bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited, Digital Presentation) Novel Technology for Halide Phosphors
Authors: Toda Kenji 
Published: November 2022

Many people believe that an ionic-diffusion in an ionic crystal is very slow around room temperature. Therefore, a conventional solid-state reaction (SSR) method requires a high temperature to synthesize the ceramic materials. Synthesis of morphology controlled phosphors can be categorized in two ways namely, chemical and physical methods. Various methods such as the sol-gel, hydro-thermal, or the polymerized complex methods are usually used to synthesize phosphor materials. However, these methods require expensive and special experimental equipment, raw materials, or solvents.
In order to perform inexpensive mass-production for new phosphor materials, we have applied novel soft chemical synthesis technique, water-assisted solid-state reaction (WASSR) method. The WASSR method is very simple and can synthesize nano-materials just by storing or mixing raw materials added a small amount (typically 10wt%) of water at low temperature below 500 K. Typical particle sizes (10 - 100 nm) of the samples prepared by the WASSR method were smaller than that (2 - 10 micrometer size) of the sample prepared by the SSR method. The most probable mechanism is new type water accelerated solid acid-base reaction on the surface. We successfully synthesized various phosphor materials ((Cs,Rb)VO3, YVO4:Eu, Ba2SiO4:Eu, LaPO4:Ce,Tb) by the WASSR method. In this study, we report the synthesis of non-oxide halide phosphors (CsPbX3, K2SiF6:Mn).
For example, a stoichiometric mixture of CsBr, PbCl2 was mixed for the WASSR synthesis of CsPbBr3 quantum dot phosphor. Then, a small amount (10 wt%) of water was added to the mixture and mixed using mortar for 1 min to synthesize a single phase of CsPbBr3. The XRD pattern of the products are in good agreement with that of single phase CsPbBr3. The QD dispersed hexane solution shows strong green emission under the excitation of UV light. Our proposed WASSR synthesis technique is a powerful tool for rapid screening and mass-production of phosphor materials.
Acknowledgment
This research was partly supported by the Ministry of Trade, Industry and Energy(MOTIE) and Korea Institute for Advancement of Technology(KIAT) through the International Cooperative R&D program(P0006844_Development of color conversion nanocrystal luminescence materials for next generation display).
References
[1] T. Kaneko, S. W. Kim, A. Toda, K. Uematsu, T. Ishigaki, K. Toda, M. Sato, J. Koide, M. Toda, Y. Kudo,T. Masaki, and D. H. Yoon, Sci. Adv. Mater., 7, 1502 (2015).
[2] S-W. Kim, T. Hasegawa, M. Watanabe, M. Muto, T. Terashima, Y. Abe, T. Kaneko, A. Toda, T. Ishigaki, K. Uematsu, K. Toda, M. Sato, E. Kawakami, J. Koide, M. Toda, Y. Kudo, T. Masaki and D. H. Yoon, Appl. Spect. Rev., 52, 1 (2017).
Electrochemical Detection of Nitrite Ions Using PEDOT Based Films
Authors: Lucero Gisella Liliana , Bund Andreas 
Published: November 2022

Poly (3,4-ethylenedioxythiophene) (PEDOT) is an important conducting polymer that is widely studied for applications in photovoltaic devices, thermoelectric materials, batteries, capacitors and sensors [1]. In the field of sensors, PEDOT and PEDOT composites synthesized by chemical and electrochemical methods have been used for the detection of organic and inorganic analytes [2]. In particular, the performance of the composites of PEDOT with nanomaterials (mono and bi-metallic nanoparticles, graphene and nanotubes) has been thoroughly investigated in the last years because the incorporation of those nanostructures can significantly improve the sensing properties of the pristine polymer [3,4]. However, to the best of our knowledge the effect of the content of hollow PdAu nanoparticles in PEDOT composites for the detection of nitrite, an important environmental pollutant, has not been reported before.
In this work, PEDOT films were prepared by cyclic voltammetry and under amperometric and potentiostatic conditions from a solution of EDOT, LiClO4 and SDS (sodium dodecyl suphate). The films were characterized by scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX). 500 nm- and 300 nm-thick PEDOT films deposited on glassy carbon were used for the electrochemical detection of nitrite by differential pulse voltammetry. 500 nm-thick films shown a higher sensitivity towards NO2
- ions (0.027 μA μM-1). Hollow nanoparticles of gold and palladium were synthesized by a galvanic replacement reaction using Na2PdCl4. PEDOT films were codeposited with the hollow PdAu nanoparticles at constant potential. The performance of the composites with different contents of the bimetallic nanoparticles (3,6,12,15,24 and 30% of the total mass of nanoparticles) were evaluated for the detection of nitrite ions in the range of 50 to 250 μM nitrite. All composites exhibited a higher performance in comparison to PEDOT films mainly in the range of 50 to 112.5 μM.
Figure 1.- SEM PEDOT films produced by (a) potentiostatic deposition, (b) constant current, (c) cyclic voltammetry and (d) DPV curves of nitrite detection with PEDOT + 15% mass percent of PdAu nanoparticles suspension

Figure 1
Separation of Azeotropic Refrigerant Mixtures Using Ionic Liquids
Authors: Shiflett Mark , Baca Kalin 
Published: November 2022

Refrigeration and air-conditioning systems are widespread throughout modern society, from the refrigerated cold chain that provides fresh foods and storage of medicines to the air conditioning of homes and buildings. Refrigeration is viewed as one of the most transformative engineering achievements of the 20th century and the demand for cooling will continue to increase as economic conditions improve and the climate continues to warm; however, refrigerants do come with an environmental cost.
In 1987, the Montreal Protocol phased out chlorofluorocarbon (CFC) refrigerants because of their high ozone depletion potential (ODP). The replacements, typically mixtures of hydrofluorocarbons (HFCs), are safe for the Earth's ozone layer, but most have high global warming potentials (GWPs). HFCs account for 7.8% of total global greenhouse gas emissions, with 63% of that from “indirect” emissions (i.e., energy for running the system). As a result, 197 countries signed the Kigali agreement in 2016 to phase out high-GWP HFCs, with the goal of reducing emissions by 80% in the next 20 years. Millions of metric tons (mts) of high-GWP refrigerants will need to be reclaimed, but there are no good methods for separating and recycling the individual components, given that many are azeotropic mixtures.
Currently, there is no means of separating azeotropic HFC mixtures, and the refrigerants will ultimately have to be incinerated. The commercial HFC mixture R-410A containing 50 wt.% HFC-32 (GWP = 675) and 50 wt.% HFC-125 (GWP = 3500) is a prime example. The HFC-32 can be reused when separated in new low-GWP products such as R-454B (69 wt% HFC-32 and 31 wt% HFO-1234yf) with a 75% lower GWP than R-410A.
Ionic liquids are being developed that can separate azeotropic HFC mixtures based on differences in solubility and used as entrainers in extractive distillation. This presentation will provide experimental data on the solubility of HFCs in ionic liquids that have been measured using gravimetric microbalances and modeling using the Peng-Robinson equation of state. ASPEN Plus simulations will show how a pilot process has been designed that can continuously separate azeotropic refrigerant mixtures such as R-410A.
(Invited, Digital Presentation) From Textile Waste to Cellulose Aerogel Beads Using Ionic Liquid
Authors: Negrier Marion , El Ahmar Elise , Sauceau Martial , Sescousse Romain , Bouet Guénaëlle , Eglin David , Budtova Tatiana 
Published: November 2022

A huge amount of waste textile is produced every year, and the majority is either burned, or buried in landfills, or downcycled. We propose making high added-value materials, aerogels, from textile waste, using ionic liquids. Aerogels are light-weight and nanostructured porous materials with high specific surface area. Depending on the type of textile, we use ionic liquid either to completely dissolve it (case of rayon or viscose), or to selectively dissolve cellulose (case of polycotton). Cellulose aerogels were made in the form of beads by prilling via dissolution in ionic liquid, coagulation and drying with supercritical CO2. Reference cellulose aerogel beads were made from microcrystalline cellulose to compare with textile-based aerogels.
The rheological properties of cellulose-ionic liquid solutions were studied to select the processing conditions. Aerogel beads of the size from 0.5 to 1.5 mm with excellent circularity were obtained. Cellulose-based aerogel beads from textile and from microcrystalline cellulose have density around 0.1 g/cm3, porosity around 90% and high specific surface area, around 300 m²/g. Cytotoxicity tests showed that these aerogels may potentially be used for life science applications.
Acknowledgements
We are grateful to Institut Carnot MINES for the financial support of this work, Julien Jaxel (PERSEE) for the drying with supercritical CO2, Antoine Perron (GALA – RAPSODEE) for the prilling and Suzanne Jacomet (CEMEF) for the help in SEM pictures.
Kinetic and Thermodynamic Properties of Ytterbium Chloride and Fluoride Complexes in Chloride Melts
Authors: Kuznetsov Sergey A , Stulov Yuriy V. , Gaune-Escard Marcelle 
Published: November 2022

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.
(Physical and Analytical Electrochemistry Division Max Bredig Award In Molten Salt and Ionic Liquid Chemistry) Of Ionic Liquids and Hydrogen Bonds
Authors: Welton Tom 
Published: November 2022

Whether it is the solubility of biopolymers, the rates of reactions, the physical properties of ionic liquids, or the formation of Deep Eutectic Solvents, the concept of the hydrogen bond often finds itself at the centre of explanations of ionic liquids’ behaviours. How strange it would seem to someone entering the field today that the idea that hydrogen bonds could form in ionic liquids was even recently controversial. So, how did this transformation come about?
In this presentation, you will meet some of the most well-known names in ionic liquids, both past and present. Key insights have only come from a variety of different techniques, both experimental and theoretical, being brought to bear on the question of whether hydrogen bonds exist or are of any use in ionic liquids and their solutions. You will also see that opposing views can turn out to both be correct and controversies are not always solved by one side ‘winning’ over the other.
Electrochemical Characterization of the Self-Assembled 4,4’-Bipyridine Layers at the Electrode | Ionic Liquid Interface
Authors: Siinor Liis , Ers Heigo , Pikma Piret , Lust Enn 
Published: November 2022

Self-assembled monolayers (SAMs) have significant importance in many modern applications1-2. The properties of SAMs depend on many aspects, such as the characteristics of individual molecules, forming the monolayer; by the interactions between these molecules; and SAM interactions with the electrolyte; the crystalline surface of the substrate; etc3. Therefore, the fundamental studies of these systems are crucial in determining the function of SAMs in various applications4-5.
The aim of the current work was to study the adsorption characteristics of 4,4’- bipyridine from ionic liquid media at different electrodes6.
Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted to characterize the electrochemical behavior of the self-assembled 4,4’-bipyridine (4,4’-BP) layers at the Sb(111) and Cd(0001) | 4,4’-BP+1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) interface. All the experiments were carried out in a three-electrode electrochemical cell in a glove-box, i.e., a nitrogen-controlled atmosphere.
CV method was used to examine the electrochemical characteristics of the system under investigation within the potential region −0.9 V < E < 0.0 V for Sb(111) and −2.1 V < E < -0.8 V for Cd(0001) vs. Ag|AgCl. The current values increase rapidly at the more negative end of the studied potential region, indicating that reduction processes started at the Sb(111) and Cd(0001) | 4,4’-BP+EMImBF4 interface. In contrast with the data measured in EMImBF4, where the system shows ideal polarisable behaviour in the whole potential range. Interfacial capacitance (C
s) values were calculated using the relation Cs=−(Z′′2𝜋f)−1

. Capacitance values calculated depend on the composition of the electrolyte (i.e., on the concentration of 4,4’-BP), electrode material as well as on applied potential. Cs
values are lower in the mixture than those measured in pure EMMImBF4 at a certain potential region in the case of both electrode materials. This effect is caused by the adsorption of 4,4’-BP molecules at the electrode surface. The shape of the phase angle vs. frequency (f) curves shows that mixed kinetic processes occur in the whole f range measured (i.e. diffusion and charge transfer steps in addition to adsorption).
Acknowledgments:
This work was supported by the Estonian Research Council grant PSG249, and by the EU through the European Regional Development Fund under project TK141 (2014-2020.4.01.15-0011).
References:

R. MacFarlane, et al.,
Energy Environ. Sci.
7, 232–250 (2014)

V. Plechkova et al., Chem. Soc. Rev.
37, 123–150 (2008)

Ulman, Chem. Rev.
96, 1533–1554 (1996)

Pikma et al., Electrochem. Commun., 61, 61-65 (2015)

Siinor et al., Electrochem. Commun., 78, 56-59 (2017)

H. Ers et al., DOI: 10.26434/chemrxiv-2022-5lcrq
(Digital Presentation) Silver Electrode Potentials in NaCl–KCl–Cscl Eutectic Melts
Authors: Volkovich Vladimir A. , Ivanov Alexander B. , Bessonova Dariya , Maltsev Dmitry S. 
Published: November 2022

Molten salts have a number of potential applications including metals’ electrowinning and electrorefining, pyrochemical spent nuclear fuels’ reprocessing. Considerable efforts were devoted over decades to investigation of various electrochemical processes in molten salts, especially in fused chlorides. Silver chloride electrode is one of convenient types of reference electrodes often employed in potentiometry measurements. This electrode has several advantages (especially compactness) compare to the standard chlorine reference electrode, potential of which in chloride melts is taken as zero. Surprisingly little attention was paid so far to the systematic study (covering the effect of temperature and concentration) of silver electrode potentials in molten chlorides, with majority of the works dating back to 1950-s and 60-s. Molten LiCl–KCl eutectic was, on obvious reasons, the best studied, and several other melts (NaCl, NaCl–KCl, LiCl–KCl–CsCl, NaCl–CsCl) were also looked at.
The present study was directed at the systematic study of silver electrochemistry in fused alkali chlorides and determining silver electrode potentials. Here we present the results of the experiments performed in the melts based on the ternary NaCl–KCl–CsCl (30–24.5–45.5 mol. %) eutectic mixture at 823–1073 K. Electrode potentials of silver were determined using the electromotive force measurements method and the following galvanic cell:
Ag|(NaCl–KCl–CsCl)+AgCl||(NaCl–KC1–CsCl)|Cl2 (C)
Concentration of silver in the electrolyte varied from 0.1 to 5 wt. %.
Silver electrode quickly equilibrated with the electrolyte and the potential remained stable over long time, Figure. Experimentally obtained electrode potentials were then used to calculate silver formal standard electrode potentials.
Figure. An example of silver electrode potential evolution over time in (NaCl–KCl–CsCl)–AgCl (5 wt. %) melt at 823 K. 2Cl–/Cl2 reference electrode.

Figure 1
Secondary FeF2-Li Batteries in Ionic Liquid Electrolytes
Authors: Olbrich Lorenz Frank , Xiao Albert Wang , Sanghadasa Mohan , Pasta Mauro 
Published: November 2022

Conventional intercalation Li-ion batteries are physico-chemically limited in their energy density and exhibit a restricted temperature operation range. To further increase energy density limit and enable reversible battery cycling at elevated temperatures, the exploitation of new cell chemistry is required. Conversion-type transition metal fluorides (TMFs) can store multiple Li-ions per metal center and thus increase the theoretical energy density by 200% to 300% compared to intercalation compounds. [1] Ionic liquids (ILs) are liquid salts (below 100°C) with improved thermal stability due to the ionic nature of its constituents, little to no flammability, and a low vapor pressure. Combining a TMF cathode with an IL electrolyte and a metallic lithium anode can provide an energy-dense, safe energy storage alternative with a broader operating temperature range and additional versatility for applications in the military, oil, and aerospace sector. [2]
In my talk, I will discuss our progress on the development and characterisation of a secondary FeF2-IL-Li-metal battery. We studied the impact of active material morphology and carbon-composite preparation techniques on the electronic conductivity and electrochemical performance in a bis(fluorosulfonyl)imide based IL electrolyte. In addition, we investigated different IL formulations for their applicability with TMFs and Li-metal. Both the cathode and anode electrolyte interphases were studied at different temperatures and their role in a full cell setup is elucidated.
[1] Olbrich, L. F., Xiao, A. W. & Pasta, M. Conversion-type fluoride cathodes: Current state of the art. Current Opinion in Electrochemistry 30, 100779 (2021).
[2] Lin, X., Salari, M., Arava, L. M. R., Ajayan, P. M. & Grinstaff, M. W. High temperature electrical energy storage: Advances, challenges, and frontiers. Chemical Society Reviews 45, 5848–5887 (2016).

Figure 1
(Invited) Pushing Lithium-Metal Batteries to the Limit: Fast Charging, Low Temperature, and Safety
Authors: Liu Ping 
Published: November 2022

The performance of lithium metal batteries has advanced significantly, thanks to continuous improvement in the lithium metal anode. Many chemical and mechanical control strategies have been employed to combat its degradation mechanisms such as parasitic reactions, dendritic growth, and formation of isolated lithium. Electrolytes with high salt concentrations, including those with non-solvating diluents (known as localized high concentration electrolytes, or LHCE), electrolyte additives, artificial coatings, 3D plating hosts Li, and applying pressures in the 100s-1000s of kPa range have all been found to be effect in yielding dense, high efficiency Li metal deposits. Despite these advancements, reported lithium metal batteries tend to be charged at low rates, operated under ambient conditions, and lacking sufficient information on their safety characteristics. In this talk, we will review our recent progress in pushing the lithium metal batteries to extreme operating conditions in term of temperature, charging rates, and shorting behavior.
To enable fast charging, we have focused on developing a nucleation agent on the surface of current collector that can induce the formation of large, uniform nucleation sites. These nanoscopic sites enable dense lithium plating at 5 mA c-2 of current density, when a planar Cu electrode will fail catastrophically. This uniform nucleation method leads to a 45 um thick Li deposit that is nearly porosity free. A lithium metal cell with a metal oxide cathode is capable of 1C charging for extended cycles.
To enable low temperature operation, we have focused on the development of new electrolyte compositions that uses weakly solvating solvents. These electrolytes, represented by monodentate ethers and LHCEs made of ethers, promote the formation of contact ion pairs after solvation over solvent separated ion pairs. These electrolytes have enabled the formation of dense lithium metal deposits at as low as -60oC, while strongly solvating electrolytes will promote the formation of dendrites and cell shorting.
Finally, any practical implementation of lithium metal batteries operating under these extreme conditions have to feature safety designs that mitigate the impact of internal shorting. In this regard, we have focused on separator designs that can detect and intercept lithium dendrites.