Search Results (138)

The sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at air cathodes severely restrict the practical application of rechargeable zinc–air batteries (ZABs). Herein, equimolar lanthanide-doped spinel Co₃O₄ bifunctional electrocatalysts were synthesized via a citric acid-assisted sol–gel method. Among Ce-, Pr-, La-, and Sm-doped catalysts, Sm-Co₃O₄ exhibits the optimal electrocatalytic performance with a high ORR half-wave potential of 0.72 V and superior OER activity with an overpotential of 1.65 V at 10 mA cm⁻², achieving a minimal potential gap ΔE of 0.93 V. Rotating ring-disk electrode (RRDE) measurements and Koutecky–Levich (K–L) analyses confirm the exclusive 4e⁻ ORR pathway. Characterizations reveal that Sm doping modulates the electronic structure and lattice distortion of Co₃O₄, raises the Co²⁺/Co³⁺ ratio (0.59) and creates abundant oxygen vacancies, thereby significantly lowering the overpotentials for both ORR and OER. This study provides new insights for designing high-performance spinel-based bifunctional electrocatalysts for ZABs. Full article

In this study, we combine experimental and computational approaches to elucidate a density functional theory (DFT)-derived mechanism for superoxide scavenging by resveratrol, piceatannol, and oxyresveratrol. Using rotating ring–disk electrode (RRDE) hydrodynamic voltammetry, the superoxide radicals are generated in situ, allowing direct measurement of antioxidant activity. Data show that the catechol-containing piceatannol is approximately four times more active than resveratrol, while resveratrol and oxyresveratrol exhibit similar efficiencies, indicating that the additional 2′-OH group in oxyresveratrol has minimal impact. Vitamin C (ascorbic acid) facilitates scavenging by acting as a proton donor for resveratrol, piceatannol, and 4′-OH oxyresveratrol, but it is unable to deprotonate the 2′OH group of oxyresveratrol. The experimental results suggest a superoxide dismutase (SOD)-like mechanism, obtained from energetically feasible DFT calculations, in which these stilbenes convert two superoxide anions into H₂O₂ and O₂, helped by vitamin C. Mechanistically, the first superoxide is reduced by abstracting a hydroxyl-group hydrogen atom, while the second undergoes oxidation via π–π interaction with the aromatic system, releasing O₂. Notably, resveratrol can be regenerated through a catalytic cycle involving vitamin C. These data underscore the SOD-mimicking properties of dietary polyphenols and suggest a need to reevaluate resveratrol’s clinical utility regardless of its low bioavailability. Full article

The morphological and structural state of rough solid electrodes usually has a complex effect on the kinetics of an electrochemical process. In order to correctly distinguish the influence of different factors on the rate of an electrode reaction, it is necessary to first separate a purely geometric current rise caused by the surface area increase. At the same time, it is necessary to take into account that surface roughness itself often not only leads to a geometric rise in the electrode area, but also contributes to a change in the kinetic parameters of the electrochemical process. As a consequence, the conclusion regarding an electrocatalytic effect will be reasonable only if the roughness effect is correctly taken into account. The most difficult problem is to establish the role of roughness when experimental electrochemical data are obtained under mixed diffusion–kinetic control of the electrode process. However, the use of appropriate theoretical approaches is required to correctly determine the kinetic characteristics of the electrochemical stage, i.e., of the charge transfer stage. This paper establishes the influence of the morphology and structure of electrodeposited copper coatings on the kinetics of the cathodic reduction of nitrate ion, which occurs in a mixed diffusion–kinetic mode, using the theoretical model of chronoamperometry of an electrochemical process on a rough electrode developed earlier by the authors. Several Cu-electrodes with roughness and structure, the parameters of which vary widely enough, were obtained by cathodic deposition from sulfate solutions of different compositions. The integral (roughness factor) and local (average roughness) characteristics of the surface morphology were determined by methods of underpotential deposition and atomic force microscopy, respectively. Structural investigation of the electrodeposited coatings was carried out by X-ray diffraction to determine their crystallographic structure and average crystallite size. The methods of voltammetry and a rotating disk electrode revealed the mixed kinetics of the electroreduction of ${\mathrm{NO}}_3^{-}$ ions. The kinetic parameters of the charge transfer stage on the copper coatings with a roughness factor of f_r ≤ 3.5 are determined for the first time in this paper by treatment of the experimental current decay curves with the non-linear theoretical equation obtained by the authors for the chronoamperogram of the process on rough electrodes. It was found that the rate constant of the charge transfer stage and the exchange current density of the nitrate ion electroreduction increase by about 50%, with an increase in the average surface roughness from 25 to 120 nm. Considering that this effect is not caused by a purely geometric increase in the true surface area of the electrode, and that the average crystallite size is approximately the same (25 ± 2 nm) for all investigated coatings, it can be concluded that the electrocatalytic activity of copper increases in the reaction of the cathodic reduction of nitrate ions during the transition to copper electrodes with the higher average surface roughness. Taking into account XRD data, the role of the structural and morphological state in the kinetics of the electroreduction of nitrate ions has been established. The smoothest polycrystalline coating was found to be the least electrocatalytically active in this reaction. On the contrary, the roughest coatings with the most prominent plane (220) show the highest activity, which increases with increasing average roughness, possibly due to the growth of defects and excess energy of such curved surfaces. Full article

Hydrogen peroxide (H₂O₂) is widely regarded as a clean and high-value chemical; however, its conventional industrial production remains both energy-intensive and environmentally unsustainable. In this study, sulfur-deficient ZnIn₂S₄ (denoted SDZIS) was developed as an efficient photocatalyst for H₂O₂ generation through oxygen reduction under visible-light irradiation. SDZIS photocatalysts with controllable sulfur-vacancy concentrations were synthesized via a one-step citric-acid-assisted hydrothermal process combined with NaOH etching. The results of transient photocurrent response and electrochemical impedance spectroscopy show that the separation efficiency of charge carriers has been improved. Compared with pristine ZnIn₂S₄, the optimized SDZIS catalyst achieved a nine-fold enhancement in the H₂O₂ production rate, reaching 2711.81 μmol g⁻¹ h⁻¹. Results of experimental and density functional theory calculations suggest that sulfur vacancies can modulate the catalyst work function and the adsorption energy of O₂. Comparative experiments indicate that an appropriate concentration of sulfur vacancies can lead to a high H₂O₂ yield. Combined with scavenger tests, DMPO-EPR, and rotating ring disk electrode measurements, these results support a sulfur-vacancy-associated enhancement in charge separation and a tendency toward a superoxide-involved 2e⁻ ORR pathway for H₂O₂ production. Full article

The PGM-free Fe–Ni–Co trimetallic catalysts developed in this study demonstrated outstanding performance for the oxygen evolution reaction (OER), achieving overpotentials as low as 300 mV at 10 mA cm⁻² in rotating disk electrode (RDE) measurements, a value competitive with the most efficient non-noble electrocatalysts reported in the literature. This study validates the strong catalytic performance of the baseline trimetallic configuration and provides important insights into the relationships among synthesis, structure, and morphology that govern catalyst activity. In particular, the findings highlight that although organic additives can be promising modifiers, the interaction between precursors and transition metals must be carefully controlled to avoid active-site isolation when designing efficient catalysts for sustainable hydrogen production. Actually, to further enhance catalytic activity, the nitrogen-rich precursor melamine was introduced into the supported trimetallic catalyst and then carbonized. However, no improvement in OER performance was observed. During carbonization, melamine promotes the formation of tip-growth carbon nanotubes, which mechanically disrupt the catalyst structure and degrade the supported active phase. Full article

Developing cost-effective and durable electrocatalysts is essential for advancing anion exchange membrane fuel cells (AEMFCs). This work evaluates Pd-based catalysts supported on β-MnO₂, Vulcan carbon (C), and their physical blend (Pd/MnO₂:Pd/C) as bifunctional electrodes for the oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR). The catalysts were synthesized via chemical reduction and characterized by TGA, ICP-OES, TEM, BET, and XRD. Rotating disk electrode studies revealed that the hybrid exhibited superior activity and kinetics, with lower Tafel slopes and higher exchange current densities compared to the individual supports. In AEMFCs, the hybrid reached 128.0 mW cm⁻² as a cathode and 221.7 mW cm⁻² as an anode, outperforming individual components. This enhanced performance arises from the synergistic interaction between Pd nanoparticles and MnO₂, where MnO₂ modulates the catalyst’s microstructure and local reaction environment while the carbon phase ensures efficient electron transport. MnO₂, although inactive for the HOR alone, acted as a structural spacer, enhancing mass transport and stability. Durability tests confirmed that the hybrid electrocatalyst retained over 99% of its initial activity after 3000 cycles. These results highlight the hybrid Pd/MnO₂:Pd/C as a promising, bifunctional, and durable electrocatalyst for AEMFC applications. Full article

The reproducibility of oxygen reduction reaction (ORR) activity assessment for platinum-based electrocatalysts using the rotating disk electrode (RDE) method is critically dependent on the quality of the fabricated catalytic layer. This work presents a comprehensive study on optimizing catalytic ink formulation—specifically the water-to-isopropanol (H₂O:IPA) solvent ratio and the ionomer-to-carbon (I/C) ratio—to achieve a homogeneous catalytic layer and ensure high data reproducibility for monometallic Pt/C and bimetallic PtCu/C catalysts. A key aspect of this research is the implementation of a simple and effective visual inspection method using a benchtop digital microscope to rapidly assess catalytic layer quality, which was shown to correlate directly with electrochemical performance. The optimal ink composition was found to be catalyst-specific. For Pt/C, the highest mass activity of 353 A/g~Pt~ was achieved with a solvent ratio of 1:3 (H₂O:IPA) and an I/C ratio of 0.3. For PtCu/C, the best performance was obtained with the same solvent ratio (1:3) but a higher I/C ratio of 0.4, yielding a mass activity of 491 A/g~Pt~. It was demonstrated that ink compositions leading to layer inhomogeneities, such as aggregates and “coffee-ring” effects, significantly impair mass transport and lead to underestimated ORR activity. The study underscores the absence of a universal ink recipe and establishes that the optimization of ink parameters for each specific catalyst is essential for obtaining reliable and reproducible electrochemical data. Full article

Anion exchange membrane fuel cells (AEMFCs) represent a promising class of clean energy devices, with their performance being critically dependent on the efficiency of the cathode oxygen reduction reaction (ORR) catalyst. Manganese-cobalt spinel (Mn_1.5Co_1.5O₄, MCS) has been demonstrated to be a highly active ORR catalyst. Herein, we report a strategy of incorporating Cu (MCCS) and Fe (MCFS) into MCS to form ternary spinel oxides for tuning ORR activity. Among them, MCS exhibits the best ORR performance, with a half-wave potential (E_1/2) of 0.736 V vs. RHE in 0.1 M KOH and a peak power density (PPD) of 248.3 mW·cm⁻² for the fuel cell test. In contrast, MCCS and MCFS show divergent behaviors in a rotating disk-ring electrode (RRDE) and fuel cell tests. X-ray diffraction (XRD) analyses and X-ray photoelectron spectroscopy (XPS) analyses reveal that the introduction of Cu²⁺ and Fe³⁺ induces a phase transformation in the spinel structure, leading to a reduction in oxygen vacancies and an increase in the valence state of Mn, thereby degrading catalytic activity. However, the incorporation of these elements also modulates the hydration capability of the catalysts, which is critical for the ion and charge transfer in the fuel cell environment and has been validated in the distribution of relaxation time (DRT) analysis of the fuel cell test. This study provides a valuable strategy for designing and synthesizing low-cost, highly efficient, and stable ternary spinel electrocatalysts for AEMFC applications, and bridges the gap between RRDE evaluation and fuel cell testing through DRT analysis. Full article

Ginger is a common spice found in many cuisines all over the world that is from the rhizome of Zingiber officinale. Additionally, it has been used in traditional medicinal practices as an aid in many ailments ranging from nausea to muscle pain. The non-volatile compounds of ginger, including zingerone, are responsible for pungency and they have widespread biomedical activities. The crystal structure of zingerone, a 6-gingerol degradation product and phenolic compound, reveals that the C4 hydroxyl group is the fulcrum for strong intermolecular interactions such as (O1-H2…O3) 2.737(2) Å. Our electrochemical results using rotating ring-disk electrode (RRDE) hydrodynamic voltammetry demonstrate that zingerone is an effective scavenger of superoxide radical anions and that zingerone, unlike powdered ginger, is a strong antioxidant with a collection efficiency slope of −6.5 × 10⁴ M⁻¹. The addition of vitamin C enhances scavenging activity for both zingerone and ginger powder, although the effect is more noticeable with zingerone. Correspondingly, the zingerone/vitamin C efficiency slope value is −5.40 × 10⁵ M⁻¹. Density Functional Theory (DFT) calculations permit the development of a plausible antioxidant mechanism for zingerone, and zingerone synergistic action with vitamin C, in which zingerone is capable of being regenerated with the assistance of protons that may be provided by ascorbic acid. This mechanism demonstrates that zingerone acts as a strong antioxidant agent by virtue of its C4 hydroxyl group and aromatic system. The scavenging chemical reaction is the same as that obtained through the dismutation of superoxide by superoxide dismutase (SOD) enzymes into hydrogen peroxide and molecular oxygen. Thus, zingerone behaves as a SOD mimic. Full article

Due to its conjugated structure, 1,4,6,8-tetrakis((E)-2-(thiophen-2-yl)vinyl)azulene (L) has a high potential for nonlinear optics and coloring. This compound was studied electrochemically using cyclic voltammetry, pulse differential voltammetry and rotating disk voltammetry in organic electrolytes. The main processes occurring during oxidation and reduction scans were highlighted and characterized. Density functional theory (DFT) calculations were conducted to assess the chemical reactivity of this compound. UV-Vis studies of L were performed in acetonitrile to establish the optical parameters in this solvent and its complexing power towards heavy metal (HM) ions. Chemically modified electrodes (CMEs) based on L were prepared by electrooxidation of L in organic electrolytes. To evaluate the electrochemical behavior of the CMEs, they were characterized with a ferrocene redox probe. They were also tested for the analysis of synthetic samples of heavy metal ions (HM): Cd(II), Pb(II), Cu(II) and Hg(II) by anodic stripping. Specific responses were obtained for Pb(II) and Cd(II) ions. The preparation conditions have an influence on the electrochemical responses. This study is relevant for the design and further development of advanced materials based on this azulene for the analysis of HMs in water samples. Electrochemical experiments and DFT calculations recommended L as a new ligand for modifying the electrode surface for the analysis of HMs. Full article

Laboratory data from in-cell tests at and near open circuit potentials (OCV) and ex-situ H₂O₂ vapor exposure tests are used to develop a fluoride emission rate (FER) model for a state-of-the-art 12-µm thin, low equivalent weight, long-chain perfluorosulfonic acid (PFSA) ionomer membrane that is mechanically reinforced with expanded PTFE and chemically stabilized with 2 mol% cerium as an anti-oxidant. The anode FER at OCV linearly correlates with O₂ crossover from the cathode and the high yield of H₂O₂ at anode potentials, as observed in rotating ring disk electrode (RRDE) studies. The cathode FER may be linked to the energetic formation of reactive hydroxyl radicals (·OH) from the decomposition of H₂O₂ produced as an intermediate in the two-electron ORR pathway at high cathode potentials. Both anode and cathode FERs are significantly enhanced at low relative humidity and high temperatures. The modeled FER is strongly influenced by the gradients in water activity and cerium concentration that develops in operating fuel cells. Membrane stability maps are constructed to illustrate the relationship between the cell voltage, temperature, and relative humidity for FER thresholds that define H₂ crossover failure by chemical degradation over a specified lifetime. Full article

Proton exchange membrane fuel cells (PEMFCs) have been widely studied as an efficient and environmentally friendly energy conversion technology in recent years. However, the high cost, easy poisoning and complex synthesis methods of noble metal catalysts have hindered their commercialization. Therefore, in this paper, a non-noble metal composite catalyst CuFeCo/C for the oxygen reduction reaction (ORR) was prepared by using a facile liquid-phase reduction method. The ORR kinetic performance of CuFeCo/C was evaluated by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and rotating ring-disk electrode (RRDE) tests. The results show that the oxygen reduction peak of CuFeCo/C appears at about 0.64 V, the half-wave potential is about 0.73 V, the limiting current density is about −16.51 A·m⁻², and the Tafel slope is about −0.08. The 10,800 s chronoamperometry test shows that the catalyst has a very good long-term cycle stability. This indicates that the CuFeCo/C composite catalyst has strong stability, good conductivity and ORR catalytic activity under alkaline conditions, which can promote the large-scale commercial application of PEMFCs. Full article

In this work, we measured the antioxidant capacity of capers (Capparis spinosa L.) and an important component, kaempferol, as scavengers of the superoxide radical anion using hydrodynamic voltammetry with a rotating ring disk electrode (RRDE). Comparing our electrochemical results to other natural products studied using this method, this work demonstrates that kaempferol is a stronger antioxidant than vitamin C, whereas caper extract has weaker antioxidant capability than olive oil. We also investigated the synergistic scavenging relationship between vitamin C and kaempferol and found it to be potent, as all the available superoxide radicals were consumed in the presence of both compounds. Such a dramatic RRDE result was observed for the first time in our laboratory. We then utilized computational Density Functional Theory (DFT) methods to establish a viable mechanism, reminiscent of that exhibited by superoxide dismutase (SOD) enzymes, for the scavenging behavior of kaempferol. In the enzymatic reaction, two molecules of the superoxide radical anion with the assistance of two protons are disproportioned into one molecule of hydrogen peroxide and one oxygen molecule. Our DFT results show kaempferol mimicking superoxide dismutase (SOD) action when one kaempferol molecule reacts with two superoxide radicals and two protons (which can be provided by ascorbic acid); i.e., kaempferol acts as a catalyst that is restored after a cycle of superoxide scavenging. This mechanism is consistent with our experimental RRDE results. Full article

The activities of Pt electrocatalysts modified with a prepared silica powder (with SiO₂ contents of 3 and 7 wt%) in the oxygen reduction reaction in the temperature range from 0 °C to 50 °C were investigated by the rotating disk electrode technique to evaluate their efficiency in the process of the cold start of a proton-exchange membrane fuel cell (PEMFC). An increase in the mass activity of the Pt-SiO₂/C electrocatalyst in comparison with Pt/C was observed, which can be attributed to a more dispersed distribution of platinum particles on the support surface and a decrease in their size. The activity values of the silica-modified electrocatalysts in the oxygen reduction reaction were approximately two-fold higher at 1 °C and four-fold higher at elevated temperatures of up to 50 °C in comparison with Pt/C, which makes their application in PEMFCs at low temperatures, including in the process of cold start, a promising avenue for further investigation. Full article

Nafion^® is a cation exchange polymer that is commonly used in aqueous energy applications such as fuel cells due to its ability to exclude anions and neutral molecules and increase apparent diffusion of cationic redox molecules. However, this behavior is not well studied in nonaqueous solutions. The behavior of platinum electrodes modified with recast Nafion^® films in nonaqueous solutions was observed to be different from its well-studied behavior in aqueous solutions. The reversible redox couple tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate was studied in the nonaqueous, aprotic solvent acetonitrile with different electrolytes (tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium hexafluorophosphate, and ammonium trifluoromethanesulfonate) using cyclic voltammetry and rotating disk voltammetry. An unmodified platinum electrode in the nonaqueous systems and a recast Nafion^®-modified platinum electrode equilibrated in an aqueous solution of tris(bipyridine)ruthenium(II)chloride hexahydrate were used as controls. Results indicate that the polymer structure in acetonitrile conditions does not allow apparent (Dahms–Ruff) diffusion but does allow significant physical diffusion that would make Nafion a great immobilization option for modifying electrodes with catalysts in nonaqueous systems. Full article