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MP2/aug-cc-pVTZ calculations were performed on systems containing a proton or a lithium cation located between two π-electron systems or between π-electron and σ-electron units. The proton or the lithium cation attached to the acetylene or its derivative may be treated as the Lewis acid unit while the remaining part of the complex, the π-electron species or the dihydrogen, act as the Lewis base through their π-electrons or σ-electrons, respectively. The complexes analysed here are linked by the π⋅⋅⋅H /Li ⋅⋅⋅π and π⋅⋅⋅H /Li ⋅⋅⋅σ interactions. It is discussed whether these interactions are classified as hydrogen and lithium bonds. Therefore, different definitions of the latter interactions are presented. The Electron Localization Function (ELF) and the Natural Bond Orbital (NBO) approaches were applied to analyse the above-mentioned complexes. The unique properties of interactions with the proton and with the lithium cation that occur in complexes analysed here are described.
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http://dx.doi.org/10.1002/cphc.202200273 | DOI Listing |
J Am Chem Soc
December 2024
Department of Chemistry, Hanyang University, Seoul 04763, Republic of Korea.
The electrochemical nitrate reduction reaction (NORR) involves multiple hydrogenation and deoxygenation steps, which compete with the hydrogen evolution reaction (HER). Therefore, NORR driven in acidic media is challenging in spite of advantageous fast hydrogen transfers in its elementary steps. The findings presented in this article first demonstrate that the NORR is significantly activated even in acidic lithium nitrate solutions at LiNO concentrations exceeding 6 m on a Pt electrode (the highly effective catalyst for HER) by the formation of a "hydronium-in-salt" electrolyte (HISE), a new type of aqueous high concentration salt electrolyte.
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December 2024
Division of Neurology, Department of Clinical Sciences Lund, Lund University, Box 117, 22100, Lund, Sweden.
Drug-induced cognitive impairment (DICI) is a well-established, yet under-recognised, complication of many types of pharmacological treatment. While there is a large body of scientific literature on DICI, most papers are about drug-induced dementia in the elderly and one specific drug class. However, DICI also comprises subclinical symptoms, domain-specific forms of cognitive impairment as well as mild cognitive impairment (MCI), and delirium.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
NUAA: Nanjing University of Aeronautics and Astronautics, Material Science and Technology, CHINA.
Proton electrochemistry holds eminent potential for developing high capacity and rate energy storage devices in the post-lithium era. However, the decomposition of water in acidic aqueous electrolytes causes electrode corrosion, leading to capacity fading. Herein, we report a judicious design of molecular micellar aggregates as non-aqueous electrolytes for stable and high-voltage electrochemical proton storage.
View Article and Find Full Text PDFSmall
December 2024
College of Materials and Chemistry, China Jiliang University, Hangzhou, 310018, China.
Biomass with naturally ion-conducting segments (e.g., hydroxyl) holds promise for sustainable batteries.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2024
Department of Chemistry-Ångström Laboratory, Uppsala University, Lägerhyddsvägen 1, P.O. Box 538, 75121 Uppsala, Sweden.
Water-in-salt electrolytes with a surprisingly large electrochemical stability window of ≤3 V have revived interest in aqueous electrolytes for rechargeable lithium-ion batteries. However, recent reports of acidic pH measured in concentrated electrolyte solutions appear to be in contradiction with the suppressed activity of the hydrogen evolution reaction (HER). Therefore, the fundamental thermodynamics of proton reactivity in concentrated electrolyte solutions remains elusive.
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