bluuebunny/crossref_metadata_2025_split huggingface dataset:
Developing Carbon Particles and WS2 Platelets Modified Gce Towards the Sensitive Electrochemical Detection of the Anticancer Drug Flutamide
Authors: Luo Yiran , Palanisamy Rupa Kasturi , Dempsey Eithne , Breslin Carmel B 
Published: December 2024

The development of electrochemical sensors capable of detecting Flutamide is of great importance in biomedical research, environmental monitoring, and drug quality control. 1,2 In this study, a composite material consisting of Actinidia-derived Carbon Particles (CPs) and Tungsten Disulfide (WS2) was utilized to modify a glassy carbon electrode (GCE) and create a highly sensitive and reliable sensor for Flutamide. This was facilitated by the electrochemical reduction of Flutamide as shown in Scheme 1.

Scheme 1. Reduction of Flutamide
The Hydrothermally derived CPs are entwinned with hydroxyl, carbonyl, and amino groups, providing excellent support for the WS2 nanoparticles. Therefore, WS2/CPs nanocomposite acts as an efficient electroactive material on the GCE surface, thereby enhancing the sensitivity. The WS2/CPs electrochemical sensor exhibits outstanding selectivity and stability towards Flutamide detection, with a linear range of 1 nM to 104 µM, enabling the accurate detection of different Flutamide concentrations with high sensitivity. Moreover, the sensor has a low Limit of Detection (LOD) of 0.89 nM, indicating its ability to detect even trace amounts of Flutamide, further emphasizing its sensitivity.
The integration of CPs and WS2 provides an impressive sensor, with high stability, reproducibility, selectivity and a wide linear range, making it a reliable tool for various applications in biomedical research, environmental monitoring, and drug quality control. These advancements contribute significantly to the field of sensors and sensing technology.

Figure 1
Mechanistic Insights into Hydrogen Transport through Metal Oxides Using Optical Microscopy
Authors: Thakkar Shreya , Sharifi Abdar Payman , Wilmer Christopher , McKone James 
Published: December 2024

Catalytic materials that are also capable of hydrogen storage are attractive because they enable unique integrated reactor architectures for electroreduction processes. Redox-active transition metal oxides are a class of compounds that can be used for this purpose. For example, tungsten oxides undergo hydrogen insertion under negative applied potential to form tungsten oxide hydrogen bronzes, which in turn drive reductive hydrogen transfer reactions. Under these conditions, bulk hydrogen insertion sites react stoichiometrically while surface sites behave catalytically. For the design of better reactive hydrogen sorbents, it is imperative to understand the underlying mechanism of hydrogen insertion and transport through these materials. We are employing optical microscopy and molecular dynamics simulations to develop these insights.
We have designed a transparent electrochemical cell using commercial microscope slides, where one slide is coated with a thin WO3 film and two gold pads—one pad acts as the source of electrons for the tungsten oxide, which is the working electrode, and the other acts as the counter electrode. The reference electrode is placed outside the sandwich cell region with connection via a flowing electrolyte bridge. This sandwich cell is placed under the microscope to directly observe the formation of a coloration front in the WO3 films from greenish yellow to dark blue that indicates the formation of the HxWO3 (0 < x < 0.625) bronze. The color change is observed immediately at the point of contact between the film and the gold and progresses along the film with time. The use of a variable-wavelength monochromatic light source and an electron-counting camera enable us to quantify with high precision the optical density, which relates directly to the degree of (local) hydrogen insertion. Thus, the time-dependent movement of the coloration front can be measured experimentally and fit to a model to obtain physical parameters associated with a complex sequence of reaction-diffusion processes.
We are also working to extend these studies to other metal oxides and identify conditions under which the rates of hydrogen insertion and transport within the film are maximized. To aid in this process, we are leveraging molecular dynamics techniques to simulate H-transport through bulk oxides under varying conditions. The resulting insights are relevant for the design of advanced oxides that can activate, store, and deliver hydrogen to a wide variety of industrially relevant hydrogenation targets.
Shift in Electrochemical Pathway Under Forced Periodic Operation of Potential Applied Due to Catalytic Resonance Effect
Authors: Chandra Kanth Sidhanth , Rebrov Evgeny V 
Published: December 2024

Sabatier's law is central to our understanding of catalysis. It states that the reactants will form reaction intermediates on the catalytic surface for a given catalytic reaction. Crucially, these intermediates must have an intermediate level of stability. If they are too stable, they will fail to decompose to form the product, and if they are too unstable, the catalyst will fail to activate the reaction1. The traditional strategy to design a catalyst for a reaction system is achieved by tuning the d-band filling of the catalyst (by making alloys, bimetallic, etc.) or by changing surface structure. Instead, this work demonstrates a constructive approach to shifting reaction pathways using the same catalyst. In the photo- and electrocatalysis, the shift in the reaction pathways (and selectivity) can also be achieved by operating the catalytic reactor using periodic modulation of one or multiple parameters around the steady state point2.
This study considers the electrochemical oxidation of formic acid over a Pt catalyst. This reaction follows a triple pathway: direct, indirect, and formate3. The indirect pathway forms CO as an intermediate, which strongly interacts with the catalyst surface. To further oxidise CO, an OH species needs to be adsorbed to form CO2, which requires a potential above 0.8 V vs RHE. Therefore in a steady-state galvanostatic operation, the reaction shows self-oscillation within a specific current range3.
This study uses a clean-electrolytic cell consisting of flame-annealed platinum wire as working and platinum mesh as a counter electrode with RHE as the reference electrode. The electrolytic cell is purged continuously with nitrogen, and gas is analysed using a gas analyser. The electrolyte consists of Suprapur 0.5 M H2SO4 and 0.2 M HCOOH. A sinusoidal voltage with a DC offset of 0.64 V vs RHE and amplitude of 0.26 V vs RHE was applied by varying frequency from 0 to 800 Hz. An enhancement in reaction rate by 1.94 times was observed at 800 Hz compared to steady-state operation at 0.9 V vs RHE. The I-V curve shows a qualitative enhancement towards the formate pathway compared to the indirect pathway above 600 Hz. The shift from indirect to formate pathway with a change in frequency above 600 Hz is further explained by the results from Electrochemical in situ Surface-enhanced attenuated total internal reflection infrared spectroscopy.
Reference

Chorkendorff, I. & Niemantsverdriet, J. W. Concepts of Modern Catalysis and Kinetics. Concepts Mod. Catal. Kinet. (2003). doi:10.1002/3527602658

Ellwood, Th., Živković, L., Denissenko Petr, Abiev, R.Sh., Rebrov E.V., Menka Petkovska, Processes 2021, 9(11), 2046; /doi.org/10.3390/pr9112046

Calderón-Cárdenas, A., Hartl, F. W., Gallas, J. A. C. & Varela, H. Modeling the triple-path electro-oxidation of formic acid on platinum: Cyclic voltammetry and oscillations. Catal. Today (2019). doi:10.1016/j.cattod.2019.04.054
Exploring on Stainless Steel Based Electrodes for Oxygen Evolution Reaction Under Alkaline Electrolyte
Authors: Choi Yong-Wook 
Published: December 2024

The clean energy, namely hydrogen, has been spotted lighted as a promising means for tackling down the problem of climate change. Alkaline Water Electrolysis (AWE) is identified as the representative method for obtaining hydrogen through sustainable way, because it needs only water and electricity (supplied from renewable energy sources such as solar light and wind). Especially, cheaper electrode materials like transition metal (Nickel) could be employed for both cathode and anode, whereas the other method (PEM-WE) should use only more expensive Pt-group materials.
Herein, we explored the possibility of stainless steel (SS) for anode under alkaline environment. SS based electrodes showed steady performance over the versatile range of current densities (from 10 mA/cm2 to 100 mA/cm2). These novel results would provide subsequent research with how to design for alternative electrode materials.

Figure 1
(Digital Presentation) Electrochemical Behavior of Ti(III) Complexes in the Chloride-Fluoride Melt
Authors: Vetrova Daria A. , Kuznetsov Sergey A 
Published: December 2024

According to numerous studies the electroreduction of Ti(IV) fluoride complexes to the metal in chloride-fluoride melts occurs in two subsequent stages:
Ti(IV) + e- ↔ Ti(III) (1)
Ti(III) + 3e- → Ti. (2)
The redox reaction (1) in chloride-fluoride melts of different composition was thoroughly investigated in our previous works [1,2].
The aim of the present investigation was the determination of reaction (2) kinetic parameters such as: coefficients of transfer, diffusion coefficients of Ti(III) and standard rate constants of charge transfer, in the (NaCl-KCl)equimol.-NaF(10 wt.%)-K2TiF6 melt. Another goal was to study the influence of the working electrode material on the kinetics of the discharge reaction.
[1] D.A. Vetrova, S.A. Kuznetsov. 2021. J. Electrochem. Soc., 168: 036517.
[2] D.A. Vetrova, S.A. Kuznetsov. 2023. J. Electrochem. Soc., 170: 086503.
Thermal Treatment As a Key Factor for Obtaining Top-Grade Core-Shell NMC Cathode Materials
Authors: Grygiel Michał , Buchberger Dominika , Winkowska-Struzik Magdalena , Firlej Natalia , Struzik Michal , Czerwiński Andrzej 
Published: December 2024

Lithium-ion batteries (LIBs) continue to be one of the main technologies in the energy storage industry, powering various devices from portable electronics to electric vehicles. However, to meet the growing demand for higher energy density, longer cycle life, and improved safety, there is a pressing need for innovative electrode materials[1]. In this presentation, we approach the development of an advanced positive electrode material for LIBs based on a core-shell structure, utilizing lithium nickel manganese cobalt oxide (NMC) with a nickel-rich core and a low-nickel shell.
The core-shell structures present a promising route for simultaneously enhancing the performance and stability of LIBs[2]. By incorporating a nickel-rich core, it is possible to leverage its high capacity, while the low-nickel shell ensures reducing undesirable side reactions, such as electrolyte decomposition and transition metal dissolution[3], thereby enhancing safety and longevity of the battery.
Our research focuses on electrochemical evaluation of various NMC compositions to determine the best materials for the core and the shell, focusing on specific capacity, rate performance and cyclability. As different stoichiometries of NMC usually require distinctive thermal treatment conditions[4,5], a careful examination is needed in order to ensure proper crystal structure of both the core and the shell. In that regard we conducted a set of in situ and ex situ XRD studies on pristine materials. In combination with electrochemical assessment these results enabled us to match high-capacity nickel-rich NMC for the core with enhanced-stability low-nickel variants for the shell in terms of the best possible compatibility of thermal treatment conditions in mind.
This allows us to further study the core-shell NMC materials characterized by both satisfactory electrochemical performance and enhanced cyclic stability. This approach opens the possibility to develop LIBs with higher energy density, prolonged cycle life, and enhanced stability, crucial for meeting the evolving demands in the advancing energy storage sector.

This work was funded by the National Science Center in Poland through the Sonata 17 programme (No.
UMO-2021/43/D/ST5/03094).

[1] M. Li, J. Lu, Z. Chen, K. Amine, Adv. Mater. 2018, 30, 1800561.
[2] H. Peiyu, Z. Hongzhou,Z. Zhongyue, Z. Lianqi,X. Xijin, J. Mater. Chem. A, 2017, 5, 4254–4279
[3] Li, T., Yuan, XZ., Zhang, L. et al. Electrochem. Energ. Rev. 3, 43–80 (2020).
[4] Noh, H. J., Youn, S., Yoon, C. S., Sun, Y. K., J. Power Sources 233, 121– 130 (2013).
[5] Zheng, J., Yan, P., Estevez, L., Wang, C, Zhang, J. G., Nano Energy 49, 538– 548 (2018).
Thermal Stability and Performance of Li-Ion Batteries at Elevated Temperatures: Separator Effects
Authors: Romero Cameron Taj , Strickland David Allen , Bachman J. Chris , Keating Michael , Biddinger Elizabeth J. , Messinger Robert J. , Jones John-Paul , West William C 
Published: December 2024

The performance and safety of lithium-ion batteries (LIBs) are significantly influenced by the stability and integrity of their components that have been optimized for a limited temperature range (ca. 0 to 40°C). At elevated temperatures, conventional LIBs exhibit issues such as rapid capacity fade, compromised electrolyte stability, and an increase in internal resistances. With the push towards net-zero emissions, it is imperative that suitable materials and cell designs be identified to allow rechargeable battery integration into operations with temperatures as high as 100°C for applications such as space exploration, drilling equipment, and automotive technologies.
In our presentation, we will report that a design of experiment (DOE) study examining several independent variables and interactions of variables in the cell design revealed that the standard polyolefin separator is associated with both decreased Coulombic efficiency and increased variability in cycling performance at elevated temperatures relative to non-polyolefin (e.g. polyimide) separators. In a separate study, electrochemical data were obtained by cycling coin cells at 100oC, varying only the separator (Fig. 1). After the first 20 cycles, the polyimide cells maintained a higher specific capacity relative to the polyolefin cells.

Figure 1. Specific capacity vs. cycle number for NMC111/graphite coin cells with Polyimide and Polyolefin separators
The nature of the separator alterations from a chemical and electrochemical perspective will be presented, which will provide valuable insight into the critical role of separators in battery design while simultaneously offering alternative materials for operations as high as 100°C.

Figure 1
Electrochemical Formation of Liquid Tb–Zn Alloys in Molten LiF–CaF2–TbF3
Authors: Kawaguchi Kenji , Nohira Toshiyuki 
Published: December 2024

Terbium (Tb) is added to neodymium magnets used in motors for electric vehicles (EVs) and hybrid electric vehicles (HEVs) to prevent deterioration of their magnetic properties at high temperatures. Tb metal added to neodymium magnets is currently produced by metallothermic reduction. As a novel method for producing Tb metal, we focused on the electrochemical reduction of Tb (III) ions using a liquid Zn electrode. In this study, the electrochemical formation of Tb–Zn Alloys was investigated at the liquid Zn electrode in molten LiF–CaF2–TbF3 at 1123 K.
Cyclic voltammetry and galvanostatic electrolysis were performed after adding TbF3 to molten LiF–CaF2 (80.5:19.5 mol%) in a graphite crucible under an Ar atmosphere at 1123 K. The working electrodes were a Mo flag (Φ 3 × 0.1 mm) and liquid Zn (7 g) held in a small boron nitride crucible. A graphite rod was placed in contact with the bottom of the graphite crucible, and the entire graphite rod and crucible were used as the counter electrode. A Ti rod was used as the quasi-reference electrode. The potential was calibrated using the Li+/Li potential. The samples obtained by galvanostatic electrolysis were analyzed by SEM/EDX.
Cyclic voltammetry was performed at Mo flag and liquid Zn electrodes. At the Mo flag electrode, in addition to the redox peaks of the deposition and dissolution of Li metal, the reduction current from c.a. 0.2 V (vs. Li+/Li) and a corresponding oxidation current were observed, which were attributed to the deposition and dissolution of Tb metal. At the liquid Zn electrode, an increase in the reduction current was observed from c.a. 1.0 V. This suggests the formation of the liquid Tb–Zn alloy. Galvanostatic electrolysis was performed using the liquid Zn electrode at –100 mA cm–
2 for 210 min. Figure 1 shows cross-sectional (a) optical image and (b) SEM image of the sample after electrolysis. The formation of the Tb–Zn alloy was confirmed by EDX analysis.
A part of this study was conducted as commission research with the New Energy and Industrial Technology Development Organization (NEDO) of Japan.

Figure 1
Evaluation of the Solid-Electrolyte Interphase Formation in a Bis(fluorosulfonyl)amide Based Ionic Liquid in the Presence Lithium Ion Using Different Redox Probes
Authors: Momose Shunosuke , Thomas Morgan L. , Serizawa Nobuyuki , Katayama Yasushi 
Published: December 2024

The solid electrolyte interphase (SEI) is formed on the anode surface of rechargeable Li batteries by the reductive decomposition of the electrolyte. Because the SEI enables the anode reactions involving lithium ions and prevents further electrolyte decomposition, the SEI is one of the important factors affecting the battery performance.
Ionic liquids (ILs) have been investigated as the electrolytes for rechargeable Li batteries because of their favorable properties such as non-flammability and non-volatility. An amide-type IL composed of 1-butyl-1-methylpyrrolodonium (BMP+) and bis(fluorosulfonyl)amide (FSA–) has attracted attention among various ILs, because BMPFSA shows a relatively low viscosity. The SEI formation on a Pt electrode in 0.5 M LiFSA/BMPFSA was investigated by the redox reaction of ferrocene (Fc) and ferrocenium (Fc+) as a redox probe[1,2]. The SEI formation affected the electron transfer rate of Fc+/Fc and was promoted by the interaction of Li+ and FSA–. Furthermore, the breakdown of the SEI formed in 2.9 M LiFSA/BMPFSA was confirmed by the redox probe method, suggesting that the SEI can be considered as a viscous and gelled layer formed by the formation and diffusion of the decomposition products dispersed and/or dissolved in the IL[3].
In the present study, the SEI formation in 0.5 M LiFSA/BMPFSA was investigated by using different redox probes. The redox reactions of some metallocenes and organic compounds on a Pt electrode were investigated by cyclic voltammetry in BMPFSA and 0.5 M LiFSA/BMPFSA. The potential was measured against a Ag|Ag(I) reference electrode, of which the potential was 0.39 V vs. Fc|Fc+[4]. Cyclic voltammograms were taken after holding the electrode at potentials ranging from –0.9 to –1.5 V at 0.1 V intervals for 1 hour. The cyclic voltammograms were uncharged in BMPFSA, indicating that BMPFSA was stable in the potential range and that the redox reactions were not affected by a change in the structure of the electric double layer. On the other hand, peak shifts due to a decrease in the electron transfer rates were observed in the presence of Li+ at the potentials more negative than –1.1 V, indicating that the SEI formation promoted by the interaction between Li+ and FSA– affects the redox reactions not only of mettallocenes but also of organic compounds that undergo outer sphere electron transfer reactions.
References
[1] S. Kato, N. Serizawa, and Y. Katayama, J. Electrochem. Soc., 169, 076509 (2022).
[2] S. Kato, N. Serizawa, and Y. Katayama, J. Electrochem. Soc., 170, 056504 (2023).
[3] S. Okazaki, N. Serizawa, and Y. Katayama, Electrochemistry, 92, 043006 (2024).
[4] S. Kato, N. Serizawa, and Y. Katayama, J. Electrochem. Soc., 170, 046504 (2023).
Electrochemical Oxygen Evolution in Chloride Melts Using Co-Based Oxide Electrodes
Authors: Tanaka Seiya , Suzuki Yuta , Fukunaka Yasuhiro , Goto Takuya 
Published: December 2024

Carbon decomposition by molten salt electrolysis has been researched for achievement of carbon negative emissions. Carbonate ions, which are derived from carbon dioxides and oxide ion in the molten salts, are reduced into carbon and oxide ions are produced at cathodes. Oxygen gas is generated from the produced oxide ions at anodes. For realizing the electrochemical carbon decomposition process, development of inert anode is essential task. In the previous research, various materials of metal, cermet and metal oxide have been tested for inert anodes to obtain low corrosion rate and high current density in electrochemical oxygen evolution. Especially, conductive oxides are expected to have both of high electrical conductivity and high corrosion resistance to produced oxygen.
In this study, we report the characteristics of Co-based oxide anodes for oxygen evolution in chloride melts. Co3O4 is one of the representative conductive oxides, which have conduction characteristic. In the experiments of molten chloride containing oxide ions at a temperature over 600℃, the cyclic voltammograms with a prepared Co3O4 anode were measured. The results show drastically increases of current density at 2.9 V vs Ca(Ⅱ)/Ca, which was approximately same to the oxygen evolution potential estimated from thermodynamic calculations. The corrosion behaviors of Co-based anodes will be discussed from the results of long-time electrochemical operation and chemical analysis using XRD, SEM, EDs, and ICP-AES analysis.