redox couple were determined by cyclic voltammetry.The standard rate constants for the redox reaction Nd(III) + e- ↔ Nd(II) were calculated on the basis of cyclic voltammetry at sweep rates corresponding to the quasy-reversible process. The nature of working electrode on the rate of charge transfer for the Nd(III)/Nd(II) redox couple was studied. It was found that the values of k s determined at a molybdenum electrode were higher than those at a glassy carbon electrode.The introduction of fluorine anions into a chloride melt at a molar ratio of F-/Nd(III) = 5 leads to the disappearance of the recharge wave and only an ascending section associated with joint discharge of neodymium complexes and sodium and potassium cations was observed. Thus, the introduction of fluorine anions leads to stabilization of the highest oxidation state of neodymium in chloride-fluoride melt and neodymium in the oxidation state +2 does not exist in the melt.Introducing of fluoride ions to the melt NaCl-KCl containing Nd(II) accompanied by reaction of disproportionation:3NdCl4 2- + 12F- ↔ 2NdF6 3- + Nd + 12Cl- (2)The standard rate constants of charge transfer for the Nd(III)/Nd(II) redox couple were compared with the values obtained for other redox couples of lanthanides and these results were discussed in connection with the strength and stability of complexes.

Insights into the charge transfer kinetics in BiVO4 photoanodes modified with transition metal-based oxygen evolution electrocatalysts

BiVO4 is a promising photoanode for photoelectrochemical (PEC) water splitting. Nevertheless, the sluggish water oxidation on its surface causes severe charge carriers recombination and thus reduces the overall efficiency. To overcome these imperfections, BiVO4 photoanodes were prepared and modified with transition metal-based oxygen evolution electrocatalysts, namely, NiFe, CoNi, and CoFe–layered double hydroxides (LDHs) oxygen evolution catalysts (OECs). The kinetics of charge transfer and recombination in the prepared photoanodes were studied by transient photocurrent and intensity-modulated photocurrent spectroscopy (IMPS). The rate constants of charge transfer and recombination were determined and correlated with the generated photocurrent to disclose the function of each electrocatalyst. It was concluded that the three investigated LDHs exhibit a comparable electrocatalytic activity at low applied potential, but CoNi–LDH has a superior passivation effect. Contrary to CoFe and NiFe–LDHs, CoNi–LDH passivates the surface states and unpins the Fermi level as proved by IMPS and photovoltage measurements. This study provides a systematic pathway to disclose the role of LDH OECs on BiVO4 surface which is an essential step for the rational design of efficient photoanodes.