The Experts below are selected from a list of 153 Experts worldwide ranked by ideXlab platform
Toshiki Tajima - One of the best experts on this subject based on the ideXlab platform.
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anodic oxidation of organic compounds based on the cation exchange reaction between kbf4 and solid supported acids
Electrochemistry Communications, 2009Co-Authors: Atsushi Nakajima, Toshiki TajimaAbstract:Abstract We have developed a novel Electrolytic System for anodic oxidation of organic compounds based on the cation exchange reaction between potassium tetrafluoroborate (KBF 4 ) and solid-supported acids. It was clarified by cyclic voltammetry as well as preparative electrolyses that hydrogen tetrafluoroborate (HBF 4 ) derived from the cation exchange reaction acts as a supporting electrolyte in MeCN. On the basis of the Electrolytic System, anodic oxidation of 1,2,4-trimethoxybenzene was carried out to provide the corresponding homocoupling product in quantitative yield. Furthermore, anodic oxidation of benzyl alcohols having not only electron-donating but also electron-withdrawing groups at the para position was successfully achieved by optimizing the reaction conditions.
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An Electrolytic System based on the anion exchange reaction between KCl and an anion exchange resin
Electrochemistry Communications, 2009Co-Authors: Atsushi Nakajima, Toshiki TajimaAbstract:We have developed a novel Electrolytic System based on the anion exchange reaction between KCl and Amberlyst A26. It was demonstrated by preparative electrolysis experiments as well as cyclic voltammetry that the anion exchange reaction offers a unique Electrolytic System for electroreduction of organic compounds. On the basis of the Electrolytic System, electroreduction of aromatic carbonyl compounds was successfully achieved by using an undivided cell to provide the corresponding coupling products as pinacols in good to high yields with high diastereoselectivity.
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indirect anodic oxidation based on the cation exchange reaction between alkaline earth metal halides and solid supported acids
Journal of Electroanalytical Chemistry, 2008Co-Authors: Atsushi Nakajima, Toshio Fuchigami, Toshiki TajimaAbstract:We have developed a novel Electrolytic System for indirect anodic oxidation based on the cation exchange reaction between alkaline (earth) metal halides and solid-supported acids. It was demonstrated that hydrogen halides derived from the cation exchange reaction act as not only a supporting electrolyte but also a mediator in acetonitrile. On the basis of the Electrolytic System, indirect anodic oxidation of various benzyl alcohols in the presence of 2,6-lutidine was successfully achieved by controlled potential electrolysis to provide the corresponding benzaldehydes in good to excellent yields.
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development of an Electrolytic System for non kolbe electrolysis based on the acid base reaction between carboxylic acids as a substrate and solid supported bases
ChemInform, 2008Co-Authors: Toshiki Tajima, Hitoshi Kurihara, Toshio FuchigamiAbstract:We have successfully developed a novel Electrolytic System for non-Kolbe electrolysis based on the acid−base reaction between carboxylic acids as a substrate and solid-supported bases. It was found that the acid−base reaction between carboxylic acids and solid-supported bases preferentially takes place to reduce the cell voltage in MeOH. On the basis of the Electrolytic System, non-Kolbe electrolysis of various carboxylic acids was carried out to provide the corresponding methoxylated products in excellent yields.
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Development of a Novel Electrolytic System Using KBr as a Mediator and Solid-Supported Acids as a Supporting Electrolyte
Electrochemistry, 2006Co-Authors: Atsushi Nakajima, Toshiki Tajima, Toshio FuchigamiAbstract:We have successfully developed a novel Electrolytic System using KBr as a mediator and solid-supported acids as a supporting electrolyte. In this System, solid-supported acids such as Amberlyst 15Dry (–SO3H) serve as not only a promoter of the dissociation of KBr but also a supporting electrolyte. Anodic oxidation of some benzyl alcohols using KBr and Amberlyst 15Dry (–SO3H) in the presence of 2,6-lutidine was successfully carried out to provide the corresponding benzaldehydes in good to excellent yields.
Toshio Fuchigami - One of the best experts on this subject based on the ideXlab platform.
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indirect anodic oxidation based on the cation exchange reaction between alkaline earth metal halides and solid supported acids
Journal of Electroanalytical Chemistry, 2008Co-Authors: Atsushi Nakajima, Toshio Fuchigami, Toshiki TajimaAbstract:We have developed a novel Electrolytic System for indirect anodic oxidation based on the cation exchange reaction between alkaline (earth) metal halides and solid-supported acids. It was demonstrated that hydrogen halides derived from the cation exchange reaction act as not only a supporting electrolyte but also a mediator in acetonitrile. On the basis of the Electrolytic System, indirect anodic oxidation of various benzyl alcohols in the presence of 2,6-lutidine was successfully achieved by controlled potential electrolysis to provide the corresponding benzaldehydes in good to excellent yields.
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a new approach to anodic substitution reaction using acoustic emulsification
Organic and Biomolecular Chemistry, 2008Co-Authors: Ryosuke Asami, Toshio Fuchigami, Mahito AtobeAbstract:We have developed a novel Electrolytic System for anodic substitution reactions using acoustic emulsification. This new System involves the generation of a carbocation by anodic oxidation of a substrate, and then its reaction with a nucleophile droplet formed by ultrasonication. In this System, even if the oxidation potential of the nucleophile is lower than that of the substrate, the substrate was predominantly oxidized to give the corresponding cation intermediate because the nucleophile phase, which was insoluble in the Electrolytic medium, was electro-inactive. In addition, the overoxidation of the desired products was considerably suppressed by the extraction of products from the electrolyte solution into the nucleophile phase. As a result, the anodic substitution reaction of several carbamates with allyltrimethylsilane was carried out to provide the corresponding products in good to moderate yields.
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development of an Electrolytic System for non kolbe electrolysis based on the acid base reaction between carboxylic acids as a substrate and solid supported bases
ChemInform, 2008Co-Authors: Toshiki Tajima, Hitoshi Kurihara, Toshio FuchigamiAbstract:We have successfully developed a novel Electrolytic System for non-Kolbe electrolysis based on the acid−base reaction between carboxylic acids as a substrate and solid-supported bases. It was found that the acid−base reaction between carboxylic acids and solid-supported bases preferentially takes place to reduce the cell voltage in MeOH. On the basis of the Electrolytic System, non-Kolbe electrolysis of various carboxylic acids was carried out to provide the corresponding methoxylated products in excellent yields.
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Development of a Novel Electrolytic System Using KBr as a Mediator and Solid-Supported Acids as a Supporting Electrolyte
Electrochemistry, 2006Co-Authors: Atsushi Nakajima, Toshiki Tajima, Toshio FuchigamiAbstract:We have successfully developed a novel Electrolytic System using KBr as a mediator and solid-supported acids as a supporting electrolyte. In this System, solid-supported acids such as Amberlyst 15Dry (–SO3H) serve as not only a promoter of the dissociation of KBr but also a supporting electrolyte. Anodic oxidation of some benzyl alcohols using KBr and Amberlyst 15Dry (–SO3H) in the presence of 2,6-lutidine was successfully carried out to provide the corresponding benzaldehydes in good to excellent yields.
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Development of a Novel Environmentally Friendly Electrolytic System by Using Recyclable Solid‐Supported Bases for In Situ Generation of a Supporting Electrolyte from Methanol as a Solvent: Application for Anodic Methoxylation of Organic Compounds
Chemistry (Weinheim an der Bergstrasse Germany), 2005Co-Authors: Toshiki Tajima, Toshio FuchigamiAbstract:We have successfully developed a novel environmentally friendly Electrolytic System using recyclable solid-supported bases for in situ generation of a supporting electrolyte from methanol as a solvent. It was found that solid-supported bases are electrochemically inactive at an electrode surface. It was also found that solid-supported bases dissociate methanol into methoxide anions and protons. Therefore, in the presence of solid-supported bases, it was clarified that methanol serves as both a solvent and a supporting electrolyte generated in situ. Anodic methoxylation of various compounds with solid-supported bases was carried out to provide the corresponding methoxylated products in good to excellent yields with a few exceptions. The methoxylated products and the solid-supported bases were easily separated by only filtration, and the desired pure methoxylated products were readily isolated simply by concentration of the filtrates. The separated and recovered solid-supported bases were recyclable for several times.
Yulin Cao - One of the best experts on this subject based on the ideXlab platform.
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transition metal hollow nanocages as promising cathodes for the long term cyclability of li o batteries
Nanomaterials, 2018Co-Authors: Amrita Chatterjee, Yulin CaoAbstract:As a step towards efficient and cost-effective electrocatalytic cathodes for Li–O2 batteries, highly porous hausmannite-type Mn3O4 hollow nanocages (MOHNs) of a large diameter of ~250 nm and a high surface area of 90.65 m2·g−1 were synthesized and their physicochemical and electrochemical properties were studied in addition to their formation mechanism. A facile approach using carbon spheres as the template and MnCl2 as the precursor was adopted to suit the purpose. The MOHNs/Ketjenblack cathode-based Li–O2 battery demonstrated an improved cyclability of 50 discharge–charge cycles at a specific current of 400 mA·g−1 and a specific capacity of 600 mAh·g−1. In contrast, the Ketjenblack cathode-based one can sustain only 15 cycles under the same Electrolytic System comprised of 1 M LiTFSI/TEGDME. It is surmised that the unique hollow nanocage morphology of MOHNs is responsible for the high electrochemical performance. The hollow nanocages were a result of the aggregation of crystalline nanoparticles of 25–35 nm size, and the mesoscopic pores between the nanoparticles gave rise to a loosely mesoporous structure for accommodating the volume change in the MOHNs/Ketjenblack cathode during electrocatalytic reactions. The improved cyclic stability is mainly due to the faster mass transport of the O2 through the mesoscopic pores. This work is comparable to the state-of-the-art experimentations on cathodes for Li–O2 batteries that focus on the use of non-precious transition materials.
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Transition Metal Hollow Nanocages as Promising Cathodes for the Long-Term Cyclability of Li–O2 Batteries
MDPI AG, 2018Co-Authors: Amrita Chatterjee, Yulin CaoAbstract:As a step towards efficient and cost-effective electrocatalytic cathodes for Li–O2 batteries, highly porous hausmannite-type Mn3O4 hollow nanocages (MOHNs) of a large diameter of ~250 nm and a high surface area of 90.65 m2·g−1 were synthesized and their physicochemical and electrochemical properties were studied in addition to their formation mechanism. A facile approach using carbon spheres as the template and MnCl2 as the precursor was adopted to suit the purpose. The MOHNs/Ketjenblack cathode-based Li–O2 battery demonstrated an improved cyclability of 50 discharge–charge cycles at a specific current of 400 mA·g−1 and a specific capacity of 600 mAh·g−1. In contrast, the Ketjenblack cathode-based one can sustain only 15 cycles under the same Electrolytic System comprised of 1 M LiTFSI/TEGDME. It is surmised that the unique hollow nanocage morphology of MOHNs is responsible for the high electrochemical performance. The hollow nanocages were a result of the aggregation of crystalline nanoparticles of 25–35 nm size, and the mesoscopic pores between the nanoparticles gave rise to a loosely mesoporous structure for accommodating the volume change in the MOHNs/Ketjenblack cathode during electrocatalytic reactions. The improved cyclic stability is mainly due to the faster mass transport of the O2 through the mesoscopic pores. This work is comparable to the state-of-the-art experimentations on cathodes for Li–O2 batteries that focus on the use of non-precious transition materials
Atsushi Nakajima - One of the best experts on this subject based on the ideXlab platform.
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anodic oxidation of organic compounds based on the cation exchange reaction between kbf4 and solid supported acids
Electrochemistry Communications, 2009Co-Authors: Atsushi Nakajima, Toshiki TajimaAbstract:Abstract We have developed a novel Electrolytic System for anodic oxidation of organic compounds based on the cation exchange reaction between potassium tetrafluoroborate (KBF 4 ) and solid-supported acids. It was clarified by cyclic voltammetry as well as preparative electrolyses that hydrogen tetrafluoroborate (HBF 4 ) derived from the cation exchange reaction acts as a supporting electrolyte in MeCN. On the basis of the Electrolytic System, anodic oxidation of 1,2,4-trimethoxybenzene was carried out to provide the corresponding homocoupling product in quantitative yield. Furthermore, anodic oxidation of benzyl alcohols having not only electron-donating but also electron-withdrawing groups at the para position was successfully achieved by optimizing the reaction conditions.
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An Electrolytic System based on the anion exchange reaction between KCl and an anion exchange resin
Electrochemistry Communications, 2009Co-Authors: Atsushi Nakajima, Toshiki TajimaAbstract:We have developed a novel Electrolytic System based on the anion exchange reaction between KCl and Amberlyst A26. It was demonstrated by preparative electrolysis experiments as well as cyclic voltammetry that the anion exchange reaction offers a unique Electrolytic System for electroreduction of organic compounds. On the basis of the Electrolytic System, electroreduction of aromatic carbonyl compounds was successfully achieved by using an undivided cell to provide the corresponding coupling products as pinacols in good to high yields with high diastereoselectivity.
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indirect anodic oxidation based on the cation exchange reaction between alkaline earth metal halides and solid supported acids
Journal of Electroanalytical Chemistry, 2008Co-Authors: Atsushi Nakajima, Toshio Fuchigami, Toshiki TajimaAbstract:We have developed a novel Electrolytic System for indirect anodic oxidation based on the cation exchange reaction between alkaline (earth) metal halides and solid-supported acids. It was demonstrated that hydrogen halides derived from the cation exchange reaction act as not only a supporting electrolyte but also a mediator in acetonitrile. On the basis of the Electrolytic System, indirect anodic oxidation of various benzyl alcohols in the presence of 2,6-lutidine was successfully achieved by controlled potential electrolysis to provide the corresponding benzaldehydes in good to excellent yields.
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Development of a Novel Electrolytic System Using KBr as a Mediator and Solid-Supported Acids as a Supporting Electrolyte
Electrochemistry, 2006Co-Authors: Atsushi Nakajima, Toshiki Tajima, Toshio FuchigamiAbstract:We have successfully developed a novel Electrolytic System using KBr as a mediator and solid-supported acids as a supporting electrolyte. In this System, solid-supported acids such as Amberlyst 15Dry (–SO3H) serve as not only a promoter of the dissociation of KBr but also a supporting electrolyte. Anodic oxidation of some benzyl alcohols using KBr and Amberlyst 15Dry (–SO3H) in the presence of 2,6-lutidine was successfully carried out to provide the corresponding benzaldehydes in good to excellent yields.
Armand Ajdari - One of the best experts on this subject based on the ideXlab platform.
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steric effects in the dynamics of electrolytes at large applied voltages i double layer charging
Physical Review E, 2007Co-Authors: Mustafa Sabri Kilic, Martin Z. Bazant, Armand AjdariAbstract:The classical Poisson-Boltzmann (PB) theory of electrolytes assumes a dilute solution of point charges with mean-field electrostatic forces. Even for very dilute solutions, however, it predicts absurdly large ion concentrations (exceeding close packing) for surface potentials of only a few tenths of a volt, which are often exceeded, e.g., in microfluidic pumps and electrochemical sensors. Since the 1950s, several modifications of the PB equation have been proposed to account for the finite size of ions in equilibrium, but in this two-part series, we consider steric effects on diffuse charge dynamics (in the absence of electro-osmotic flow). In this first part, we review the literature and analyze two simple models for the charging of a thin double layer, which must form a condensed layer of close-packed ions near the surface at high voltage. A surprising prediction is that the differential capacitance typically varies nonmonotonically with the applied voltage, and thus so does the response time of an Electrolytic System. In PB theory, the differential capacitance blows up exponentially with voltage, but steric effects actually cause it to decrease while remaining positive above a threshold voltage where ions become crowded near the surface. Other nonlinear effects in PB theory are also strongly suppressed by steric effects: The net salt adsorption by the double layers in response to the applied voltage is greatly reduced, and so is the tangential "surface conduction" in the diffuse layer, to the point that it can often be neglected compared to bulk conduction (small Dukhin number).
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Steric effects in the dynamics of electrolytes at large applied voltages. I. Double-layer charging
Physical Review E - Statistical Nonlinear and Soft Matter Physics, 2007Co-Authors: Mustafa Sabri Kilic, Martin Z. Bazant, Armand AjdariAbstract:The classical Poisson-Boltzmann (PB) theory of electrolytes assumes a dilute solution of point charges with mean-field electrostatic forces. Even for very dilute solutions, however, it predicts absurdly large ion concentrations (exceeding close packing) for surface potentials of only a few tenths of a volt, which are often exceeded, e.g. in microfluidic pumps and electrochemical sensors. Since the 1950s, several modifications of the PB equation have been proposed to account for the finite size of ions in equilibrium, but in this two-part series, we consider steric effects on diffuse charge dynamics (in the absence of electro-osmotic flow). In this first part, we review the literature and analyze two simple models for the charging of a thin double layer, which must form a condensed layer of close-packed ions near the surface at high voltage. A surprising prediction is that the differential capacitance typically varies non-monotonically with the applied voltage, and thus so does the response time of an Electrolytic System. In PB theory, the capacitance blows up exponentially with voltage, but steric effects actually cause it to decrease above a threshold voltage where ions become crowded near the surface. Other nonlinear effects in PB theory are also strongly suppressed by steric effects: The net salt adsorption by the double layers in response to the applied voltage is greatly reduced, and so is the tangential "surface conduction" in the diffuse layer, to the point that it can often be neglected compared to bulk conduction (small Dukhin number).