Article
Chemistry, Physical
Salhah H. Alrefaee
Summary: Through DFT computational study, it was found that imidazolium and pyridinium based ionic liquids exhibit good anticorrosive potential, with corrosion inhibition performance depending on the nature of alkyl groups and halide ions. Among the studied ionic liquids, certain compounds were found to show the best corrosion inhibition performance in both imidazolium and pyridinium based categories.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Multidisciplinary
Yuval Simha, Gil Daniels, Amalya Goldman, Elihay Kuniavsky, Dmitry Tsvelikhovsky
Summary: A new strategy for direct access to fully substituted polycyclic imidazolium salts using alpha-enaminones and proline as the reagents is reported. This open-flask operation is a catalyst-, metal-, and Lewis acid-free green process, which does not require an ion-exchange step. It can produce good yields with minimal formation of side products, and is not limited to aryl substituents.
Article
Environmental Sciences
Rajendra B. Mujmule, Hern Kim
Summary: The recent increase in CO2 levels has had a significant impact on the environment, leading to a demand for an effective catalyst to convert CO2 into valuable chemical products. This study demonstrates a simple method for the chemical fixation of CO2 into cyclic carbonates using a one-pot synthesized tri-functional-imidazolium bromide ionic liquid, without the need for solvents, metals, or additives.
JOURNAL OF ENVIRONMENTAL MANAGEMENT
(2022)
Review
Chemistry, Analytical
Ahmad Husaini Mohamed, Nur Athirah Noorhisham, Kamariah Bakar, Noorfatimah Yahaya, Sharifah Mohamad, Sazlinda Kamaruzaman, Hasnah Osman
Summary: Imidazolium-based poly(ionic liquids) (PILs) are versatile materials that have attracted considerable attention in dispersive solid-phase extraction (DSPE) techniques. They offer a wide range of functionalities and show potential for development in new adsorbent materials.
MICROCHEMICAL JOURNAL
(2022)
Article
Spectroscopy
Md. Abrar Siddiquee, Juhi Saraswat, Mehraj ud din Parray, Prashant Singh, Savita Bargujar, Rajan Patel
Summary: In this study, the interaction between levofloxacin (LVF) and two imidazolium-based ionic liquids (ILs), 1-butly-3-methylimidazolium chloride ([Bmim][Cl]) and 1-decyl-3-methylimidazolium chloride ([Dmim][Cl]), was investigated using spectroscopic techniques and computational methods. The results showed the formation of fluorescent complexes between LVF and ILs. UV-Vis spectroscopy confirmed the complex formation, and cyclic voltammetry results indicated a strong interaction between LVF and ILs. Density functional theory (DFT) calculations were performed to study the structure and molecular orbitals of the ILs, LVF, and their complexes.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Chemistry, Physical
Nikolett Bagany, Aleksandar Tot, Milan Vranes, Slobodan Gadzuri
Summary: For the first time, a carboxyl-functionalized ionic liquid was synthesized and characterized, with experimental and computational determination of its acidity constant. The introduction of carboxyl group was found to enhance hydration and structure-making properties of the imidazolium-based ionic liquids, as supported by viscosity measurements and computational simulations.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Physical
Sukanya Das, Niharika Kashyap, Sangeeta Kalita, Debanga Bhusan Bora, Ruli Borah
Summary: Twelve N-SO3H functionalised ammonium and imidazolium based Bronsted acidic ionic liquids with varying anions were synthesized and characterized. The effects of different cations and anions on the properties of the ILs were studied. The conductivity of the ILs in different solvents was measured and correlated with solvatochromic parameters of the solvents. The polarity of the ILs was studied using fluorescence emission spectroscopy. The electrochemical stability of the ILs in different solvents was determined. Among the four types of anions, CF3COO(- )and Cl- were found to have higher thermal stability.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Applied
Fei Ren, Jinwei Wang, Jinglin Yu, Cheng Zhong, Fengwei Xie, Shujun Wang
Summary: This study demonstrates the synthesis of acetylated maize starches (AMS) with different degrees of substitution (DS) in the presence of ionic liquids (ILs) without catalyst. The DS and reaction efficiency of AMS increase with decreasing alkyl chain length of cations or anions. AMS synthesized in imidazolium-based ILs exhibit higher hydrophobicity and thermal stability. The viscosity of ILs and the interactions between acetic anhydride molecules are crucial for the acetylation of starch.
CARBOHYDRATE POLYMERS
(2022)
Article
Engineering, Environmental
Nuzahat Habibul, Yan-Yun Hu, Yi Hu, Guo-Ping Sheng
Summary: This study investigated the uptake and toxicity of imidazolium based ionic liquids (ILs) with different alkyl chain lengths by ryegrass. Results showed that long alkyl chain ILs had stronger growth inhibition on plants compared to short chain ILs, which were more easily absorbed and accumulated in plant tissues.
JOURNAL OF HAZARDOUS MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Gina Stuhrmann, Jannik Schneider, Kilian Schmidt, Stefanie Dehnen
Summary: In recent years, chalcogenido metalate compounds based on tetrahedral clusters have been extensively studied due to their rich structural chemistry and uncommon chemical and physical properties. This study expands the mild alkylation approach and successfully achieves selective propylation, pentylation, and hexylation of sulfido-oxo stannate clusters. The effect of the organic groups attached to the cluster and present in the counterions of the products on the compounds' structural and opto-electronic properties is discussed. Well-soluble cluster salts [Sn10O4S16(SR)4]4- (R = propyl, pentyl, hexyl) are obtained from the treatment of Na4[SnS4]·14H2O with symmetrically bis-alkyl-functionalized imidazolium-based ionic liquids.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Yiqiang Deng, Ying Liu, Yaju Chen, Lihua Cheng, Weili Dai, Hongbing Ji
Summary: Towards a carbon-neutral future, the anthropogenic recycling of captured carbon dioxide into valuable chemicals and materials is an attractive pathway. A zeolitic imidazolate framework (ZIF-9-ImBr) with electrophilic cobalt ions and CO2-philic nitrogen-rich units was synthesized and used as a catalyst for the solvent-free synthesis of cyclic carbonates. The ZIF-9-ImBr exhibited good catalytic performance and could be easily recycled. This work highlights the potential of functional ZIF-based materials for CO2 capture and conversion.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Gina Stuhrmann, Jannik Schneider, Kilian Schmidt, Stefanie Dehnen
Summary: Chalcogenido metalate compounds based on tetrahedral clusters have been extensively studied. It has been shown that partial butylation of the inorganic cluster core allows access to tetrahedral sulfido-oxo stannate clusters with reasonable solubility in conventional solvents. In this study, selective propylation, pentylation, and hexylation of sulfido-oxo stannate clusters were achieved using symmetrically bis-alkyl-functionalized imidazolium-based ionic liquids. The effect of attached organic groups and counterions on the structural and opto-electronic properties of the compounds was discussed.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Abobakr K. Ziyada, Abdelbagi Osman, Abdullah Ahmed Elbashir, Fahd Rajab, Abdul Majeed Khan, Mei Musa Ali Omar, Cecilia Devi Wilfred
Summary: This study synthesized propanenitrile imidazolium-based ionic liquids with different functional groups (allyl, ethoxyl, and benzyl) and incorporating dioctylsulfosuccinate (DOSS) anion. The elemental analysis and NMR results confirmed the synthesized IL structures. The properties of these ILs, including density, viscosity, refractive index, and several thermodynamic properties, were measured and analyzed. The findings provide valuable insights into the properties and potential applications of these ILs.
Article
Chemistry, Physical
Onajite T. Diejomaoh Abafe, Muhammad Mohsin Azim, Bice S. Martincigh, Annegret Stark
Summary: This study investigates the physicochemical properties of a series of cation-fluorinated ionic liquids and provides experimental evidence for nanosegregation and triphilicity in these liquids. The introduction of fluoroalkyl chains enhances hydrogen bond interactions between anions and cations and leads to structural rearrangements. The study also demonstrates the use of a group contribution method to predict the density of the liquids.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Polymer Science
Kathryn E. O'Harra, Emily M. DeVriese, Erika M. Turflinger, Danielle M. Noll, Jason E. Bara
Summary: This study introduces a series of vinyl-imidazolium-based polyelectrolyte composites modified with multivalent imidazolium-benzene ionic liquids or crosslinked with novel cationic crosslinkers. The composites exhibited enhanced CO2 permeabilities and selectivities against N-2 or CH4, demonstrating the potential for tuning the properties and transport behaviors of ionic polymers using ionic liquid-inspired small molecules.
Article
Chemistry, Physical
Kohei Yamanoi, Satoshi Shibuta, Atsushi Shiro, Masao Noumi, Melvin John F. Empizo, Marilou Cadatal-Raduban, Nobuhiko Sarukura, Keiko Nishikawa, Takeshi Morita
Summary: Fluoropolymers have diverse applications in various industries. Neat fluoropolymers and fluorinated copolymers were synthesized using suspension polymerization method, with an increase in structural disorder observed at a slower rate with higher VdF content in the copolymer. The copolymer with the highest VdF content showed similar crystallinity before and after the stimulus, indicating good thermal stability and microvoid tolerance.
JOURNAL OF SUPERCRITICAL FLUIDS
(2022)
Article
Chemistry, Physical
Keiko Nishikawa, Kozo Fujii, Taisei Yamada, Masahiro Yoshizawa-Fujita, Kazuhiko Matsumoto
Summary: This study investigated the structures of three IPCs using powder crystal diffraction data and discussed the motion modes of different ions, indicating the possibility of estimating ion movement in IPCs.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Multidisciplinary Sciences
Naoto Kitamura, Yoichiro Konishi, Wenli Ma, Naoya Ishida, Toshihiko Mandai, Chiaki Ishibashi, Yasushi Idemoto
Summary: In this study, Mg-Fe-O and Mg-Ni-O were investigated as positive-electrode materials for magnesium rechargeable batteries. The crystal structures and electrochemical properties of these materials were studied. The results showed that Mg-Fe-O exhibited higher discharge capacity and good cycle performance, which might be attributed to its specific crystal structure.
SCIENTIFIC REPORTS
(2022)
Article
Nanoscience & Nanotechnology
Xiatong Ye, Hongyi Li, Takuya Hatakeyama, Hiroaki Kobayashi, Toshihiko Mandai, Norihiko L. Okamoto, Tetsu Ichitsubo
Summary: Rechargeable magnesium batteries are promising candidates for future batteries due to their abundant resources and high energy density. This study compares the reaction behavior of different MnO2 cathodes in two electrolytes and highlights the importance of interfacial stability for practical applications.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Hiroaki Kobayashi, Yu Fukumi, Hiroto Watanabe, Reona Iimura, Naomi Nishimura, Toshihiko Mandai, Yoichi Tominaga, Masanobu Nakayama, Tetsu Ichitsubo, Itaru Honma, Hiroaki Imai
Summary: Ultraporous and ultrasmall cubic spinel MgMn2O4 (MMO) is fabricated through a freeze-dry assisted room-temperature alcohol reduction process. Heat-treatment removes surface hydroxy groups and activates MMO, increasing its discharge capacity from 160 mAh g(-1) to 270 mAh g(-1), close to the theoretical value. The ultraporous, ultrasmall particles stabilize the metastable cubic spinel phase, promoting Mg2+ insertion/deintercalation and reversible transformation between cubic spinel and cubic rock-salt phases.
Article
Physics, Applied
Takeshi Morita, Teruki Kadota, Kouhei Kusano, Yoshitada Tanaka, Keiko Nishikawa
Summary: Density fluctuation is crucial for understanding disordered systems, and supercritical fluid is a typical disordered system with high inhomogeneity. This study proposes a methodology to determine the density fluctuations, fluid density, normalized scattering intensity, and small-angle scattering signals absolutely from a scattering experiment. The validity of this method is confirmed through the analysis of supercritical carbon dioxide and the quantitative determination of the density fluctuations of supercritical methanol for the first time.
JAPANESE JOURNAL OF APPLIED PHYSICS
(2023)
Article
Chemistry, Analytical
Yasushi Idemoto, Mina Takamatsu, Chiaki Ishibashi, Naoya Ishida, Toshihiko Mandai, Naoto Kitamura
Summary: Mg1.33V1.67-xMnxO4 (x= 0.1 to 0.4) was synthesized for the first time using a solid-phase method under high vacuum conditions. The crystal structures were confirmed to be spinel with Fd3(-)m space group through powder X-ray diffraction analysis, and the chemical compositions were found to be uniform through STEM observation and elemental analysis. Charge and discharge cycle tests revealed that the discharge capacity depended on the cycle number, Mn composition, and working temperature. Among them, Mg1.33V1.57Mn0.1O4 (x=0.1) exhibited the highest discharge capacity of 256 mAh g(-1) at the 13th cycle, while the initial capacity was only 73 mAh g(-1) at 90 degrees C. The local structure was analyzed using EXAFS spectra, which showed that Mg1.33V1.57Mn0.1O4 had the smallest lattice distortion due to Mn at 16d sites, and XAFS spectra indicated a significant change in the oxidation state of V during the charge/discharge cycles. The particularly stable crystal structure and large contribution of charge compensation by V may contribute to the excellent charge-discharge performance of Mg1.33V1.57Mn0.1O4.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Toshihiko Mandai, Hiroko Naya, Hyuma Masu
Summary: The electrolyte material for high-energy-density rechargeable batteries should have sufficient stability against metallic negative electrodes. Weakly coordinating anion (WCA)-based electrolytes have shown excellent performance due to their strong interaction with metal cations. In this study, the valency of paired cation species was found to affect the transport properties and electrochemical characteristics of the electrolytes, with divalent electrolytes exhibiting higher conductivity than monovalent electrolytes. The combination of magnesium cations and [B(HFIP)4]- anion showed outstanding performance in ethereal solutions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Toshihiko Mandai, Masaru Yao, Keitaro Sodeyama, Akiko Kagatsume, Yoshitaka Tateyama, Hiroaki Imai
Summary: Rechargeable magnesium batteries (RMBs) have the potential to be a sustainable energy storage technology due to the abundance of magnesium metal and its excellent energy storage properties. However, to compete with lithium-ion batteries, their energy density needs to be improved. This study explores the use of different organic solvent-based electrolytes to design anodically stable ether-based electrolyte solutions for RMB applications. Anodically stable electrolytes were successfully developed by combining suitable fluorinated glyme-based solvents with appropriate conducting salts, achieving a remarkable anodic limit and suppressing corrosion of current collectors. However, these electrolytes were not suitable for RMBs with high-voltage oxide-based cathodes due to catalytic decomposition during charging.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Naomi Nishimura, Kazumasa Masaki, Wei Tan, Reona Iimura, Hiroaki Kobayashi, Kei Nishikawa, Toshihiko Mandai, Hidetoshi Somekawa, Yoichi Tominaga
Summary: To improve the cycle performance of Mg metal batteries, a polymer coating (PSTFSI-Mg) was applied on the surface of spinel-type MgMn2O4 cathode. The polymer coating promoted electron transfer between particles, as confirmed by transmission electron microscopy. Density functional theory calculations revealed that the polymer reduced the energy gap between the valence band maximum of MgMn2O4 and the highest occupied molecular orbital level of the electrolyte, thus suppressing electrolyte degradation.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Energy & Fuels
Chao Zhang, Jun Cheng, Yiming Chen, Maria K. Y. Chan, Qiong Cai, Rodrigo P. Carvalho, Cleber F. N. Marchiori, Daniel Brandell, C. Moyses Araujo, Ming Chen, Xiangyu Ji, Guang Feng, Kateryna Goloviznina, Alessandra Serva, Mathieu Salanne, Toshihiko Mandai, Tomooki Hosaka, Mirna Alhanash, Patrik Johansson, Yun-Ze Qiu, Hai Xiao, Michael Eikerling, Ryosuke Jinnouchi, Marko M. Melander, Georg Kastlunger, Assil Bouzid, Alfredo Pasquarello, Seung-Jae Shin, Minho M. Kim, Hyungjun Kim, Kathleen Schwarz, Ravishankar Sundararaman
Summary: New materials for electrochemical energy storage and conversion play a crucial role in the electrification and sustainable development of modern societies. Molecular modelling, based on the principles of quantum mechanics and statistical mechanics and empowered by machine learning techniques, allows us to understand, control, and design electrochemical energy materials with atomic precision.
JOURNAL OF PHYSICS-ENERGY
(2023)
Article
Chemistry, Physical
Takahiro Okuo, Toshihiko Mandai, Hiroyasu Masunaga, Noboru Ohta, Hidetoshi Matsumoto
Summary: In this study, magnesiated perfluorosulfonated ionomer (Nafion-Mg) gel electrolytes swollen in magnesium bis(trifluoromethanesulfonyl)amide/triglyme (Mg(TFSA)(2)/G3) solutions were prepared and characterized. The swollen Nafion gel electrolytes exhibited good ionic conductivity and reversible Mg deposition/dissolution behavior. This is the first study on the structural and electrochemical characterization of magnesium ion-exchanged Nafion swollen in a Mg(TFSA)(2)/glyme solution.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Toshihiko Mandai, Mariko Watanabe
Summary: The compatibility of rechargeable magnesium batteries with atmospheric conditions (except moisture) has not been thoroughly studied. In this study, we investigated the impact of atmospheric conditions on the electrochemical dissolution-deposition behavior of magnesium in non-aqueous electrolytes. Oxygen, even in trace amounts in the electrolyte, was found to be a detrimental impurity for reversible magnesium electrochemistry.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Electrochemistry
Toshihiko Mandai, Hidetoshi Somekawa
Summary: The practical energy density of batteries incorporating elemental metals as anode active materials is largely influenced by the thickness of the metal anodes. However, the use of ultrathin magnesium foils is challenging due to the brittleness and unworkability of magnesium. This study successfully fabricated crack-free ultrathin magnesium foils with favorable microstructure by controlling the initial microstructure and rolling temperature, and demonstrated their excellent electrochemical characteristics as anode materials.
BATTERIES & SUPERCAPS
(2022)
Article
Chemistry, Physical
Takeshi Morita, Hitomi Okada, Taisei Yamada, Ryo Hidaka, Takeshi Ueki, Kazuyuki Niitsuma, Yuzo Kitazawa, Masayoshi Watanabe, Keiko Nishikawa, Kenjirou Higashi
Summary: This study investigates the interaction between poly(benzyl methacrylate) (PBnMA) and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C(2)mim][NTf2]), using magic-angle spinning NMR spectroscopy and small-angle scattering techniques. The results reveal that PBnMA adopts a random coil conformation and exhibits low mobility in [C(2)mim][NTf2]. Furthermore, the binding between PBnMA and the ionic liquid is strengthened at higher temperatures.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
