bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Intercalation of Fluoride-Ions into Oxyfluorosulfide Via Electrolyte Solution for Liquid-Based Fluoride-Ion Battery
Authors: Zhang Shicong , Okazaki Ken-ichi , Zhong Chengchao , Shimoda Keiji , Orikasa Yuki 
Published: December 2024

Rechargeable batteries with high energy density have been required for recent applications such as battery electric vehicles. Fluoride ion batteries (FIBs) can achieve high energy density by using monovalent fluoride ions as charge carriers and multi-electron reactions of electrode active materials, and have attracted much attention as a candidate to surpass the performance of the current lithium-ion battery (LIB). However, FIB using the metal/metal fluoride conversion reaction, which has a high potential for energy density, has not been fabricated with good reversibility as the current LIB. On the other hand, the FIB using a crystal capable of intercalation (insertion-extraction) reaction of fluoride ions as the active material has been developed [1]. Recently, an all-solid-state fluoride ion battery using an oxyfluorosulfide (Sr2F2Fe2OS2; SFFOS) as the intercalation-type positive active material has been reported, and the battery has operated with high capacity and good reversibility at 413 K [2]. In this study, SFFOS was evaluated as an active material for liquid-based FIB. In particular, the thermal effect on the intercalation reaction of SFFOS in ionic liquid-based electrolyte solution was measured.
The SFFOS was synthesized from four kinds of powder, SrF2, SrO, Fe and S, with molar ratio of 1:1:2:2 referring to the previous papers [2, 3]. These powders were mechanically ground under argon and pressed at 6 MPa to form a pellet. The resulting pellet was vacuum sealed in a quartz tube and sintered at 1073 K for 36 hours to obtain the SFFOS. PbSnF4 as the counter electrode material was prepared from PbF2 and SnF2 by mechanical milling at 600 rpm for 6 h using a planetary ball mill, and then calcined at 673 K for 1 h under an argon atmosphere. The electrolyte solution was prepared by dissolving anhydrous tetramethylammonium fluoride (TMAF) in an ionic liquid, N,N,N-trimethyl-N-propylammonium-bis(trifluoromethanesulfonyl)amide (TMPA-TFSA), at various concentrations such as 0.075 mol/dm3 (the molar ratio of TMAF:TMPA-TFSA=1:50). The working and counter electrodes were prepared by mixing of SFFOS or PbSnF4 with acetylene black and PVdF, respectively. The galvanostatic intercalation reaction of fluoride ions into SFFOS was measured using a three-electrode cell with a Pb|PbF2 reference electrode at 298, 373, and 423 K.
The galvanostatic intercalation reaction (corresponding to a charging reaction) of the SFFOS/AB/PVdF composite electrode showed the charging plateau at about 0.5 V vs. Pb|PbF2. The following deintercalation (discharging) reaction, the discharge plateau was observed around 0 V. The intercalation/deintercalation plateaus were similar to those of the previously reported all-solid-state FIB, well [2].
References:
[1] M. Nowroozi et al., Chem. Mater., 2017, 29, 3441-3453.
[2] Z. Cao, et al., Chem. Mater., 2024, 36, 1928-1940.
[3] H. Kabbour et al., J. Am. Chem. Soc., 2008, 130, 8261-8270.
A Novel Process to Achieve Enhanced Mechanical and Electrical Properties of (Mn,Co)3O4-Based Electrical Contact Layer for Solid Oxide Cells
Authors: Adjah-Tetteh Christabel , Wang Yudong , He Zizhou , Xu Nengneng , Zhou Xiao-Dong 
Published: December 2024

To reduce ohmic losses and increase power output in an SOFC stack, electrical contact materials have been employed between the interconnect and oxide cathode. One of the possible candidate materials for the electrical contact layer is (Mn, Co)3O4, which is also used as the interconnect coating in an SOFC stack, due largely to its coefficient of thermal expansion that matches with the interconnect and cathode [1, 2]. The (Mn, Co)3O4 is electrically conducting, yet its conductivity remains several orders of magnitude lower than certain perovskite counterparts, such as (La, Sr)CoO3. In addition, (Mn, Co)3O4 often requires high sintering temperature (≥ 1000°C) when the oxide powders are used as starting materials [1, 3]. There is a need to develop novel processes to reduce the sintering temperature of (Mn, Co)3O4 to about 850°C, at which the sealing glass is sintered. In this work, we employ a new approach to fabricate (Mn, Co)3O4 spinels as the electrical contact materials. This innovation significantly enhanced the conductance of the contact layer and its bonding strength. The bonding strength with interconnect is evaluated by evaluating the maximum shear stress when the spinel layer is sandwiched by two 430 stainless steel coupons. Electrical resistance is measured for the contact layer with different Mn-Co ratios.

References

[1] J. H. Zhu and H. Ghezel-Ayagh, "Cathode-side electrical contact and contact materials for solid oxide fuel cell stacking: A review," International Journal of Hydrogen Energy, vol. 42, no. 38, pp. 24278-24300, 2017.
[2] Z. Yang, G. Xia, and J. W. Stevenson, "Mn1. 5Co1. 5 O 4 spinel protection layers on ferritic stainless steels for SOFC interconnect applications," Electrochemical and Solid-State Letters, vol. 8, no. 3, p. A168, 2005.
[3] A. Petric and H. Ling, "Electrical conductivity and thermal expansion of spinels at elevated temperatures," Journal of the American Ceramic Society, vol. 90, no. 5, pp. 1515-1520, 2007.
Activity and Stability of Ruir Binary Oxides with Different Ir/Ru Ratios for Oxygen Evolution Reaction in Acidic Environmental
Authors: Banno Akichika , Negishi Mayu , Maruyama Takahiro , Saida Takahiro 
Published: December 2024

Proton exchange membrane water electrolysis (PEMWE) is one answer for the mass production of hydrogen. However, PEMWE requires relatively high electric power because the oxygen evolution reaction (OER) at the anode has a high overpotential. In addition, IrO2, used as the general anode catalyst of PEMWE, is very expensive. Although it is known that RuO2 shows higher OER activity and lower cost than that of IrO2, the stability of RuO2 is quite low. Naturally, it is desirable to improve the OER activity in IrO2 or to enhance the stability of RuO2.
Wu et al. reported that the RuIr nano coral with 6% Ir content showed high OER activity and stability [1]. In contrast, the majority of previous reports employed around 50% Ir contents, and the variation range of Ir contents in RuIr catalyst was large, such as 25%, 50%, and 75% of Ir. Therefore, it is difficult to judge the effect of a tiny amount of Ir content on OER activity and stability at this time. The OER activity and stability of RuIr nano coral may originate from the nano coral shape rather than Ir content.
This study focused on the Ir/Ru ratio in RuIr binary oxide to investigate the effects of a tiny quantity of Ir atoms in RuO2 on OER activity and stability. The catalyst shape limited the nanoparticle and excluded the effect from the shape.
The different compositions of RuIr binary oxides were synthesized by the Adams method. The Ir ratio was controlled at about 1%, 2%, 5%, 10%, and 50%, respectively. The atomic composition of synthesized samples was estimated using XRF analysis. The electrochemical measurement was conducted by a three-electrode cell composed of a working electrode, a Pt wire counter electrode, an Ag/AgCl reference electrode, and 0.5 M H2SO4 (room temp.). In addition, a working electrode was rotating at 4,000 rpm during the electrochemical measurements. In this study, the potential was converted to vs. RHE from vs. Ag/AgCl.

All synthesized catalysts had a rutile-type crystal structure. With the increase in Ir contents, the crystallite size increased from ~1 nm to 3.6 nm. The Ir rates relative to total metal atoms in the synthesized samples were 1.3%, 1.8%, 4.5%, 13.5%, and 46.8%. OER activity at the initial state was improved in comparison with RuO2 when the Ir ratio was 5%. On the other hand, stability at 1.7 V was decreased in samples with a low Ir ratio. In the case of stability, a relatively high Ir ratio sample would be favored.
The results of this study could indicate that initial OER activity is dependent on the Ir ratio of RuIr binary oxide, and stability may be affected by the catalyst shape.
[1] Dongshuang Wu et al, nature comunication (2021) 1-9.
The Influence of Fluoroalkyl Group in Alcohol on the Interaction between Alcohols and Fluoride Ion
Authors: Yoneda Nozomi , Tada Kohei , Matsumoto Kazuhiko 
Published: December 2024

Fluoride ion combined with large cations shows high basicity and reactivity. Taming F− with a hydrogen bonding donor such as an alcohol can moderate its basicity, sometimes enabling its effective use in chemical and electrochemical reactions.[1][2] Alkali metal fluoride−alcohol systems are interesting candidates because of its high solubility of F−, basicity, and chemical and electrochemical stability, and simple preparation. This study focuses on CsF−IP (2-propanol) and CsF−HFIP (1,1,1,3,3,3-hexafluoro-2-propanol) systems. Electrochemical behavior of HFIP-based electrolytes was investigated recently owing to its high oxidative stability.[3][4]

In this study, the structural and physical properties of the CsF−HFIP and CsF−IP systems were comparatively discussed. The interaction energy calculations revealed that the interaction between HFIP and F− is stronger than that between IP and F−, which involves the conformational change of HFIP. The peak shift in IR and 1H NMR spectra and the decrease in activity coefficient of alcohols upon the addition of CsF also identified the strong OH∙∙∙F− interaction in the CsF−HFIP system. All these observations suggested that introduction of fluoroalkyl group to an alcohol strengthens the interaction between the OH and F−, which facilitates the dissociation of the cation and anion and enhances the ionic conductivity as also indicated by the diffusion coefficient measurements. On the other hand, IP can also dissolve CsF to a high concentration but the cation and anion highly associate in the solution without giving a sufficient number of conductive species compared to CsF−HFIP system.
References:
[1] J. W. Lee, M. T. Oliveira, H. B. Jang, S. Lee, D. Y. Chi, D. W. Kim, C. E. Song., Chem. Soc. Rev.
45, 4638-4650 (2016).
[2] K. M. Engle,V. Gouverneur., Chem Sci , 6, 5293-5302 (2015).
[3] R. Francke, D. Cericola, R. Kötz, D. Weingarth, S. R. Waldvogel, Electrochim. Acta, 62, 372-380 (2012).
[4] N. Shida, H. Takenaka, A. Gotou, T. Isogai, A. Yamauchi, Y. Kishikawa, Y. Nagata, I. Tomita, T. Fuchigami, S. Inagi, J. Org. Chem., 86, 16128-16133 (2021).
Advancements in Paper-Based Electrochemical Sensors for Cancer Biomarker Detection
Authors: Begay Makeiyla , Wilson Katelyn , Platero Justin , Platero Joshua , Plummer Dallen , Billey Wayant , Soundappan Thiagarajan 
Published: December 2024

Cancer is currently the third leading cause of death among the people of the Navajo Nation and is the most common cause of death worldwide. American Indians are often diagnosed when cancer has reached the advanced stages compared to other communities. Major contributors for the cancer inside the Navajo Nation is the exposure to uranium, other heavy metals, and radon gas. In the Navajo Nation, uranium mining boomed from 1944 to 1986; decades later, uranium tailings and toxic waste from the milling process have caused an increased rate of cancer in the Navajo Nation.
Further cancer detection and monitoring remain critical challenges in healthcare. This research explores the fabrication of paper-based electrochemical sensors modified with nanoparticles and antigens at the Nanoelectrochemical Analysis and Energy Storage Laboratory (NEST LAB) at Navajo Technical University (NTU) for the sensitive and selective detection of cancer biomarkers.
These electrochemical sensors harness the unique qualities of paper, such as low cost and ease of fabrication, combined with the specific binding capabilities of nanoparticles and antigens. Modifying paper electrode surfaces enhances sensitivity and selectivity, making these sensors a cost-effective and portable option for early cancer detection. In contrast to traditional methods like imaging and biopsies, electrochemical sensors are low-cost, offer minimally invasive screening, high sensitivity, and affordability, making them valuable tools in the early diagnosis and management of cancer. These sensors' accessibility and potential to detect cancer at its earliest stages can significantly improve patient outcomes, particularly in resource-limited areas such as Native American reservations.

Keywords: Cancer biomarkers, paper-based electrochemical sensors, nanoparticle modification, antigen modification, early detection, point-of-care diagnostics, cost-effective healthcare.
(Invited) Photocatalytic Water Splitting to Form Green Hydrogen
Authors: Kudo Akihiko 
Published: December 2024

Photocatalytic water splitting is a promising reaction to solve resources, energy, and environment issues, and achievement of carbon neutrality, because it produces green hydrogen. This reaction is regarded as artificial photosynthesis because light energy is converted to storable chemical energy. There are several systems for green hydrogen production; a PV cell + electrolyzer system, a photoelectrochemical cell, and a photocatalyst system. Among them, the powder-based photocatalyst system is expected to be a low-cost technology. In the present paper, various metal oxide and sulfide powdered photocatalysts for water splitting are introduced and discussed.
Rh0.5Cr1.5O3/AgTaO3 (BG 3.4 eV) of a valence-band-controlled metal oxide photocatalyst gave 40% of a quite high apparent quantum yield at 340 nm as a single particulate photocatalyst [1]. However, a solar to hydrogen conversion efficiency was 0.13% because this photocatalyst with a wide band gap responds to only UV light. It is a challenging topic to develop photocatalysts responding to light with long wavelength. Rh and Sb-codoped SrTiO3 photocatalyst loaded with IrO2 cocatalyst was active for water splitting into H2 and O2 under visible light and simulated sunlight irradiations as a single particle type photocatalyst [2]. This photocatalyst responds to 520 nm of visible light. Moreover, we have recently developed Ir-doped SrTiO3 that showed the activity for water splitting responding up to 600 nm of visible light.
There are Z-scheme photocatalyst systems for water splitting under visible light irradiation. SrTiO3:Rh and several metal sulfides of a H2-evolving photocatalyst and BiVO4 of an O2-evolving photocatalyst constructed various type of Z-schematic photocatalyst systems with Fe3+/Fe2+, [Co(bpy)3]3+/2+, [Co(phen)3]3+/2+, and a conductive reduced graphene oxide (RGO) as an electron mediator and even without an electron mediator [3]. Various types of Z-scheme systems for water splitting under visible light irradiation were also successfully developed by employing Rh- and Ir-doped metal oxide powdered materials with relatively narrow energy gaps (EG) to utilize wide range of visible light [4].

References

[1] K. Watanabe, A. Iwase, A. Kudo, Chem. Sci.,
2020
,11, 2330.
[2] R. Asai, H. Nemoto, Q. Jia, K. Saito, A. Iwase, A. Kudo, Chem. Commun. Chem.,
2014
, 50, 2543.
[3] T. Kato, Y. Hakari, S. Ikeda, Q. Jia, A. Iwase, A. Kudo, J. Phys. Chem. Lett.,
2015
, 6, 1042.
[4] A. Kudo, S. Yoshino, T. Tsuchiya, Y. Udagawa, Y. Takahashi, M. Yamaguchi, I. Ogasawara, H. Matsumoto, A. Iwase, Faraday Discussions, 2019, 215, 345.
(Invited) The Impact of "Fujishima-Honda Effect" in the Early Stage of Photoelectrochemical Research
Authors: Uosaki Kohei 
Published: December 2024

Studies on semiconductor electrochemistry have been actively carried out since the 1950's mainly from fundamental points of view. Many reviews and books were published by the early 1970s (1-7). The paper by Fujishima and Honda on "Electrochemical Photolysis of Water at a Semiconductor Electrode" was published in Nature in 1972 (8) and it became very important as the 1st oil crisis took place in 1973 as this paper suggested that solar energy may be directly converted to chemical energy, hydrogen, by using semiconductor/aqueous electrolyte solution/metal cells.
In this talk, I will describe the impact of the "Fujishima and Honda Effect" in the early days of photoelectrochemical research.
References

Green, in Modem Aspects of Electrochemistry, No. 2. Ed. by J. O'M. Bockris, Butterworths, London, 343-407 (1959).

F. Dewald. in Semiconductors. ACS Monograph, No. 140, Ed. by N. B. Hannay, Reinhold, New York, 727-752 (1959).

Gerischer.in Adv. Electrochem. Electrochem. Eng., Vol. 1, Ed. by P. Delahay, lnterscience, New York, 139-232 (1961).

P. Holmes. Ed., The Electrochemistry of Semiconductors, Academic. London, 1962.

V. Myamlin and Yu.V. Pleskov, Electrochemistry of Semiconductors. Plenum, New York. 1967.

Gerischer, in Physical Chemistry: An Advanced Treatise, Vol. IXA. Ed. by H. Eyring. Academic. New York. 1970, Chap. 5.

R. Morrison, Prog. Surf. Sci., 1(1971) 105.

Fujishima and K. Honda, Nature, 238 (1972) 37.

PV 77-3, "Semiconductor Liquid-Junction Solar Cells", by A. Heller.

PV 82-3, "Photoelectrochemistry: Fundamental Processes and Measurement Ed. by W. L. Wallace, A. J. Nojik, and S. K. Deb.

PV 88-14, "Photoelectrochemistry and Electrosynthesis on Semiconducting Materials", by D.S. Ginley, A. Nojik, N. Armstrong, K. Honda, A. Fujishima, T. Sakata, and T. Kawai.
(Invited) Investigation of Borophene-like 2D Materials for Electronic Devices and Electrocatalysis
Authors: Kambe Tetsuya , Sallier de la Tour Nicole , Masaoka Shigeyuki 
Published: December 2024

Graphene has been the focus of countless research efforts across multiple fields. Nowadays, various 2D materials, including metal complex nanosheets, have been reported. In our previous work, we investigated the bottom-up synthesis of metal complex nanosheets (1) and atomicity-controlled clusters.(2) In this study, we achieved a single-layer material like graphene by using boron elements.(3) The prepared atomic boron nanosheet also demonstrated a liquid crystalline nature.(4) The properties are attractive for the application of electronic devices and the support of catalysts.
The atomically flat boron network skeleton was synthesized through a simple solution-based method from KBH4. X-ray diffraction analysis, electron microscopy, IR spectroscopy, and atomic force microscopy revealed the 2D structure, wherein layers of boron atoms with oxygen atoms to form a hexagonal 2D network were sandwiched between layers of potassium cations. The characteristic conducting properties of stacked borophene sheets were also revealed through temperature dependence experiments. Additionally, the liquid crystalline feature was achieved through chemical modification. The obtained liquid crystal exhibited high thermal stability and was applied to a switching device driven by electronic stimuli. In this presentation, we also show the details of a composite with a pentanuclear iron complex (5) with high activity for electrocatalytic water oxidation.
[References] (1) T. Kambe, et al.
J. Am. Chem. Soc.
2013, 135, 2462; J. Am. Chem. Soc.
2014, 136, 14357. (2) T. Kambe, et al. Nat. Commun.
2017, 8, 2046. (3) T. Kambe, et al.
J. Am. Chem. Soc.
2019, 141, 12984; Dalton Trans., 2023, 52, 15297. (4) T. Kambe, et al.
Nat. Commun.
2022, 13, 1037. (5) S. Masaoka, et al.
Nature
2016, 530, 465.
Bipolar Membrane Development and Applications: A Review
Authors: Black Julian , Song Qilei 
Published: December 2024

Bipolar membranes (BPMs) are a versatile technology with the ability to drive water dissociation and ion transport, making them valuable for applications in energy storage, carbon capture, and water treatment. BPMs consist of a cation exchange membrane, an anion exchange membrane, and a catalyst layer between the two. This composite membrane enables water dissociation where an applied electric field can drive H+ and OH- ions out of the BPM in opposite directions. The pH gradient developed by the BPM’s water dissociation and ion transport enables chemical reactions that would otherwise require extreme conditions. BPMs can be used to operate the anode and cathode at a different pH, providing ideal conditions for electrocatalysts. This makes them a promising technology for electrolysers and fuel cells. BPMs are also being researched for use in CO2 capture and electrolysis. Current industrial uses include desalination, pH adjustment in water treatment, acid-base synthesis, and a variety of other applications where a pH gradient is required.
In this review poster we survey current research on BPMs, from materials development to fabrication techniques. We also discuss their current applications in industry and promising technologies utilising BPMs. We review the materials development for high performance BPMs, looking in particular at how catalysts and membranes are developed and can work together to efficiently transport ions and perform water dissociation. Different catalysts from literature are surveyed and compared by their water dissociation performance. The latest cation and anion exchange membranes with high ion conductivity, high permselectivity, and good stability are reviewed. Finally, we describe different methods of fabricating BPMs, including layer-by-layer assembly, solution casting, hot pressing, and electrospinning. We map out the current state of the art and discuss potential avenues for research, including the use of novel catalysts and membranes, and advanced fabrication techniques for improved efficiency.