We report on the structures of Li-ion complexes in salt-concentrated aqueous electrolytes based on lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), particularly focusing on the anion coordination behavior of the ion-pair complexes in the high concentration region c > 3.0 mol dm. Quantitative data analysis of the Raman spectra revealed the following. (1) Li ions do not coordinate with TFSA anions at lower c (<3.0 mol dm) to exist as ion pair-free ions. (2) In the concentrated region (c = 3.0 - 4.0 mol dm), the TFSA anions coordinate as monodentate ligands (mono-TFSA) with Li ions to form ion-pair complexes and coexist with free TFSA in the bulk. (3) Further increasing the c (4.0 - 5.2 mol dm) results in both monodentate and bidentate coordination (bi-TFSA) modes of TFSA anions to Li ions, yielding complicated ion-pair complexes in the first coordination sphere. The Walden plots, based on ionic conductivity and viscosity data, implied that the ion-conducting mechanism in the highly salt-concentrated region was considerably different from that in the dilute region (i.e., vehicle mechanism).
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http://dx.doi.org/10.2116/analsci.18P407 | DOI Listing |
Proc Natl Acad Sci U S A
January 2025
Department of Physics, The Hong Kong University of Science and Technology, Hong Kong, China.
Dissolution of CO in water followed by the subsequent hydrolysis reactions is of great importance to the global carbon cycle, and carbon capture and storage. Despite numerous previous studies, the reactions are still not fully understood at the atomistic scale. Here, we combined ab initio molecular dynamics (AIMD) simulations with Markov state models to elucidate the reaction mechanisms and kinetics of CO in supercritical water both in the bulk and nanoconfined states.
View Article and Find Full Text PDFChem Sci
January 2025
Materials Science and Engineering Program, The Graduate School, Florida State University 2005 Levy Ave. Tallahassee FL 32310 USA
Solid electrolytes (SEs) are crucial for advancing next-generation rechargeable battery technologies, but their commercial viability is partially limited by expensive precursors, unscalable synthesis, or low ionic conductivity. Lithium tetrahaloaluminates offer an economical option but exhibit low Li conductivities with high activation energy barriers. This study reports the synthesis of lithium aluminum chalcohalide (LiAlClS) using inexpensive precursors one-step mechanochemical milling.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Sorbonne Université, CNRS, Physicochimie des Électrolytes et Nanosystèmes Interfaciaux, F-75005 Paris, France.
We developed a systematic polarizable force field for molten trivalent rare-earth chlorides, from lanthanum to europium, based on first-principle calculations. The proposed model was employed to investigate the local structure and physicochemical properties of pure molten salts and their mixtures with sodium chloride. We computed densities, heat capacities, surface tensions, viscosities, and diffusion coefficients and disclosed their evolution along the lanthanide series, filling the gaps for poorly studied elements, such as promethium and europium.
View Article and Find Full Text PDFMikrochim Acta
January 2025
Jiaxing Key Laboratory of Molecular Recognition and Sensing, College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, 314001, People's Republic of China.
A novel Ru-FeO nanozyme with enhanced peroxidase-like (POD-like) activity was synthesized through a hydrothermal method. Ru-FeO nanozyme was effectively utilized for the detection of thiophanate-methyl (TM) using a colorimetric technique. The POD-like activity of Ru-FeO was found to be superior compared to FeO, Rh-FeO, and Pd-FeO.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China.
Intensified host-guest electronic interplay within stable metal-organic cages (MOCs) presents great opportunities for applications in stimuli response and photocatalysis. Zr-MOCs represent a type of robust discrete hosts for such a design, but their host-guest chemistry in solution is hampered by the limited solubility. Here, by using pyridinium-derived cationic ligands with tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (BAr) as solubilizing counteranions, we report the preparation of soluble Zr-MOCs of different shapes (1-4) that are otherwise inaccessible through a conventional method.
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