bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dependence of Cation Structures on Electrochemical Polymerization of Aniline in Phosphonium Ionic Liquids
Authors: Hori Katsuki , Ito Daiki , Nawate Shoki , Matsumoto Mitsuhiro , Tsuchida Yusuke , Tsunashima Katsuhiko , Yamada Hirohisa 
Published: December 2024

Ionic liquids (ILs) are known to possess unique physicochemical and abundant design properties. When ILs are used as electrolytes in the electropolymerization reactions of aromatic compounds to form conducting polymers, the grown film properties are significantly dependent of the combination of cations and anions. Typical researches on the IL-based electrolytes have been described for nitrogen-based ILs;1) on the other hand, phosphonium-based ILs have also attracted attention in recent years. We have reported the preliminary electrochemical investigation for electropolymerization of aniline (ANi), indicating that the phosphonium ILs were able to be employed as potential electrolytes.2) In this work, various phosphonium ILs ( Fig. 1) including typical two phosphonium ILs such as triethylpenthylphosphonium bis(trifluoromethanesulfonyl)amide (P2225-TFSA) and tributylmethylphosphonium bis(trifluoromethanesulfonyl)amide (P4441-TFSA) 3) are selected for the electrooxidative polymerization of ANi, in order to investigate the influence of the physicochemical properties of the phosphonium ILs on the electropolymerization processes and the grown polyaniline (PANi) films.
The phosphonium ILs were synthesized and purified according to a previously published paper.3) The electrolytes were prepared by adding 2.0 M of ANi monomer and 1.0 M of 1,1,1-trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide (HTFSA) as a proton source. The electropolymerization was carried out by cyclic voltammetry (CV) using a three-electrode cell with a platinum disc or an indium tin oxide (ITO) as a working electrode, a Ag/Ag+ as a reference electrode and a platinum wire as a counter electrode (potential sweep rate: 0.1 V s-1, potential range: -0.5~+1.5 V). The morphology of the electropolymerized PANi films on the ITO electrode were observed by scanning electron microscopy (SEM).
Fig. 2 shows the cyclic voltammograms for electrooxidative polymerization of ANi in typical P2225-TFSA and P4441-TFSA. It was found that the P4441-TFSA based electrolyte tended to give relatively low oxidation currents, forming the uniform PANi film on the electrode surface as shown in Fig. 3. The voltammograms for the electropolymerization measured in various phosphonium ILs will be discussed, demonstrating the influence of the transport property of the phosphonium IL electrolytes.
References
[1] K. Sekiguchi, M. Atobe and T. Fuchigami, J. Electroanal. Chem., 557, 1 (2003).
[2] K. Tsunashima, D. Ito, M. Matsumiya and Y. Ono, ECS Meet. Abstr., MA2016-01 1889.
[3] K. Tsunashima and M. Sugiya, Electrochem. Commun., 9, 2353 (2007).

Figure 1
Electrodeposition of Aluminum-Silicon Films in Chloroaluminate Ionic Liquids
Authors: Venkatesh Krishna , Ispas Adriana , Bund Andreas 
Published: December 2024

Aluminum and its alloys are interesting materials for the automotive industry due to their relative low density compared to steel. The weight of vehicles can be drastically reduced by utilizing aluminum and its alloys in the construction of their body parts instead of steel. Moreover, we could previously prove in our group that some aluminum alloys, such as Al-Zn, showed improved resistance against corrosion compared to pure aluminum (1) when electrodeposited onto steel substrates. Aluminum-silicon alloys manufactured by casting have excellent mechanical properties and corrosion resistance. However, one of the problems that can occur during the cooling/solidifying phase in casting is the formation of micro- and macropores or the growth of Al-dendrites (2).
An alternative technique to obtain Al-Si alloys is the electrodeposition technique. Due to the negative reduction potentials of both Al and Si, they cannot be electrodeposited from aqueous solution. They can be obtained by electrolysis in molten salt electrolytes at temperatures above 960°C (3).
In this study we investigated the deposition Al-Si alloys at room temperature in 1-ethyl-3-methylimidazolium chloride, [EMIm]Cl: AlCl3 (1:1.5). Different precursors for Si such as SiCl4, SiBr4 and SiI4 were studied. We found that the type of precursor and its concentration influenced the maximum amount of Si in the alloy, as well as the morphology of the layers. Furthermore, the deposition technique (direct current plating or pulse plating) had a significant effect on the quality of the deposits.
Acknowledgments: The authors gratefully acknowledge the financial support of the Federal Ministry for Economic Affairs and Climate Action, BMWK, Germany, within the project CastCo (FKZ 03LB2046E).

R. Böttcher, A. Ispas, and A. Bund, Metals
13(2) (2023) 377

P.D. Lee, A. Chirazi, and D. See, J. Light Met.
1 (2001) 15

O. Awayssa, G. Saevarsdottir, R. Meirbekova, and G. M. Haarberg, J. Electrochem. Soc.
168 (2021) 046506
Ion Transport Properties in Glyme-Based Highly Concentrated Electrolyte with Asymmetric Li Imide Salts
Authors: Matsuyama Yuna , Philippi Frederik , Sudoh Taku , Tsuzuki Seiji , Watanabe Masayoshi , Ueno Kazuhide 
Published: December 2024

The spread of electric vehicles is being expanded around the world with the aim of reducing carbon dioxide emissions toward carbon neutrality by 2050. This trend requires even higher performance for Li secondary batteries. Previous research has focused on increasing ionic conductivity of the electrolyte. It is now clear that the Li ion transference number is equally important to further improve the performance of batteries for automotive applications[1]. However, the relationship between the structure of Li salts and ion transport properties is not understood well, and there is no established method to systematically increase the Li ion transference number. Here we show how the structure of the Li salt affects the ion transport properties for an equimolar mixture of a novel Li salt and tetraglyme (G4). We have synthesized a new Li imide salt, Li (N-(trifluoromethyl)sulfonyl)acetamide) (Li[TfNAc]), having both sulfonyl and carbonyl groups. For the novel highly concentrated electrolyte [Li(G4)][TfNAc], we observed a high Li ion transference number of 0.65 at the cost of a low ionic conductivity of 0.21 mS cm−1. This trade-off between ionic conductivity and transference number is in line with previous empirical observations made in our group[2][3]. Ab initio molecular orbital calculations of lithium affinity in comparison with anions in established electrolytes revealed the order [TFSA]− < [BF4]− < [TfNAc]− < [TFA]−, consistent with the qualitative order observed in ionic transport properties. Thus, ion transport is affected significantly by small changes to the anion structure. We observed that the solvate structure of [Li(G4)][TfNAc] is dominated by correlated motion in ion pairs and larger aggregates, in line with previous studies.[3] Based on the concepts of ionicity (inverse Haven ratio) and Onsager transport coefficients[4], we were able to quantify the impact of ion interactions on the macroscopic transport properties.
[1]K. M. Diederichsen et al, ACS Energy Lett., 2017, 2, 2563.
[2]K. Shigenobu, et al., Phys. Chem. Chem. Phys., 2020, 22, 15214.
[3] K. Shigenobu, et al., Phys. Chem. Chem. Phys., 2021, 23, 2622.
[4] Dong, D.; Sälzer, F.; Roling, B.; Bedrov, D., Phy. Chem. Chem. Phy., 2018, 20, 29174.
Ionic Liquid and Plastic Crystal Battery Electrolytes Utilising New Cation and Anion Structures
Authors: Pringle Jenny , Vallana Federico , Azad Faezeh Makhlooghi , Sourjah Sithy M , Warrington Anna , Forsyth Maria 
Published: December 2024

It is well known that the nature of the cations and anions used to make ionic liquid (IL) electrolytes can have a significant impact on their chemical and physical properties and on their performance in devices, for example when used in lithium or sodium batteries. The same is true for organic ionic plastic crystals (OIPCs); these salts are structurally analogous to ILs, but they are solid at room temperature and display dynamics that can allow their use as solid state electrolytes. However, the structure-property relationships are arguably even less well understood in OIPCs. Furthermore, the addition of different lithium or sodium salts to ILs and OIPCs, to enable their use in lithium or sodium batteries, introduces further complexities in terms of understanding and optimising the thermal, electrochemical and transport properties.
To advance the understanding and application of IL and OIPC-based electrolytes it is important to continue to design and investigate new cation and anion structures. For example, we have recently developed new families of IL and OIPC electrolytes using cations such as the hexamethylguanidinium, cyano- or ether-functionalised ammoniums, oxazolidiniums and morpholiniums, in combination with a range of fluorinated and non-fluorinated anions. Furthermore, a new and seldom explored family of materials can be created by tethering the cation and anion together to form zwitterions.
This presentation will give an overview of our recent work making new families of non-volatile electrolytes based on ILs, OIPCs and zwitterions and understanding the impact of structure on device performance. Highlights will include the excellent properties and performance imparted by small oxygen-containing cations, and the promising new results using more environmentally friendly, non-fluorinated salts for Li and Na batteries.
References
[1] A. Warrington, M. Hasanpoor, A. Balkis, P. C. Howlett, O. E. Hutt, M. Forsyth, J. M. Pringle, Energy Storage Materials 2023, 63, 102984
[2] A. Sourjah, C. S. M. Kang, C. M. Doherty, D. Acharya, L. A. O’Dell, J. M. Pringle, Phys. Chem. Chem. Phys., 2023, 25, 16469
[3] F. Makhlooghiazad, L. A. O’Dell, L. Porcarelli, C. Forsyth, N. Quazi, M. Asadi, O. Hutt, D. Mecerreyes, M. Forsyth, J. M. Pringle, Nat. Mater., 2022, 21, 228
Finding Diffusivity and Solubility of Impurities inside ILs By MD
Authors: Aryal Dipak , Rotondaro Antonio , Nakano Takeo , Morimoto Tamotsu 
Published: December 2024

Ionic liquids (ILs) are promising candidates for use in the semiconductor industry because of their unique and tunable physicochemical properties. They are a novel class of salts with desirable features such as being in liquid phase at room temperature, nonflammability, high ionic conductivity, high thermal stability, and low to negligible vapor pressures. Their physical, chemical, solubility, transport, and solvation properties can be tuned by altering the cations or anions to tailor for applications in the semiconductor industry, including the process of liquid/gas separations, extraction of impurities, and cleaning under vacuum. Selecting suitable ILs to enhance the efficiency of the target semiconductor processes and tools is crucial.
One possible application is to use ILs as a barrier or protective liquid film that does not evaporate in low-pressure conditions. For this application, we need a better understanding of the molecular scale of the behavior of the ILs at different temperature ranges. To develop such a new process, the knowledge of absorbing/desorbing impurities (such as O2, CO2, and H2O, including their mixtures and other organic materials) in the ILs and their transport (diffusion coefficients) properties inside the ILs at different temperatures is essential from the surface protection film point of view. This work seeks to answer these essential questions at the nanometer scale by showing the results from molecular dynamics (MD) simulations of the diffusivity and solubility of impurities inside ILs. Examples of MD simulation models for this study are shown in Figure 1, where impurities with the same concentration are placed on both sides of ILs, and the transport behavior of impurities inside ILs is extracted. From these nanoscale results, we can better understand and predict the diffusivity and solubility of impurities inside ILs and find the conditions at which impurities can be removed from ILs for recycling purposes.

Figure 1
Simulation of Voltammetric Measurements of Uranium Electrodeposition in Molten LiCl-KCl Eutectic
Authors: Stoddard Michael , Mejia Carlos , Rappleye Devin 
Published: December 2024

The electrochemical behavior of uranium in high-temperature molten salts is central to the development of advanced nuclear reactors (e.g., molten salt reactors) and reprocessing technologies (e.g., pyroprocessing). Numerous studies have been performed on uranium in molten salts, especially LiCl-KCl eutectic. However, many studies rely on models, such as Berzins-Delahay model, which assume mass transfer by diffusion only and a pure deposit (i.e., unit activity for the reduced species).1 In many situations, these assumptions may not be appropriate for analyzing electrochemical data in molten salts and may introduce significant error in the estimation of properties, such as diffusion coefficients. For example, a foreign substrate, such as tungsten or molybdenum, is often used as the working electrode in electroreduction of uranium ions to metal in molten salts. Hence, nucleation effects and incomplete coverage of the WE can affect measurements, especially at dilute concentrations. Additionally, macro electrodes are often used in molten salts due to a lack of compatible insulating material for construction of microelectrodes. This results in large currents which can introduce significant ohmic losses despite the relatively low ohmic resistance of molten salts. Furthermore, additional effects, such as migration and natural convection, can significantly impact electrochemical measurements in molten salts containing a heavy analyte, such as uranium ions.
To address these challenges, a model was developed specifically for electrodeposition in molten salts based on the Nernst-Plank equation, Nernst equation, adsorption isotherms, and activity models. The initial iteration of the model has been designed to account for the combined effects of diffusion, migration, ohmic resistance, deposition onto a foreign substrate, and activity of non-ideal solutions. The significance of each effect and combination of effects has been examined for linear sweep voltammetry at various uranium ion concentrations and scan rates. Furthermore, the model has been validated against uranium electrodeposition measurements on a tungsten WE in molten LiCl-KCl eutectic.
1. T. Berzins and P. Delahay, J. Am. Chem. Soc., 75, 555–559 (1953) http://dx.doi.org/10.1021/ja01099a013.
(Invited) Extending the Success of Halide Perovskites to Photoelectrochemical and Photocatalytic Solar Fuel Production
Authors: Eslava Salvador 
Published: December 2024

To address the pressing global energy demands with clean and sustainable methods, solar-powered photoelectrochemical and photocatalytic transformations of water and carbon dioxide present viable solutions. Achieving this requires the development of cost-effective photoelectrodes and photocatalysts capable of efficiently harnessing solar light and promoting charge transfer to drive water and carbon dioxide reactions. In this presentation, I will outline the advances my team has made in the field, focusing on novel halide perovskites like CsPbBr3, Cs2AgBiBr3, and Cs3Bi2Br9 and bulk heterojunctions of organic semiconductors. These materials exhibit high solar light absorption and outstanding optoelectronic properties, making them excellent candidates for photoelectrochemical and photocatalytic uses. We have developed innovative approaches to enhance their stability in aqueous environments, such as encapsulating halide perovskites and organic bulk heterojunctions within carbon layers modified with Ni nanopyramids and NiFeOOH, a water-oxidation catalyst. This approach exploits different carbon allotropes, from mesoporous carbon to graphite, glassy carbon and boron-doped diamond, in order of chemical and mechanical stability. The use of layers and sheets of these carbon allotropes has led to the creation of photoanodes with low onset potentials and high photocurrents, efficiently translating excellent photocurrents and photovoltages from solar cells to photoelectrodes. For example, organic bulk heterojunction devices result in 25 mA/cm2 photocurrents in three-electrode systems and unassisted 5% solar to hydrogen in two-electrode systems Our approaches significantly extend the lifespan of photoanodes, maintaining for example a projected operation of months with CsPbBr3. In the field of photocatalysts, we have employed mechanochemical synthesis and antisolvent crystallization to create innovative composites like CsPbBr3/Cu-RGO, Cs2AgBiBr3/Cu-RGO, Cs2AgBiBr3/bismuthene, and Cs3Bi2Br9/RGO/g-C3N4, demonstrating efficient activity in converting CO2 into CO and CH4. Through thorough material characterization, we have shed light on their structural and charge-transfer properties, laying a solid foundation for their ongoing development and practical application.
Daboczi, M.; Eisner, F.; Luke, J.; Yuan, S.W.; Al Lawati, N.; Müller, J.S.; Kim, J.S. Nelson, J.; Eslava, S. under review
Zhu, Daboczi, Chen, Xuan, Liu and Eslava, Nat. Commun. 2024, 2791.
Daboczi, M.; Cui, J.; Temerov, F.; Eslava, S. Adv. Mater. 2023, 2304350
Baghdadi, Y.; Temerov, F.; Cui, J. Daboczi, M.; Rattner, E.; Sena, M.S.; Eslava, S. Chem. Mater. 2023, 35, 20, 8607
Sena, M.S.; Cui, J.; Baghdadi, Y.; Rattner, E.; Daboczi, M.; Lopes-Moriyama, A.L.; dos Santos, A.G.; Eslava, S. ACS Appl. Energy Mater. 2023, 6, 10193.
Kumar, S.; Hassan, I.; Regue, M.; Gonzalez-Carrero, S.; Rattner, E.; Isaacs, M.A.; Eslava, S. J. Mater. Chem. A 2021, 9, 12179
Data-Driven Analysis of Contributing Factors in Spectra Toward Quantitative Prediction of Photocatalytic Activity of BaTaO₂N
Authors: Yamada Musashi , Yamada Tetsuya , Yanagisawa Kazumichi , Tipplook Mongkol , Hayashi Fumitaka , Teshima Katsuya 
Published: December 2024

Photocatalytic hydrogen production via water splitting has attracted attention as an energy infrastructure independent of fossil resources. However, it has not yet reached the practical energy conversion efficiency level (5%), necessitating the enhancement of photocatalyst materials. Various crystal characteristics such as crystal shape, surface state, and lattice defects are known to be influencing factors on the performance of photocatalysts. However, their quantitative correlation and synergistic effects of each factor on performance are unclear. Understanding the quantitative correlation of crystal properties with photocatalytic activity would give effective crystal design for improvement. In this study, we aimed to extract crystallographic properties and understand their correlation with photocatalytic water splitting by multivariate analysis. BaTaO2N (BTON), which responds to visible light, was selected as a model material for photocatalysis.
First, internal crystal information was collected from X-ray diffraction (XRD) patterns and Ultraviolet-Visible (UV-Vis) absorption spectra. Interpretable feature values, such as intensity ratio and full width at half maximum at the diffraction peak, impurity, absorption edge wavelength and its area were automatically extracted using Python. The factors contributing to water splitting were then identified by using LASSO regression. These feature values were used to depict a two-dimensional dimension reduction diagram (t-SNE diagram), which describe photocatalytic activity as color map. The t-SNE diagram confirmed the clustering of data with similar water splitting activity, indicating that this diagram can be used as an effective guide to explore the crystal properties with high photocatalytic activity. Next, scanning electron microscopy (SEM) was analyzed to extract additional feature values. Image analysis was carried out for the comprehensive extraction of crystal surface information. Gray-Level Co-occurrence Matrix (GLCM) texture analysis was an effective method for detecting boundary parts, thus used to extract abstract crystal surface information. In addition, Variational Autoencoder (VAE) was used to extract specific crystal surfaces. The extracted feature values can contain information about crystal surface structures such as crystal morphology, particle agglomeration, and co-catalyst support state. Correlation analysis between these feature values and photocatalytic activity is now underway and will be reported in the presentation.
Acknowledgement
This work was partly supported by the Strategic Innovation Program (SIP) of the Cabinet Office, the NEDO Green Innovation fund projects, and collaborative research with companies.
Construction of ITO Nanoparticle Immobilized Substrates and Evaluation of Their Photocurrent Responses
Authors: Kanaizuka Katsuhiko , Yamaguchi Mei 
Published: December 2024

Near-infrared (NIR) light can be used in a variety of fields, including energy conversion devices and medicines. However, there are only a limited number of compounds with NIR absorption, and research into their effective use remains unexplored. Previous research in our laboratory has reported the enhancement of visible light absorption in devices based on the combination of metal nanoparticles and functional molecules. In this study, we applied the system of the previous study to investigate the fabrication conditions of composite substrates of indium cubic tin oxide nanoparticles (ITO NPs), which have localized surface plasmon resonance (LSPR) absorption in the NIR region, and silicon naphthalocyanine derivative (SiNPc), which absorbs NIR light, and the photocurrent of the fabricated substrates.
ITO NPs were synthesised by a solvothermal method using ethylene glycol. SiNPc was synthesised by mixing SiNPcCl2 with 1-octanol. The conductive substrates were sonically cleaned, ozonated and then surface treated by the immersion in a 3-Aminopropyltrimethoxysilane (3-APTMS) solution. ITO NPs immobilized substrates were constructed by spin-coating method. This substrate was immersed in a SiNPc solution to construct the conductive substrate/3-APTMS/ITO NPs/SiNPc composite substrate.
The synthesized nanoparticles were confirmed to be cubic ITO NPs with high crystallinity and approximately 30 nm per side from XRD and TEM images. The UV-Vis-NIR spectrum of the fabricated substrates showed the absorption of the soret band of SiNPc at 340 nm and the LSPR absorption of ITO NPs in the NIR region, indicating that the conductive substrate/3-APTMS/ITO NPs/SiNPc composite substrate was fabricated. Photocurrent measurements were carried out using NIR light, and the cathode current was observed.