Observation of a Large Current on the Cyclic Voltammetry of Acylaminoferrocenes in the Solid State: An Efficient Electron-Transfer Pathway through Continuous NH···O=C Hydrogen-Bond Chains and π-Conjugation

2005 ◽  
Vol 78 (7) ◽  
pp. 1270-1278 ◽  
Author(s):  
Taka-aki Okamura ◽  
Keiko Sakauye ◽  
Mototsugu Doi ◽  
Hitoshi Yamamoto ◽  
Norikazu Ueyama ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Electron Transfer ◽  
Cyclic Voltammetry ◽  
Solid State ◽  
Electron Transfer Pathway ◽  
Large Current

Experimental Assessment of the Practical Oxidative Stability of Lithium Thiophosphate Solid Electrolytes

2019 ◽  
Author(s):  
Georg Dewald ◽  
Saneyuki Ohno ◽  
Marvin Kraft ◽  
Raimund Koerver ◽  
Paul Till ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Solid State ◽  
Oxidative Stability ◽  
Photoelectron Spectroscopy ◽  
Solid Electrolytes ◽  
Stability Limit ◽  
Lithium Ion ◽  
High Energy ◽  
Redox Activity ◽  
Solid State Batteries

<p>All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use <i>stepwise</i><i>cyclic voltammetry </i>to obtain information on the practical oxidative stability limit of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>, a Li<sub>2</sub>S‑P<sub>2</sub>S<sub>5</sub>glass, as well as the argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The <i>stepwise cyclic voltammetry</i>approach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes. </p>

Experimental Assessment of the Practical Oxidative Stability of Lithium Thiophosphate Solid Electrolytes

2019 ◽  
Author(s):  
Georg Dewald ◽  
Saneyuki Ohno ◽  
Marvin Kraft ◽  
Raimund Koerver ◽  
Paul Till ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Solid State ◽  
Oxidative Stability ◽  
Photoelectron Spectroscopy ◽  
Solid Electrolytes ◽  
Stability Limit ◽  
Lithium Ion ◽  
High Energy ◽  
Redox Activity ◽  
Solid State Batteries

<p>All-solid-state batteries are often expected to replace conventional lithium-ion batteries in the future. However, the practical electrochemical and cycling stability of the best-conducting solid electrolytes, i.e. lithium thiophosphates, are still critical issues that prevent long-term stable high-energy cells. In this study, we use <i>stepwise</i><i>cyclic voltammetry </i>to obtain information on the practical oxidative stability limit of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>, a Li<sub>2</sub>S‑P<sub>2</sub>S<sub>5</sub>glass, as well as the argyrodite Li<sub>6</sub>PS<sub>5</sub>Cl solid electrolytes. We employ indium metal and carbon black as the counter and working electrode, respectively, the latter to increase the interfacial contact area to the electrolyte as compared to the commonly used planar steel electrodes. Using a stepwise increase in the reversal potentials, the onset potential at 25 °C of oxidative decomposition at the electrode-electrolyte interface is identified. X‑ray photoelectron spectroscopy is used to investigate the oxidation of sulfur(-II) in the thiophosphate polyanions to sulfur(0) as the dominant redox process in all electrolytes tested. Our results suggest that after the formation of these decomposition products, significant redox behavior is observed. This explains previously reported redox activity of thiophosphate solid electrolytes, which contributes to the overall cell performance in solid-state batteries. The <i>stepwise cyclic voltammetry</i>approach presented here shows that the practical oxidative stability at 25 °C of thiophosphate solid electrolytes against carbon is kinetically higher than predicted by thermodynamic calculations. The method serves as an efficient guideline for the determination of practical, kinetic stability limits of solid electrolytes. </p>

Vapochromism induced by intermolecular electron transfer coupled with hydrogen-bond formation in zinc dithiolene complex

2020 ◽  
Vol 8 (42) ◽  
pp. 14939-14947
Author(s):  
So Yokomori ◽  
Shun Dekura ◽  
Tomoko Fujino ◽  
Mitsuaki Kawamura ◽  
Taisuke Ozaki ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Electron Transfer ◽  
Bond Formation ◽  
Intermolecular Electron Transfer ◽  
Hydrogen Bond Formation ◽  
Complex Crystal

A novel vapochromic mechanism by intermolecular electron transfer coupled with hydrogen-bond formation was realized in a zinc dithiolene complex crystal.

scholarly journals Oligosilanylated Silocanes

Molecules ◽  
2021 ◽  
Vol 26 (1) ◽  
pp. 244
Author(s):  
Mohammad Aghazadeh Meshgi ◽  
Alexander Pöcheim ◽  
Judith Baumgartner ◽  
Viatcheslav V. Jouikov ◽  
Christoph Marschner
Keyword(s):  
Cyclic Voltammetry ◽  
Solid State ◽  
Xrd Analysis ◽  
29Si Nmr ◽  
Single Crystal Xrd ◽  
Substitution Pattern ◽  
Silyl Group ◽  
Steric Factors ◽  
Single Crystal Xrd Analysis ◽  
29Si Nmr Spectroscopy

A number of mono- and dioligosilanylated silocanes were prepared. Compounds included silocanes with 1-methyl-1-tris(trimethylsilyl)silyl, 1,1-bis[tris(trimethylsilyl)silyl], and 1,1-bis[tris(trimethylsilyl)germyl] substitution pattern as well as two examples where the silocane silicon atom is part of a cyclosilane or oxacyclosilane ring. The mono-tris(trimethylsilyl)silylated compound could be converted to the respective silocanylbis(trimethylsilyl)silanides by reaction with KOtBu and in similar reactions the cyclosilanes were transformed to oligosilane-1,3-diides. However, the reaction of the 1,1-bis[tris(trimethylsilyl)silylated] silocane with two equivalents of KOtBu leads to the replacement of one tris(trimethylsilyl)silyl unit with a tert-butoxy substituent followed by silanide formation via KOtBu attack at one of the SiMe3 units of remaining tris(trimethylsilyl)silyl group. For none of the silylated silocanes, signs of hypercoordinative interaction between the nitrogen and silicon silocane atoms were detected either in the solid state. by single crystal XRD analysis, nor in solution by 29Si-NMR spectroscopy. This was further confirmed by cyclic voltammetry and a DFT study, which demonstrated that the N-Si distance in silocanes is not only dependent on the energy of a potential N-Si interaction, but also on steric factors and through-space interactions of the neighboring groups at Si and N, imposing the orientation of the pz(N) orbital relative to the N-Si-X axis.

Studies on electrooxidation of lignin and lignin model compounds. Part 1: Direct electrooxidation of non-phenolic lignin model compounds

Holzforschung ◽  
2012 ◽  
Vol 66 (3) ◽  
Author(s):  
Takumi Shiraishi ◽  
Toshiyuki Takano ◽  
Hiroshi Kamitakahara ◽  
Fumiaki Nakatsubo
Keyword(s):  
Electron Transfer ◽  
Cyclic Voltammetry ◽  
Carbonyl Compounds ◽  
Model Compounds ◽  
Lignin Model Compounds ◽  
Bulk Electrolysis ◽  
Lignin Model ◽  
Dimeric Compound ◽  
High Yields ◽  
Short Time

Abstract The direct anodic oxidation of non-phenolic lignin model compounds was investigated to understand their basic behaviors. The results of cyclic voltammetry (CV) studies of monomeric model, such as 1-(4-ethoxy-3-methoxyphenyl)ethanol, are interpreted as the oxidation for Cα-carbonylation did not proceed in the reaction without a catalyst, but a base promotes this reaction. Indeed, the bulk electrolyses of the monomeric lignin model compounds with 2,6-lutidine afforded the corresponding Cα-carbonyl compounds in high yields (60–80%). It is suggested that deprotonation at Cα-H in the ECEC mechanism (E=electron transfer and C=chemical step) is important for Cα-carbonylation. In the uncatalyzed bulk electrolysis of a β-O-4 model dimeric compound, 4-ethoxy-3-methoxyphenylglycerol-β-guaiacyl ether, the corresponding Cα-carbonyl compound was not detected but as a result of Cα-Cβcleavage 4-O-ethylvanillin was found in 40% yield. In the electrolysis reaction in the presence of 2,6-lutidine (as a sterically hindered light base), the reaction stopped for a short time unexpectedly. These results indicate the different electrochemical behavior of simple monomeric model compounds and dimeric β-O-4 models. The conclusion is that direct electrooxidation is unsuitable for Cα-carbonylation of lignin.

Refinement of hydrogen atomic position in a hydrogen bond using a combination of solid-state NMR and computation

2003 ◽  
pp. 2834 ◽  
Author(s):  
Robin K. Harris ◽  
Phuong Y. Ghi ◽  
Robert B. Hammond ◽  
Cai-Yun Ma ◽  
Kevin J. Roberts
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Solid State Nmr ◽  
Atomic Position
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