A Titanium(III) Phosphite Exhibits Polymorph-Distinct Redox Activity Involving Proton-Coupled Electron Transfer

2021 ◽  
Author(s):  
Ling-I Hung ◽  
Tsung-Hsiu Hsieh ◽  
Jhao-Yang Syu ◽  
Pei-Lin Chen ◽  
Chia-Her Lin ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Solid State ◽  
Redox Activity ◽  
Proton Distribution ◽  
Proton Coupled Electron Transfer

A novel titanium(III) phosphite with intriguing polymorphism and solid-state proton-coupled electron transfer (PCET) oxidation is presented. The polymorphs show structure-dependent PCET reactivity, interpretable by proton distribution in channels. Combined with...

Ca2[Ti(HPO4)2(PO4)]·H2O, Ca[Ti2(H2O)(HPO3)4]·H2O, and Ti(H2PO2)3: Solid-State Oxidation via Proton-Coupled Electron Transfer

2022 ◽  
Author(s):  
Ling-I Hung ◽  
Dai-Yi Hsieh ◽  
Tsung-Hsiu Hsieh ◽  
Pei-Lin Chen ◽  
Chia-Her Lin ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Solid State ◽  
Proton Coupled Electron Transfer

Solid-State Magnetic Switching Triggered by Proton-Coupled Electron-Transfer Assisted by Long-Distance Proton-Alkali Cation Transport

2014 ◽  
Vol 136 (17) ◽  
pp. 6231-6234 ◽  
Author(s):  
Pauline Higel ◽  
Françoise Villain ◽  
Michel Verdaguer ◽  
Eric Rivière ◽  
Anne Bleuzen
Keyword(s):  
Electron Transfer ◽  
Solid State ◽  
Cation Transport ◽  
Alkali Cation ◽  
Long Distance ◽  
Proton Coupled Electron Transfer ◽  
Magnetic Switching

Guanidines as Reagents in Proton-Coupled Electron-Transfer Reactions and Redox Catalysts

Synlett ◽  
2018 ◽  
Vol 29 (15) ◽  
pp. 1957-1977 ◽  
Author(s):  
Hans-Jörg Himmel
Keyword(s):  
Electron Transfer ◽  
Transfer Reactions ◽  
Redox Activity ◽  
Coupling Reactions ◽  
Proton Coupled Electron Transfer ◽  
Redox Catalysts ◽  
Dehydrogenative Coupling ◽  
Redox Active ◽  
Organic Electron ◽  
Donor Acceptor

Redox-active guanidines are ideal proton-coupled electron-transfer (PCET) reagents, since they combine a high Brønsted basicity with a low and tunable redox potential. In this article, the development of redox-active guanidines (especially guanidino-functionalized aromatics, GFAs) in the last ten years is summarized, and their properties compared to other organic Brønsted bases and organic electron donors. First, some applications in organic chemistry that purely use the redox activity (formation of organic donor–acceptor materials and photochemical reductive C–C coupling reactions) are presented. Then, reactions that involve both proton and electron transfer are reviewed. In stoichiometric reactions, redox-active guanidines are used for the dehydrogenative coupling of thiols and phosphanes. The first redox catalytic applications are discussed, using dioxygen as green oxidizing reagent.1 Introduction2 Redox-Active Amines and Guanidines3 Brønsted Basicity of Amines and Guanidines4 Variations of GFA Compounds5 GFA Compounds in Organic Donor–Acceptor Materials and as Reducing Reagents in Organic Synthesis6 Stoichiometric Dehydrogenative Coupling Reactions with Redox-Active Guanidines7 Guanidines as Redox Catalysts8 Conclusions and Outlook

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>

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