Molecular Engineering on Solvation Structure of Carbonate Electrolyte toward Durable Sodium Metal Battery at −40 °C

Carbonate electrolytes have excellent chemical stability and high salt solubility, which are ideally practical choice for achieving high-energy-density sodium (Na) metal battery at room temperature. However, their application at ultra-low temperature (−40 °C) is adversely affected by the instability of solid electrolyte interphase (SEI) formed by electrolyte decomposition and the difficulty of desolvation. Here, we designed a novel low-temperature carbonate electrolyte by molecular engineering on solvation structure. The calculations and experimental results demonstrate that ethylene sulfate (ES) reduces the sodium ion desolvation energy and promotes the forming of more inorganic substances on the Na surface, which promote ion migration and inhibit dendrite growth. At −40 °C, the Na||Na symmetric battery exhibits a stable cycle of 1500 hours, and the Na||Na₃V₂(PO₄)₃ (NVP) battery achieves 88.2 % capacity retention after 200 cycles.     

Murahashi Cross-Coupling at −78 °C: A One-Pot Procedure for Sequential C−C/C−C,C−C/C−N,and C−C/C−S Cross-Coupling of Bromo-Chloro-Arenes

The coupling of organolithium reagents, including strongly hindered examples, at cryogenic temperatures (as low as −78 °C) has been achieved with high-reactivity Pd-NHC catalysts. A temperature-dependent chemoselectivity trigger has been developed for the selective coupling of aryl bromides in the presence of chlorides. Building on this, a one-pot, sequential coupling strategy is presented for the rapid construction of advanced building blocks. Importantly, one-shot addition of alkyllithium compounds to Pd cross-coupling reactions has been achieved, eliminating the need for slow addition by syringe pump.     

The Dissociation Constant of Antimonic Acid at 10–40 °C

The hydrolytic behavior of antimonic acid, Sb(OH)₅^o, was experimentally investigated, at fixed temperatures within the range 10–40 °C, by both titration of dilute Na-antimonate solutions with HClO₄ and single-point pH measurements of diluted Sb(OH)₅^o solutions. The thermodynamic constants, K _a, for the reaction:

Phase Equilibria in the Ternary System Fe-Gd-Mo at 600 °C

 Phase equilibria in the ternary system Fe-Gd-Mo at 600 °C were determined. The phase composition for different element concentrations were quantitatively determined from the diffraction patterns by means of the multi-phase Rietveld-refinement as well as through evaluation of the microstructure images obtained by the scanning electron microscopy. Both methods are compared with each other with respect to their precision and limitations. The complete isothermal section at 600 °C includes one ternary phase τ (ThMn₁₂-type of structure), four pseudo-binary phases (Fe,Mo)₁₇Gd₂, (Fe,Mo)₂₃Gd₆, (Fe,Mo)₃Gd and (Fe,Mo)₂Gd and binary phases Fe₂Mo and μ-(Fe,Mo). The ternary phase τ forms the tie-lines with the solid solutions α-Fe, (Mo)-, Fe₂Mo and μ-(Fe,Mo) phases as well as with the pseudo-binary Fe-Gd compounds. Three phases (Fe,Mo)₂Gd, (Mo) and Gd coexist in a wide concentrations range. The homogeneity region of the ternary phase τ as well as the solubilities of the third element in the binary phases were determined.     

Ultra-stable Zinc Metal Anodes at −20 °C through Eutectic Solvation Sheath in Chlorine-functionalized Eutectic Electrolytes with 1,3-Dioxolane

The brain-storm of designing low-cost and commercialized eutectic electrolytes for zinc (Zn)-based electrochemical energy storage (ZEES) remains unresolved and attractive, especially when implementing it at low temperatures. Here, we report an appealing layout of advancing chlorine-functionalized eutectic (Cl-FE) electrolytes via exploiting Cl anion-induced eutectic interaction with Zn acetate solutions. This novel eutectic liquid shows high affinity to collaborate with 1,3-dioxolane (DOL) and is prone to constitute Cl-FE/DOL-based electrolytes with a unique inner/outer eutectic solvation sheath for the better regulation of Zn-solvating neighboring and reconstruction of H-bonding. The side reactions are effectively restricted on Zn anodes and a high Coulombic efficiency of 99.5 % can be achieved over 1000 cycles at −20 °C with Zn//Cu setups. By prototyping scale-up Zn-ion pouch cells using the optimal eutectic liquid of 3ZnOAc_1.2Cl_1.8-DOL, we obtain improved electrochemical properties at −20 °C with a high capacitance of 203.9 F g⁻¹ at 0.02 A g⁻¹ in a range of 0.20–1.90 V and long-term cycling ability with 95.3 % capacitance retention at 0.2 A g⁻¹ over 3,000 cycles. Overall, the proposal of ideal Cl-FE/DOL-based electrolytes guides the design of sub-zero and endurable aqueous ZEES devices and beyond.     

Polymerization and decomposition of terephthaloyl chloride and p-phenylenediamine at 500 °C

In order to synthesize the high temperature solid lubricating film by gas-phase polymerization at 500?°C with two kinds of gasified monomers for use in airplane and rocket engines, the polymerizing activity of terephthaloyl chloride (TPC) and p-phenylenediamine (PPD) at 500?°C and their polymerized product poly-p-phenyleneterephthamide (PPTA) as well as its decomposed solid residues were researched. It was proved by FT-IR and ¹HNMR on the solid residues after the 10?min experiment of the both monomers in muffle furnace at 500?°C and PPTA synthesized by conventional method that at 500?°C the polymerization tendency of these monomers should trump their decomposition tendency. The solid residues after the 10?min experiment mainly consisted of polymerized products which would decline as the experimental period increases, while the content of decomposed and carbonized products would raise. FT-IR and elemental analysis revealed a similar structure of the solid residues after the both monomers or PPTA calcined for 60?min at 500?°C, which further demonstrated the polymerized products would degrade, decompose and carbonize after the prophase polymerization. Finally, effects of experimental temperature and monomers molar ratio on amounts and structures of the solid residues were discussed to propose preliminary mechanisms of polymerization and decomposition.     

Cycling a Lithium Metal Anode at 90 °C in a Liquid Electrolyte

Stable operation at elevated temperature is necessary for lithium metal anode. However, Li metal anode generally has poor performance and safety concerns at high temperature (>55 °C) owing to the thermal instability of the electrolyte and solid electrolyte interphase in a routine liquid electrolyte. Herein a Li metal anode working at an elevated temperature (90 °C) is demonstrated in a thermotolerant electrolyte. In a Li|LiFePO₄ battery working at 90 °C, the anode undergoes 100 cycles compared with 10 cycles in a practical carbonate electrolyte. During the formation of the solid electrolyte interphase, independent and incomplete decomposition of Li salts and solvents aggravate. Some unstable intermediates emerge at 90 °C, degenerating the uniformity of Li deposition. This work not only demonstrates a working Li metal anode at 90 °C, but also provides fundamental understanding of solid electrolyte interphase and Li deposition at elevated temperature for rechargeable batteries.     

Metal-Free Intermolecular C−H Borylation of N-Heterocycles at B−B Multiple Bonds

Carbene-stabilized diborynes of the form LBBL (L=N-heterocyclic carbene (NHC) or cyclic alkyl(amino)carbene (CAAC)) induce rapid, high yielding, intermolecular ortho-C−H borylation at N-heterocycles at room temperature. A simple pyridyldiborene is formed when an NHC-stabilized diboryne is combined with pyridine, while a CAAC-stabilized diboryne leads to activation of two pyridine molecules to give a tricyclic alkylideneborane, which can be forced to undergo a further H-shift resulting in a zwitterionic, doubly benzo-fused 1,3,2,5-diazadiborinine by heating. Use of the extended N-heteroaromatic quinoline leads to a borylmethyleneborane under mild conditions via an unprecedented boron-carbon exchange process.     

New Physico-Chemical Properties of Extremely Diluted Solutions. Electromotive Force Measurements of Galvanic Cells Sensible to the Activity of NaCl at 25 °C

The mean ionic activity coefficients for sodium chloride in the NaCl+H₂O binary system have been experimentally determined at 298.15 K, from electromotive force measurements of the cell:

Zinc–Organic Battery with a Wide Operation-Temperature Window from −70 to 150 °C

Aqueous zinc (Zn) batteries have been considered as promising candidates for grid-scale energy storage. However, their cycle stability is generally limited by the structure collapse of cathode materials and dendrite formation coupled with undesired hydrogen evolution on the Zn anode. Herein we propose a zinc–organic battery with a phenanthrenequinone macrocyclic trimer (PQ-MCT) cathode, a zinc-foil anode, and a non-aqueous electrolyte of a N,N-dimethylformamide (DMF) solution containing Zn²⁺. The non-aqueous nature of the system and the formation of a Zn²⁺–DMF complex can efficiently eliminate undesired hydrogen evolution and dendrite growth on the Zn anode, respectively. Furthermore, the organic cathode can store Zn²⁺ ions through a reversible coordination reaction with fast kinetics. Therefore, this battery can be cycled 20 000 times with negligible capacity fading. Surprisingly, this battery can even be operated in a wide temperature range from −70 to 150 °C.     

Transition Metal-Free Aromatic C−H,C−N,C−S and C−O Borylation

Aromatic organoboron compounds are highly valuable building blocks in organic chemistry. They were mainly synthesized through aromatic C−H and C−Het borylation, in which transition metal-catalysis dominate. In the past decade, with increasing attention to sustainable chemistry, numerous transition metal-free C−H and C−Het borylation transformations have been developed and emerged as efficient methods towards the synthesis of aromatic organoboron compounds. This account mainly focuses on recent advances in transition metal-free aromatic C−H, C−N, C−S, and C−O borylation transformations and provides insights to where further developments are required.     

Reversible Addition of Carbon Dioxide to Main Group Metal Complexes at Temperatures about 0 °C

The reaction of dialane [LAl-AlL] ( 1 ; L=dianion of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, dpp-bian) with carbon dioxide results in two different products depending on solvent. In toluene at temperatures of about 0 °C, the reaction gives cycloadduct [L(CO₂)Al-Al(O₂C)L] ( 2 ), whereas in diethyl ether, the reaction affords oxo-bridged carbamato derivative [L(CO₂)(Et₂O)Al(μ-O)AlL] ( 3 ). The DFT and QTAIM calculations provide reasonable explanations for the reversible formation of complex 2 in the course of two subsequent (2+4) cycloaddition reactions. Consecutive transition states with low activation barriers were revealed. Also, the DFT study demonstrated a crucial effect of diethyl ether coordination to aluminium on the reaction of dialane 1 with CO₂. The optimized structures of key intermediates were obtained for the reactions in the presence of Et₂O; calculated thermodynamic parameters unambiguously testify the irreversible formation of the product 3 .     

Acridinium Ion Ionization at Elevated Temperatures and Pressures to 200 °C and 2000 bar

The temperature and pressure dependences of pK for acridine ion ionization were determined up to 200 °C and 2000 bar. The UV-Vis measurements at high temperatures and pressures were conducted in flow-through spectrophotometric cells. Two independent series of experiment were performed: one in a Ti–Pd cell with silica quartz windows for measurements in the ultraviolet region, and another in a Ti grade 5 cell with sapphire windows for use at higher pressures, which permitted measurements in the visible region. Combined chemometric and thermodynamic analyses of the UV-Vis spectrophotometric data were used to extract the ionization constants as well as the changes in molar volume ΔV° for acridine protonation as functions of temperature and pressure. Values of pK decrease from 5.52 to 3.74 with increasing temperature from 25 to 200 °C at saturated water-vapor pressure. The pressure dependence of acridinium ion ionization is small (e.g., pK=5.5 at 25 °C and 2000 bar) and is characterized by positive ΔV°≤1.2 cm³⋅mol⁻¹, which is not surprising for this type of isocoulombic reaction involving a large molecule.     

Instability of the DNPH-formaldehyde derivative in the certified reference material BCR-551 stored at −70 °C but not at −20 °C

During the post-certification stability monitoring of the certified reference material (CRM) BCR-551 (DNPH derivatives dissolved in acetonitrile), a decreased concentration of one of the analytes of this CRM, the DNPH-formaldehyde derivative, was detected in reference samples (stored at ?70 °C), while the concentration of normal “on-sale” samples (stored at ?20 °C) remained stable. This behaviour is contrary to the expectation of better stability at lower temperatures. Apparently, the DNPH-formaldehyde derivative reacts with dinitrophenylhydrazine (DNPH) remaining from the synthesis phase to produce two new substances. These substances have been identified as C₁₃H₁₂N₈O₈ (substance 1) and C₂₀H₁₆N₁₂O₁₂ (substance 2) which, based on their structure, are suggested to be produced consecutively: DNPH + DNPH-formaldehyde derivative → substance 1 and substance 1 + DNPH-formaldehyde derivative → substance 2. Since acetonitrile freezes at ?45 °C, reference samples are frozen at ?70 °C, while normal samples are still liquid at ?20 °C. We believe that this leads to a cryo-concentration of the solutes above the eutectic point and thus to an increased reaction rate in the reference samples. This case demonstrates that care should be taken when extrapolating stability results towards conditions that never have been tested, especially if phase transitions are involved, even at temperature as low as ?70 °C. Furthermore, a slower degradation rate at lower temperatures can be overcompensated by a higher concentration due to cryo-concentration above the eutectic temperature.     

Photo-Induced Ruthenium-Catalyzed C−H Benzylations and Allylations at Room Temperature

The ruthenium-catalyzed synthesis of diarylmethane compounds was realized under exceedingly mild photoredox conditions without the use of exogenous photocatalysts. The versatility and robustness of the ruthenium-catalyzed C−H benzylation was reflected by an ample scope, including multifold C−H functionalizations, as well as transformable pyrazoles, imidates and sensitive nucleosides. Mechanistic studies were indicative of a photoactive cyclometalated ruthenium complex, which also enabled versatile C−H allylations.     

Spectrophotometric Determination of the Ionization Constants of Aqueous Nitrophenols at Temperatures up to 225 °C

The UV-visible spectra of aqueous o-, m-, and p-nitrophenol were measured as a function of pH at temperatures from 50 to 225 °C at a pressure of 7 MPa. These were used to determine equilibrium constants for the acid ionization reaction of each isomer. The new results were combined with literature data on the ionization of nitrophenols and used for parameter optimization in the thermodynamic model of Marshall and Franck (J. Phys. Chem. Ref. Data 10:295–304, [1981]), to describe the dependence of ionization properties on temperature and pressure. The model yields predictions of the ionization constants for o-, m-, and p-nitrophenol, log ₁₀ K _a, to at least 250 °C and 20 MPa with an estimated uncertainty in log ₁₀ K _a of less than ±0.06.     

The ionization of sulfurous acid in Na−Mg−Cl solutions at 25°C

The stoichiometric pK ₁ ^* and pK ₂ ^* for the ionization of sulfurous acid has been determined from emf measurements in NaCl solutions with varying concentrations of added MgCl₂ (m=0.1, 0.2 and 0.3) from I=0.5 to 6.0 molal at 25°C. These experimental results have been treated using both the ion pairing and Pitzer's specific ion-interaction models. The Pitzer parameters for the interaction of Mg²⁺ with SO₂ and HSO ₃ ^– yielded =0.085±0.004, ⁽⁰⁾ = 0.35±0.02, ⁽¹⁾ = 1.2±0.04, and C = –0.072±0.007. The Pitzer parameters ⁽⁰) = –2.8±0.4, ⁽¹⁾ = 12.9±2.9 and ⁽²⁾ = –2071±57 have been determined for the interactions of Mg²⁺ with SO ₃ ^2– . The calculated values of pK ₁ ^* and pK ₂ ^* using Pitzer's equations reproduce the measured values to within ±0.04 pK units. The ion pairing model with log K_MgSO3=2.36±0.02 and log_MgSO3 = 0.1021, reproduces the experimental values of pK ₂ ^* to ±0.01. These results demonstrate that treating the data by considering the formation of MgSO₃ yields a better fit of the experimental measurements with fewer adjustable parameters. With these derived coefficients obtained from the Pitzer equations and the ion pairing model, it is possible to make reliable estimates of the activity coefficients of HSO ₃ ^– and SO ₃ ^2– in seawater, brines and marine aerosols containing Mg²⁺ ions.     

Construction of Rich Conductive Pathways from Bottom to Top: A Highly Efficient Charge-Transfer System Used in Durable Li/Na-Ion Batteries at −20 °C

The construction of potential electrode materials with wide temperature property for high-energy-density secondary batteries has attracted great interest in recent years. Herein, a hybrid electrode, consisting of a nitrogen-doped carbon/α-MnS/flake graphite composite (α-MnS@N-C/FG), is prepared through a post-sulfurization route. In the α-MnS@N-C/FG composite, α-MnS nanoparticles wrapped by the N−C layer are uniformly embedded onto FG, forming a novel nanofoam structure. The as-obtained α-MnS@N-C/FG shows excellent lithium/sodium storage performance, with a specific capacity of 712 mA h g⁻¹ in the 700th cycle at 1.0 A g⁻¹ or 186.4 mA h g⁻¹ in the 100th cycle at 100 mA g⁻¹ using lithium or sodium foil as the counter electrode, respectively. Moreover, even operated at −20 °C, the α-MnS@N-C/FG can still attain a high specific capacity of 350 mA h g⁻¹ after 50 cycles at 100mA g⁻¹ for LIBs. This exceptional electrochemical response is attributed to the synergetic effect of the smart design of a hybrid nanofoam structure, in which the FG skeleton and N-C coating layer can significantly enhance the conductivity of the whole electrode from bottom to top. Accordingly, the enhanced redox kinetics endow the electrode with pseudocapacitive-dominated electrochemical behavior, leading to fast electrode reactions and robust structural stability in the whole electrode.     

Biocatalytic Intramolecular C−H aminations via Engineered Heme Proteins: Full Reaction Pathways and Axial Ligand Effects

Engineered heme protein biocatalysts provide an efficient and sustainable approach to develop amine-containing compounds through C−H amination. A quantum chemical study to reveal the complete heme catalyzed intramolecular C−H amination pathway and protein axial ligand effect was reported, using reactions of an experimentally used arylsulfonylazide with hemes containing L=none, SH⁻, MeO⁻, and MeOH to simulate no axial ligand, negatively charged Cys and Ser ligands, and a neutral ligand for comparison. Nitrene formation was found as the overall rate-determining step (RDS) and the catalyst with Ser ligand has the best reactivity, consistent with experimental reports. Both RDS and non-RDS (nitrene transfer) transition states follow the barrier trend of MeO⁻<SH⁻<MeOH<None due to the charge donation capability of the axial ligand to influence the key charge transfer process as the electronic driving forces. Results also provide new ideas for future biocatalyst design with enhanced reactivities.     

Magnetische Kernresonanzuntersuchungen an Ti−C−H-Legierungen

Ohne ZusammenfassungMit 4 Abbildungen