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The introduction of allyl fluorides as alternative electrophiles in asymmetric allylic alkylation reactions has recently attracted significant interest. Despite the intrinsic thermodynamically demanding C–F bond-cleavage event, the fluorophilic nature of the silicon atom is key in assisting the activation and cleavage of the allylic C–F bond. Thus, the use of silylated compounds as unconventional nucleophiles, together with the Lewis basicity of fluorine when acting as a leaving group, enables the development of innovative chemical transformations within mild and selective catalytic schemes. This Synpacts article summarizes the diverse defluorinative asymmetric allylic alkylations with allyl fluorides reported to date under both chiral Lewis base and transition-metal catalysis. [ABSTRACT FROM AUTHOR]

An innovative approach to electrolyte engineering in carbonate electrolytes is introduced by incorporating high donor number dual anion additives into the conventional electrolyte system (1 M NaPF6 EC:PC). The active engagement of anions in the primary solvation shell effectively hinders the reduction of solvent molecules by reducing the Lowest Unoccupied Molecular Orbital (LUMO) of Na+‐solvent‐anion complex as compared to the LUMO of pure solvents or Na+‐solvent complex. The participation of anions leads to the formation of a thinner and an inorganic‐rich Solid Electrolyte Interphase on the hard carbon anode enhancing Initial Coulombic Efficiency and significantly improving its kinetics. Moreover, the system with dual anion additives exhibits oxidative stability up to 4.5 V, effectively mitigating the undesired side reactions at high voltage operation of the layered sodium nickel manganese oxide cathode. The addition of dual anion additives proves instrumental in suppressing structural degradation and transition metal dissolution during the long cycling performance of the layered oxide cathode in a sodium‐ion full cell. The synergistic effects of this dual anion additive added electrolyte on both the anode and the cathode ultimately ensured prolonged cycling of the sodium‐ion full cell. The electrolyte engineering approach outlined in this study opens the door to advancing next‐generation high‐voltage sodium batteries. [ABSTRACT FROM AUTHOR]

The utilization of hybrid aqueous electrolytes has significantly broadened the electrochemical and temperature ranges of aqueous batteries, such as aqueous zinc and lithium‐ion batteries, but the design principles for extreme operating conditions remain poorly understood. Here, we systematically unveil the ternary interaction involving salt‐water‐organic co‐solvents and its intricate impacts on both the atomic‐level and macroscopic structural features of the hybrid electrolytes. This highlights a distinct category of micelle‐like structure electrolytes featuring organic‐enriched phases and nanosized aqueous electrolyte aggregates, enabled by appropriate low donor number co‐solvents and amphiphilic anions. Remarkably, the electrolyte enables exceptional high solubility, accommodating up to 29.8 m zinc triflate within aqueous micelles. This configuration maintains an intra‐micellar salt‐in‐water setup, allowing for a broad electrochemical window (up to 3.86 V), low viscosity, and state‐of‐the‐art ultralow‐temperature zinc ion conductivity (1.58 mS cm−1 at −80 °C). Building upon the unique nature of the inhomogeneous localized aggregates, this micelle‐like electrolyte facilitates dendrite‐free Zn plating/stripping, even at −80 °C. The assembled Zn||PANI battery showcases an impressive capacity of 71.8 mAh g−1 and an extended lifespan of over 3000 cycles at −80 °C. This study opens up a promising approach in electrolyte design that transcends conventional local atomic solvation structures, broadening the water‐in‐salt electrolyte concept. [ABSTRACT FROM AUTHOR]

The reaction mechanism for the formation of the pseudo‐silaazatriene 1 (LN(SiMe3)2−Si−N−Si(L)NSiMe3; L=PhC−(NtBu)2) by the reaction of 1 equivalent of bis‐silylene (LSi−SiL; L=PhC(NtBu)2) with 3 equivalents of azide Me3SiN3 has been explored at M06/def2‐TZVPP//BP86‐D3(BJ)/def2‐TZVPP level of theory. The reaction mechanism is guided by the high Lewis basicity of the silicon lone pair and the high Lewis acidic character of Si−N bonds, as well as by the high tendency to eliminate N2 from Me3SiN3. The first step of the reaction is the formation of [3+1] cycloaddition product (I1) by the synergetic interactions of the lone pair on the silylene silicon with the π* molecular orbital of Me3SiN3 which is majorly localized on the terminal nitrogen atom, and the donation of the σ‐type lone pair on the nitrogen atom connected to the SiMe3 group with the Si−N σ* orbital on silylene. The elimination of N2 from I1 results in the formation of pseudo‐silaimine intermediate I2 having a dicoordinated, monovalent nitrogen atom. The most favourable pathway involves the second addition of Me3SiN3 followed by N2 elimination resulting bis‐silaimine intermediate I4‐P2. The highly reactive lone pair on the dicoordinated, monovalent nitrogen atom can be coordinated to the Si−N σ* MO of the second silylene moiety resulting in Si−N bond formation and Si−Si bond cleavage. This step is similar to the SN2′ reaction where the incoming nucleophile and the leaving group are on the same side resulting in the formation of silaimine I5. Further, the [3+1] cycloaddition of one more molecule of Me3SiN3 followed by N2 elimination results in the formation of silaimine intermediate I7. I7 undergoes 1,3‐silyl migration leading to the final product 1. The lone pairs on di‐ and tricoordinated nitrogen centres of all the intermediates are stabilized by hyperconjugative interactions. The delocalized hyperconjugative interaction stabilizes the lone pairs in 1. [ABSTRACT FROM AUTHOR]

The Lewis basicity of a μ3-oxo ligand for (μ3-O)[Rh(cod)]3(μ4-O)M (cod = 1,5-cyclooctadiene) complexes was controllable by metal species on the μ4-oxo ligand locating at the opposite site of the μ3-oxo ligand. Coordination of the μ3-oxo ligand of [(μ3-O){Rh(cod)}3(μ4-O){Au(PPh3)}][BF4] (1) to [Au(PPh3)]+ indicated sufficient Lewis basicity of the μ3-oxo ligand in 1 to form [{(Ph3P)Au}(μ3-O){Rh(cod)}3(μ4-O){Au(PPh3)}][BF4] (2). In contrast, the addition of Li+ to 1 induced elimination of the originally coordinated [Au(PPh3)]+ due to the weak Lewis basicity of the μ3-oxo ligand for (μ3-O){Rh(cod)}3(μ4-O)Li(THF)3, in which a pentanuclear species, [{(Ph3P)Au}(μ3-O){Rh(cod)}3(μ4-O){Li(THF)3}][BF4] (3), was assumed to be generated in situ before the dissociation of [Au(PPh3)]+. [ABSTRACT FROM AUTHOR]

Hexadentate poly-Lewis acids (PLA) based on the bowl-shaped tribenzotriquinacene (TBTQ) have been synthesised. The introduction of three n-propyl groups into the benzhydrylic positions of the TBTQ backbone has significantly increased the solubility of the subsequently derived compounds. Semi-flexible PLAs containing boron and aluminium were obtained by hydrometallation of the corresponding 2,3,6,7,10,11-hexaalkynyl-TBTQ. Other rigid hexadentate PLAs were synthesised by stannylation of the corresponding alkyne units with Me3SnNMe2 followed by tin-element exchange reactions. The Lewis acidity of these PLAs was investigated in host–guest experiments with pyridine. Further experiments with bidentate bases showed correlations between their flexibility, their Lewis basicity and the complexation behaviour towards the synthesised PLAs. Addition of bis((dimethylphosphino)methyl)dimethylsilane (BisPhos) to solutions of the rigid alkynyl PLAs led to the formation of 3 : 1 adducts. Single crystal X-ray diffraction was used to further elucidate the host–guest connectivtiy. In addition, a sixfold pnictogen-bonding donor was synthesised by tin-antimony exchange. [ABSTRACT FROM AUTHOR]

The electrolytes for lithium metal batteries (LMBs) are plagued by a low Li+ transference number (T+) of conventional lithium salts and inability to form a stable solid electrolyte interphase (SEI). Here, we synthesized a self‐folded lithium salt, lithium 2‐[2‐(2‐methoxy ethoxy)ethoxy]ethanesulfonyl(trifluoromethanesulfonyl) imide (LiETFSI), and comparatively studied with its structure analogue, lithium 1,1,1‐trifluoro‐N‐[2‐[2‐(2‐methoxyethoxy)ethoxy)]ethyl]methanesulfonamide (LiFEA). The special anion chemistry imparts the following new characteristics: i) In both LiFEA and LiETFSI, the ethylene oxide moiety efficiently captures Li+, resulting in a self‐folded structure and high T+ around 0.8. ii) For LiFEA, a Li−N bond (2.069 Å) is revealed by single crystal X‐ray diffraction, indicating that the FEA anion possesses a high donor number (DN) and thus an intensive interphase "self‐cleaning" function for an ultra‐thin and compact SEI. iii) Starting from LiFEA, an electron‐withdrawing sulfone group is introduced near the N atom. The distance of Li−N is tuned from 2.069 Å in LiFEA to 4.367 Å in LiETFSI. This alteration enhances ionic separation, achieves a more balanced DN, and tunes the self‐cleaning intensity for a reinforced SEI. Consequently, the fast charging/discharging capability of LMBs is progressively improved. This rationally tuned anion chemistry reshapes the interactions among Li+, anions, and solvents, presenting new prospects for advanced LMBs. [ABSTRACT FROM AUTHOR]

For the lithium (Li) metal anode, constructing a strong and durable protective layer with lithium‐ion permeability is crucial, especially in high donor number (DN) solvent system. High DN solvent‐based electrolytes can support both higher capacity and lower charge overpotential in the rechargeable lithium–oxygen batteries (LOBs). However, Li anodes in high DN solvent system suffer from severe corrosion and uncontrolled dendrite growth due to the unstable solid‐electrolyte interphase (SEI). Typically, this interface is formed in situ through electrochemical processes with complicated component and spatial distribution. Here, a functional molecule is introduced to construct an ion‐wall (IW) on Li surface by prechemical sequential reactions (p‐CSRs), through which the crystalline nanoparticles as bricks and amorphous hybrid compounds as the mortar can be produced to build such a "wall." Different from the conventional SEI, this wall is not only compact and uniform, but also possess high strength, excellent passivation properties and high ionic conductivity. With these properties, the IW could suppress Li dendrites and inhabit the side reaction, supporting highly reversible Li plating/stripping behavior in high DN solvent system. As a result, the cycle stability of LOBs based on the IW protected Li anode is significantly improved. [ABSTRACT FROM AUTHOR]

The use of experimental parameters to quantify solvent properties, for example in linear free energy relationships, is well established and several scales of solvent acidity, basicity and polarity/polarizability have been developed. The success of this approach raises questions of which molecular properties contribute to particular solvent parameters and whether these contributions are found in all parameters representing a particular solvent property. In the present study, Catalan's hydrogen bond basicity and acidity parameters, SB and SA, and Gutmann's acceptor number, AN, a measure of a solvent's Lewis acidity, are correlated with molecular properties derived from computational chemistry. The results are compared with the results of similar correlations with Kamlet and Taft's β and α Solvent Scales, Gutmann's donor number DN) and Abraham's B and A solute scales. The results show that measures of solvent basicity, SB, β and DN all correlate strongly with the partial charge on the most negative atom in the solvent molecule and the energy of the donor orbital and, in all cases, the parameter values for hydrogen-bonded solvents are anomalous. Abraham's B, a measure of solute hydrogen basicity, depends only on the partial charge on the most negative atom and there is no anomaly in the values for solutes that, in the pure state, form hydrogen-bonded liquids. Similarly, all measures of solvent acidity, SA, α and AN, and Abraham's A, a measure of solute hydrogen bond acidity, depend on the partial charge on the most positive hydrogen on the molecule. [ABSTRACT FROM AUTHOR]

The deep separation between In(III) and Fe(III) ions is considered as an important technological challenge in the engineering fields. The In(III) ions are closer to the soft acid in terms of Lewis acidity due to the smaller polarizability and greater deformability than the Fe(III) ions, which facilitates the possibility of separating them. Herein, the Lewis basicity of the N‐containing adsorption sites is regulated by the fluorine‐containing group to better match with the In(III) ions rather than Fe(III) ions, causing a significant discrepancy in the binding of the adsorption sites to them. Moreover, targeted programmed desorption techniques based on the potential energy differences of the adsorption sites can achieve the deep separation of In(III) and Fe(III) ions, and reach an exceptional concentration of 20.7 mmol L−1 for In(III) ions in the initial desorption solution with extremely high mass ratio (mIn/mFe = 151.7). This work provides a novel technique for in‐depth separation of In(III) and Fe(III) ions from mixed systems, and a new strategy for separating metal ions with similar or close properties. [ABSTRACT FROM AUTHOR]

We demonstrate herein a reported syntheses pathway for form unsubstituted boron subnaphthalocyanines (BsubNcs) since their discovery in 1995 and to avoid random bay-position halogenation. This was achieved through the use of triphenyl borates as the macrocyclic templating reagent avoiding the formation of random bay-position halogenated BsubNc by-products. We also outline a method to screen boron templating reagents by computing their Lewis acidity using the fluoride ion affinity method as well as the screening of the macrocyclic precursor by determining its Lewis basicity using a boron trifluoride affinity scale of various organic macrocyclic precursors in order to balance these parameters to enable macrocycle formation. We find that a balancing of these parameters enabled multiple methods for the synthesis of unsubstituted BsubNc. For this study, we isolated the axially fluorinated and axially pentafluorophenoxylated BsubNcs and characterize their photophysical and electrochemical properties as there was no random bay-position substitutions. For this study, we also demonstrated as a 'part 2' the versatility in the synthetic methods developed through the synthesis of boron subphthalocyanines (BsubPcs), other BsubNcs and a hybrid materials of BsubPc + BsubNc called Bsub(Pc3-p + Ncp). We also explored an industrially relevant synthesis method of triphenyl borates and found it to be successful in the processes outlined herein providing a potential route to improving the sustainability of this class of triphenyl borate materials. [ABSTRACT FROM AUTHOR]

The interplay of two proximate gallium centres equips the bimetallic complex CyL2Ga2 (1, CyL2 = 1,2-trans-Cy[NC(Me)C(H)C(Me)N(Dip)]2, Dip = 2,6-i-Pr2C6H3) with increased Lewis basicity and higher reducing power compared to the monometallic gallanediyl LGa (2, L = HC[MeCN(Dip)]2) as evidenced by cross-over experiments. Quantum chemical calculations were employed to support the experimental findings. [ABSTRACT FROM AUTHOR]

The interplay of two proximate gallium centres equips the bimetallic complex CyL2Ga2 (1, CyL2 = 1,2-trans-Cy[NC(Me)C(H)C(Me)N(Dip)]2, Dip = 2,6-i-Pr2C6H3) with increased Lewis basicity and higher reducing power compared to the monometallic gallanediyl LGa (2, L = HC[MeCN(Dip)]2) as evidenced by cross-over experiments. Quantum chemical calculations were employed to support the experimental findings. [ABSTRACT FROM AUTHOR]

SrO has attracted attention for its use as a heterogeneous catalyst in producing biodiesel from transesterification owing to its high alkaline character and low solubility in methanol. In studies conducted in this decade, reaction conditions such as the methanol–oil molar ratio, reaction time, catalyst loading and temperature have been optimized in these systems. Furthermore, several works have been carried out to improve the physicochemical properties and increase the leaching resistance of this material. Thus, the new trends in using SrO in transesterification reactions are that this oxide should be supported or combined with Al2O3, TiO2, ZrO2, or Fe2O3, CaO, metal–organic frameworks, zeolites or La2O3. It has been observed that strontium can form mixed crystalline phases with these oxides by increasing the (M2+O2−) pairs and Lewis basicity of the oxygens, resulting in increased basicity and catalytic activity. Moreover, the transition metal oxides may provide Lewis acidity. Hence, these strontium‐containing catalytic systems have demonstrated a bifunctionality that can perform esterification and transesterification reactions at the same time. In addition, the combination of these oxides decreases the leaching of the catalyst. Other materials such as metal–organic frameworks, zeolites, and La2O3 have been studied as SrO supports, showing that they can be used in oil transesterification reactions. [ABSTRACT FROM AUTHOR]

Ether‐based electrolytes have good compatibility for lithium metal, which is widely used in lithium metal batteries (LMBs). However, the electrolyte is not suitable for high voltage (>4.0 V) due to its poor anti‐oxidation behavior. Herein, an anion chemistry strategy is designed for a typical 1,2‐dimethoxyethane (DME)‐based electrolyte with 1 m lithium bis(fluorosulfonyl)imide (LiFSI), by using nitrate anion (NO3−) with a high donor number (DN) value to regulate the coordination of DME and FSI–. It is evidenced that the interaction between them is weakened due to the competitive advantage of NO3−, therefore a weakly solvating electrolyte is achieved. It promotes the formation of an inorganic‐rich passivation layer on the cathode and facilitates the de‐solvation process, thus it is suitable for high voltage even at 4.5 V. The anion‐regulated weakly solvating electrolyte (ARWSE) designed here is different from the high‐concentration electrolyte (HCE), localized HCE, and WSE which are of high cost and complexity. The ARWSE is demonstrated to be an adjustable electrolyte system, effectively improving the interfacial chemistry of LMBs. [ABSTRACT FROM AUTHOR]

The design of pyridine‐derived organocatalysts aims at the increase of their Lewis basicity, however such an approach is not always efficient. For example, strongly Lewis basic DMAP is completely inefficient as catalyst in the cyclopropanation reaction. Herein we disclose an alternative approach that relies on attenuation of DMAP Lewis basicity. Specifically, the replacement of 4‐dimethylamino substituent in DMAP for 4‐MeO group delivered a highly efficient catalyst for cyclopropanation of electron‐deficient olefins with α‐bromoketones. Kinetic studies provide compelling evidence that the superior catalytic efficiency of 4‐MeO pyridine (MOPY) is to be attributed to the favorable balance between Lewis basicity and leaving group ability. The use of chiral, enantiomerically pure MOPY catalyst has helped to achieve high enantioselectivities (up to 91 : 9 er) in the previously unreported pyridine‐catalyzed cyclopropanation reaction. [ABSTRACT FROM AUTHOR]

We have quantum chemically investigated the boron‐boron bonds in B2, diborynes B2L2, and diborenes B2H2L2 (L=none, OH2, NH3) using dispersion‐corrected relativistic density functional theory at ZORA‐BLYP‐D3(BJ)/TZ2P. B2 has effectively a single B−B bond provided by two half π bonds, whereas B2H2 has effectively a double B=B bond provided by two half π bonds and one σ 2p–2p bond. This different electronic structure causes B2 and B2H2 to react differently to the addition of ligands. Thus, in B2L2, electron‐donating ligands shorten and strengthen the boron‐boron bond whereas, in B2H2L2, they lengthen and weaken the boron‐boron bond. The aforementioned variations in boron‐boron bond length and strength become more pronounced as the Lewis basicity of the ligands L increases. [ABSTRACT FROM AUTHOR]

The DFT‐level computational investigations into Gibbs free energies (ΔG) demonstrate that as the dielectric constant of the solvent increases, the stabilities of [M(NH3)n]2+/3+ (n = 4, 6; M = selected 3d transition metals) complexes decrease. However, there is no observed correlation between the stability of the complex and the solvent donor number. Analysis of the charge transfer and Wiberg bond indices indicates a dative‐bond character in all the complexes. The solvent effect assessed through solvation energy is determined by the change in the solvent accessible surface area (SASA) and the change in the charge distribution that occurs during complex formation. It has been observed that the SASA and charge transfer are different in the different coordination numbers, resulting in a variation in the solvent effect on complex stability in different solvents. This ultimately leads to a change between the relative stability of complexes with different coordination numbers while increasing the solvent polarity for a few complexes. Moreover, the findings indicate a direct relationship between ΔΔG (∆Gsolvent‐∆Ggas) and ΔEsolv, which enables the computation of ΔG for the compounds in a particular solvent using only ΔGgas and ΔEsolv. This approach is less computationally expensive. [ABSTRACT FROM AUTHOR]

Calcium ion batteries (CIBs) are considered as an important candidate for post‐lithium energy storage devices due to their abundance of resources and low cost. However, CIBs still suffer from slow kinetics due to the large solvation structure and high desolvation energy of Ca2+ ions. Here, a solvation regulation strategy based on donor number (DN) is reported to achieve easy‐desolvation and rapid storage of Ca2+ in sodium vanadate (Na2V6O16·2H2O, NVO). Specially, the solvent with a low DN, represented by propylene carbonate (PC), forms the first solvation shell of calcium ions with weak binding energy and small shell structure, which facilitates the migration of Ca2+ in the electrolyte. More importantly, the low DN solvent is preferentially desolvated at the cathode/electrolyte interface, promoting the insertion of Ca2+ into the NVO electrode. Mechanism studies further confirm the highly reversible uptake/release of Ca2+ in the NVO cathode, along with the VO distance change in the coordination structure. Therefore, the NVO cathode achieves high capacity (376 mAh g−1 at 0.3 A g−1) and high‐rate performance (151 mAh g−1 at 5 A g−1). The weak solvation effect strategy further improves the electrochemical performance and provides great importance for the design of the long‐term development of CIBs. [ABSTRACT FROM AUTHOR]

A cross-linkable solubilizer with a high Gutmann donor number is applied to facilitate the dissolution of insoluble LiNO 3 in carbonate-based electrolytes, and to form gel polymer electrolytes through in situ polymerization process. The Li+ solvation structure of GPEs is regulated by LiNO 3 and DMAA, which suppresses the decomposition of LiPF 6 and promotes the formation of an inorganic-rich SEI. [Display omitted] High-voltage lithium metal batteries (LMBs) have been considered promising next-generation high-energy–density batteries. However, commercial carbonate electrolytes can scarcely be employed in LMBs owing to their poor compatibility with metallic lithium. N , N -dimethylacrylamide (DMAA)—a crosslinkable solubilizer with a high Gutmann donor number—is employed to facilitate the dissolution of insoluble lithium nitrate (LiNO 3) in carbonate-based electrolytes and to form gel polymer electrolytes (GPEs) through in situ polymerization. The Li+ solvation structure of the GPEs is regulated using LiNO 3 and DMAA, which suppresses the decomposition of LiPF 6 and facilitates the formation of an inorganic-rich solid electrolyte interface. Consequently, the Coulombic efficiency (CE) of the Li||Cu cell assembled with a GPE increases to 98.5% at room temperature, and the high-voltage Li||NCM622 cell achieves a capacity retention of 80.1% with a high CE of 99.5% after 400 cycles. The bifunctional polymer electrolytes are anticipated to pave the way for next-generation high-voltage LMBs. [ABSTRACT FROM AUTHOR]

Designing chiral ligands with an axial symmetry higher than C2‐rotational symmetry is one of the most crucial approaches to improving enantioselectivity in asymmetric synthesis. Herein, C3‐symmetric chiral cage‐shaped phosphites are reported. Their Lewis basicity and chiral environment are precisely controlled by the tethered group. The cage‐shaped phosphites successfully worked as chiral ligands in Rh‐catalyzed asymmetric conjugate additions, realizing acceptable yields with excellent enantioselectivity, and were used to synthesize a pharmacologically important molecule. [ABSTRACT FROM AUTHOR]

In order to synthesize chemical filters for the selective removal of volatile fluorides, commercial magnesium fluoride MgF2 with high specific surface area (HSA) was investigated. The amount of -OH groups substituting fluorine is not negligible, partly due to the high surface area, but also due to the synthesis route. These hydroxyl groups induce a Lewis basicity on the surface of metal fluorides. The amount of these Lewis basic sites has been tailored using fluorination with F2 gas. The sorption of VOF3, used as model gas, onto these fluorides was investigated. The versatility of surface chemistry as a function of a number of Lewis basic sites opens the way to filter selectivity mixture of volatile fluorides depending on their Lewis acidity. HSA MgF2 acts as a stable matrix towards the gas to be purified, and the selectivity may be achieved by a higher Lewis acidity of the gaseous impurity. [ABSTRACT FROM AUTHOR]

Dimension growth of metal halides is important for its properties and applications. However, such dimension control of the metal halides is rarely reported in the literature and the growth mechanism is not clear yet. A minute difference of solvent properties can tremendously alter the process of nucleation and growth of crystals. Herein, an intriguing phenomenon of dimension tuning for Ag‐based metal halides is reported. The 1D Cs2AgCl3 crystals can be obtained in pure DMF while the 2D CsAgCl2 crystals are obtained in pure DMSO. Both exhibit bright yellow emission, which are derived from self‐trapping excitons (STEs). The photoluminescence quantum yield (PLQY) of Cs2AgCl3 (1D) and CsAgCl2 (2D) are 28.46 % and 20.61 %, respectively. In order to understand the mechanism of the dimension change, additional solvents (N,N‐dimethylacetamide, DMAC, 1,3‐Dimethyl‐Tetrahydropyrimidin‐2(1H)‐one, DMPU) are also selected to process the precursor for crystal growth. By comparing the functional group, dielectric constant, and donor number among the four solvents, we find the donor number plays the predominant role in nucleation process for Cs2AgCl3 and CsAgCl2. This research reveals the relationship between coordination ability of the solvent and the dimension of metal halides. [ABSTRACT FROM AUTHOR]

Micron-sized Si anode promises a much higher theoretical capacity than the traditional graphite anode and more attractive application prospect compared to its nanoscale counterpart. However, its severe volume expansion during lithiation requires solid electrolyte interphase (SEI) with reinforced mechanical stability. Here, we propose a solvent-induced selective dissolution strategy to in situ regulate the mechanical properties of SEI. By introducing a high-donor-number solvent, gamma-butyrolactone, into conventional electrolytes, low-modulus components of the SEI, such as Li alkyl carbonates, can be selectively dissolved upon cycling, leaving a robust SEI mainly consisting of lithium fluoride and polycarbonates. With this strategy, raw micron-sized Si anode retains 87.5% capacity after 100 cycles at 0.5 C (1500 mA g−1, 25°C), which can be improved to >300 cycles with carbon-coated micron-sized Si anode. Furthermore, the Si||LiNi0.8Co0.1Mn0.1O2 battery using the raw micron-sized Si anode with the selectively dissolved SEI retains 83.7% capacity after 150 cycles at 0.5 C (90 mA g−1). The selective dissolution effect for tailoring the SEI, as well as the corresponding cycling life of the Si anodes, is positively related to the donor number of the solvents, which highlights designing high-donor-number electrolytes as a guideline to tailor the SEI for stabilizing volume-changing alloying-type anodes in high-energy rechargeable batteries. The severe volume expansion during the lithiation of micron-sized Si in Li-ion batteries requires a solid electrolyte interphase with reinforced mechanical stability. Here, the authors propose a solvent-induced selective dissolution strategy to regulate the mechanical properties of the interphase. [ABSTRACT FROM AUTHOR]

Li‐metal batteries (LMB), although providing high energy density, face the grand challenge of identifying good electrolyte solvents for cycling. Common solvents are either only stable against lithium metal anode or only stable against LiNixMnyCo1‐x‐yO2 (NMC) cathode. There is significant effort trying to increase the cathode stability for ether electrolytes, which are in general stable against lithium metal anode. In comparison, there is much less effort trying to increase the anode stability of electrolytes that are stable against NMC cathode. One example is the sulfone‐based electrolyte. It has good cathode stability but is hindered from practical application because of (1) high viscosity and poor wetting capability and (2) poor anode stability. Here, we solve these issues by modifying the sulfone molecules using resonance and electron withdrawing effect. The viscosity is significantly reduced by delocalizing the electrons through introducing additional oxygen on the molecular backbone and applying appropriate fluorination. The resulting molecule 2,2,2‐trifluoroethyl mesylate (TFEM) has decreased Lewis basicity and less reactivity toward Li+. The electrolyte based on TFEM as single solvent enables cycling of LMB under harsh conditions of low N/P ratio (21 mg/cm2 NMC811 and 50 μm Li) with 90 % capacity retention after 160 cycles at C/3 discharge rate. [ABSTRACT FROM AUTHOR]

The phosphine complexes of beryllium chloride, bromide and iodide, [(PMe2Ph)2BeX2], [(PMePh2)2BeX2] and [(PPh3)BeX2]2 (X=Cl, Br, I) were prepared and characterised with multinuclear NMR spectroscopy. Additionally the molecular structure of dinuclear [(PPh3)BeCl2]2 was determined with single crystal X‐ray diffraction techniques. The threshold cone angle of the phosphines, below which two ligands can coordinate to the beryllium dihalide fragments, is between 136° and 145°. Halide‐chloride exchange in dichloromethane is observed for [(PPh3)BeBr2]2 and [(PPh3)BeI2]2, which leads to the formation of [(PPh3)BeCl2]2. Due to the relatively low Lewis basicity of PPh3, it almost exclusively acts as a spectator ligand with only little formation of phosphonium cations. [ABSTRACT FROM AUTHOR]

Three types of metal-doped ETS-10 zeolites including Ni-ETS-10, Al-ETS-10, and Ga-ETS-10 were successfully synthesized by one-pot template-free hydrothermal treatments. The effect of doping metals on the crystallinity, morphology, textural property, and basicity of the produced zeolites was systematically studied. It was found that doping with an appropriate amount of Ni could enhance the crystallinity and basicity of ETS-10 zeolites in comparison with Al and Ga, and the Ni species mainly existed in two forms of framework coordination and exchange site connection within Ni-ETS-10. The catalytic evaluation by the liquid Knoevenagel condensation reaction of benzaldehyde with ethyl cyanoacetate confirmed the superiority of ETS-10 and metal-doped ETS-10 in comparison with the contrast base zeolites of NaY and KY. And the 0.4Ni-ETS-10 catalyst exihibted the best performance with 75.6 % yield of ethyl ɑ-cyanocinnamate (ECC) among all the synthesized (metal-doped) ETS-10 zeolites. It is reasonable to expect that the demonstrated work has important implications for the design and facile synthesis of new-type high-performance base zeolite catalysts.

Passivation of the sulfur cathode by insulating lithium sulfide restricts the reversibility and sulfur utilization of Li−S batteries. 3D nucleation of Li2S enabled by radical conversion may significantly boost the redox kinetics. Electrolytes with high donor number (DN) solvents allow for tri‐sulfur (S3⋅−) radicals as intermediates, however, the catastrophic reactivity of such solvents with Li anodes pose a great challenge for their practical application. Here, we propose the use of quaternary ammonium salts as electrolyte additives, which can preserve the partial high‐DN characteristics that trigger the S3⋅− radical pathway, and inhibit the growth of Li dendrites. Li−S batteries with tetrapropylammonium bromide (T3Br) electrolyte additive deliver the outstanding cycling stability (700 cycles at 1 C with a low‐capacity decay rate of 0.049 % per cycle), and high capacity under a lean electrolyte of 5 μLelectrolyte mgsulfur−1. This work opens a new avenue for the development of electrolyte additives for Li−S batteries. [ABSTRACT FROM AUTHOR]

Balancing the activation of H2O is crucial for highly selective CO2 electroreduction (CO2RR), as the protonation steps of CO2RR require fast H2O dissociation kinetics, while suppressing hydrogen evolution (HER) demands slow H2O reduction. We herein proposed one molecular engineering strategy to regulate the H2O activation using aprotic organic small molecules with high Gutmann donor number as a solvation shell regulator. These organic molecules occupy the first solvation shell of K+ and accumulate in the electrical double layer, decreasing the H2O density at the interface and the relative content of proton suppliers (free and coordinated H2O), suppressing the HER. The adsorbed H2O was stabilized via the second sphere effect and its dissociation was promoted by weakening the O−H bond, which accelerates the subsequent *CO2 protonation kinetics and reduces the energy barrier. In the model electrolyte containing 5 M dimethyl sulfoxide (DMSO) as an additive (KCl‐DMSO‐5), the highest CO selectivity over Ag foil increased to 99.2 %, with FECO higher than 90.0 % within −0.75 to −1.15 V (vs. RHE). This molecular engineering strategy for cation solvation shell can be extended to other metal electrodes, such as Zn and Sn, and organic molecules like N,N‐dimethylformamide. [ABSTRACT FROM AUTHOR]

All-solid-state batteries (ASSBs) are promising to be next-generation battery that provides high energy density and intrinsic safety. Research in the field of ASSBs has so far focused on the development of highly conductive solid electrolytes (SEs). The commercialization of ASSBs requires well-established large-scale manufacturing for sulfide SEs with high ionic conductivity. However, the synthesis for sulfide SEs remains at the laboratory scale with limited scalability owing to their air sensitivity. The liquid-phase synthesis would be an economically viable manufacturing technology for sulfide SEs. Herein, we review a chemical perspective in liquid-phase synthesis that offers high scalability, low cost, and high reaction kinetics. This review provides a guideline for desirable solvent selection based on the solubility and polarity characterized by the donor number and dielectric permittivity of solvents. Additionally, we offer a deeper understanding of the recent works on scalable liquid-phase synthesis using solubilizers and reactant agents. We present an outlook on a universal liquid-phase synthesis of sulfide SEs toward the commercialization of sulfide-based ASSBs. [ABSTRACT FROM AUTHOR]

We have investigated the effect of microsolvation on the π* shape resonances of uracil, referred to as π 1 * and π 2 * in the order of increasing energy. Our study considered uracil–water aggregates with six solvent molecules obtained from Monte Carlo simulations in the liquid phase. To explore the ensemble statistics, we combined scattering calculations, performed in the static exchange and static exchange plus polarization approximations, with linear regressions of virtual orbital energies to the scattering results. In general, the solvent molecules stabilize the anion states, and the lower lying π 1 * resonance becomes a bound state in most of the solute–water clusters. We also discuss how the strength of the H bonds can affect the energies of the anion states, in addition to the number and donor/acceptor characters of those bonds. The thermal distributions for the vertical attachment energies, obtained from 133 statistically uncorrelated solute–solvent clusters, are significantly broad in the energy scale of the autoionization widths. The distributions for the π 1 * and π 2 * anion states slightly overlap, thus giving rise to a quasi-continuum of attachment energies below ≲2.5 eV, in contrast to the gas phase picture of electron attachment to well separated resonances below the electronic excitation threshold. Both the stabilization of the anion states and the spread of attachment energies could be expected to favor the dissociative electron attachment processes believed to underlie the electron-induced damage to biomolecules. [ABSTRACT FROM AUTHOR]

Understanding the origin of the strong difference of electrical parameters between as grown and annealed undoped ZnO films prepared at a temperature range of 100–200 °C by thermal atomic layer deposition is essential for their future applications. In this paper, we show that the conductivity drop by up to 4 orders of magnitude as effect of post-growth annealing is accompanied by multiple simultaneous effects like a two orders of magnitude decrease of hydrogen impurity content, a strong width reduction of the luminescence peaks, and an increase of crystallite sizes influencing the carrier scattering. We show that a level of structural and optical improvement as well as the final electrical parameters of annealed films strongly depend on the previously employed growth temperature, which is related to transition from oxygen- to zinc-rich conditions influencing a type and concentration of native point defects. The growth temperature does not only influence the bandgap energy but also the binding energies of existing donors and the relative ratio between the number of donors and acceptors; hence, it determines the final electrical characteristics of the films. This means that electrical properties of undoped ZnO-atomic layer deposition films can be tuned by native defects engineering. [ABSTRACT FROM AUTHOR]

Seawater is one of the most important CO2 sequestration media for delivering value‐added chemicals/fuels and active chlorine; however, this scenario is plagued by sluggish reaction rates and poor product selectivity. Herein, we first report the synthesis of nitrogen‐doped BiOCl atomic layers to directly split carbon‐sequestrated natural seawater (Yellow Sea, China) into stoichiometric CO (92.8 μmol h−1) and HClO (83.2 μmol h−1) under visible light with selectivities greater than 90 %. Photoelectrons enriched on the exposed BiOCl{001} facet kinetically facilitate CO2‐to‐CO reduction via surface‐doped nitrogen bearing Lewis basicity. Photoholes, mainly located on the lateral facets of van der Waals gaps, promote the selective oxidation of Cl− into HClO. Sequestrated CO2 also maintains the pH of seawater at around 4.2 to prevent the alkaline earth cations from precipitating. The produced HClO can effectively kill typical bacteria in the ballast water of ocean‐going cargo ships, offering a green and safe way for onsite sterilization. [ABSTRACT FROM AUTHOR]

Artificial intelligence/machine learning (AI/ML) applied to battery research is considered to be a powerful tool for accelerating the research cycle. However, the development of appropriate materials descriptors is often the first hurdle toward implementing meaningful and accurate AI/ML. Currently, rational solvent selection remains a significant challenge in electrolyte development and is still based on experiments. The dielectric constant (ε) and donor number (DN) in electrolyte design are insufficient. Finding theoretically computable solvent descriptors for evaluating Li+ solvation is a significant step toward accelerating electrolyte development. Here, based on the electrostatic interaction between Li+ and solvent, the electrostatic potential (ESP) of electrolyte solvent is calculated by density functional theory calculations and reveals significant regularity. ESP as a direct and simple solvent descriptor for conveniently designing electrolytes is proposed. The lowest negative electrostatic potential (ESPmin) ensures the nucleophilic capacity of the solvating solvent and the weak ESPmin means decreased solvation energy. Weak ESPmin and strong highest positive electrostatic potential (ESPmax) are the main characteristics of non‐solvating antisolvents. Using the plot of ESPmin – ESPmax strong solvating solvent, weakly solvating solvent, or antisolvent are identified that have been used in electrolyte engineering. This solvent descriptor can boost AI/ML to develop high performance electrolytes. [ABSTRACT FROM AUTHOR]

Salt anions with a high donor number (DN) enable high sulfur utilization in lithium‐sulfur (Li‐S) batteries by inducing three‐dimensional (3D) Li2S growth. However, their insufficient compatibility with Li metal electrodes limits their cycling stability. Herein, a new class of salt anion, thiocyanate (SCN−), is presented, which features a Janus character of electron donor and acceptor. Due to a strong Li+ coordination by SCN− and the direct interaction of SCN− with polysulfide anions, the LiSCN electrolyte has a remarkably high lithium polysulfide solubility. This electrolyte induces 3D Li2S formation and ameliorates cathode passivation, even more than Br−, a typical high DN anion. Moreover, SCN− forms a Li3N‐enriched stable SEI layer at the surface of the Li metal electrode, enhancing cycling stability. A Li‐S battery with the LiSCN electrolyte shows high current density operation (2.54 mA cm⁻2) with high discharge capacity (1133 mAh g⁻1) and prolonged cycle life (100 cycles). This work demonstrates that the cathode and anode performance in a Li‐S battery can be simply and concurrently enhanced by the single salt anion. [ABSTRACT FROM AUTHOR]

Perovskite film with high crystal quality is fundamental to achieving high‐performance solar cells. A fast nucleation process is crucial to improving the crystallization quality. Here, we propose a self‐driven prenucleation strategy to achieve fast nucleation. This is realized through rational solvent design. The key characteristics of different solvents are systematically evaluated. Among them, formamide, with ultra‐high dielectric constant, low Gutman donor number, and a high boiling point, is selected as the co‐solvent. These unique characteristics render formamide a double‐face solvent that is a good solvent for formamidinium iodide (FAI) and CsI while a poor solvent for PbI2. As a result, formamide induces the self‐driven prenucleation of PbI2‐DMSO seeding crystals and accelerates the nucleation, improving the crystalline quality of perovskite film. The efficiency of the hole transport layer‐free carbon‐based perovskite solar cells is boosted beyond 19 % for the first time. [ABSTRACT FROM AUTHOR]

The performance of aqueous Zn ion batteries (AZIBs) is highly dependent on inner Helmholtz plane (IHP) chemistry. Notorious parasitic reactions containing hydrogen evolution reactions (HER) and Zn dendrites both originate from abundant free H2O and random Zn deposition inside active IHP. Here, we report a universal high donor number (DN) additive pyridine (Py) with only 1 vol. % addition (Py‐to‐H2O volume ratio), for regulating molecule distribution inside IHP. Density functional theory (DFT) calculations and molecular dynamics (MD) simulation verify that incorporated Py additive could tailor Zn2+ solvation sheath and exclude H2O molecules from IHP effectively, which is in favor of preventing H2O decomposition. Consequently, even at extreme conditions such as high depth of discharge (DOD) of 80 %, the symmetric cell based on Py additive can sustain approximately 500 h long‐term stability. This efficient strategy with high DN additives furnishes a promising direction for designing novel electrolytes and promoting the practical application of AZIBs, despite inevitably introducing trace organic additives. [ABSTRACT FROM AUTHOR]

Harmful Sn(IV) vacancies and uncontrolled fast crystallization commonly occur in tin–lead alloyed perovskite films. The typical dimethyl sulfoxide (DMSO) processing solvent is suggested to be the primary source of problems. Here, a DMSO‐free solvent strategy is demonstrated to obtain high‐performance Cs0.25FA0.75Pb0.5Sn0.5I3 solar cells. A rational solvent selection process via Hansen solubility parameters and Gutmann's donor number shows that N,N′‐dimethylpropyleneurea (DMPU) has a strong coordinate ability to form complete complexation with organic (formamidinium iodide) and inorganic (CsI, PbI2, and SnI2) components. This treatment suppresses the iodoplumbate (PbIn2‐n) or iodostannate (SnIn2‐n) preformed in precursor solution, thereby promoting pure intermediate complexes and retarding crystallization, realizing enlarged grain size, and improved film crystallinity. Additionally, it is demonstrated that DMPU‐based solvent system can further inhibit the oxidation of Sn(II) and reduced Sn(IV) content by nearly 75% due to its superior thermal and chemical stability. This DMSO‐free strategy generates a record efficiency of 22.41%, with a Voc of 0.88 V and a FF of 82.72% for the MA‐free Sn–Pb alloyed device. The unencapsulated devices display much‐improved humidity stability at 30 ± 5% relative humidity in air for 240 h, impressive thermal stability at 85 °C for 500 h, and promote continuous operation stability at maximum power point for 150 h. [ABSTRACT FROM AUTHOR]

[Display omitted] Platinum-based (Pt) catalysts are the most common commercial catalysts for oxygen reduction reactions (ORR). Unfortunately, their high price, scarcity and poor durability hinder their further development. Therefore, the development of effective and economical ORR electrocatalysts has received increasing attention. Here, carbon dots (CDs) enriched in amino functional groups were successfully loaded onto carbon nanotubes (CNTs) with a large surface area and helical structure through a surface state engineering strategy. The resulting composites (CD/CNTs) are 0D/1D nano heterojunction structures. The CD/CNTs showed superior ORR activity compared with CNTs and CDs (E oneset = 0.95 V, E 1/2 = 0.81 V and limiting current density = 4.74 mA cm−2). In addition, the stability of CD/CNTs in an alkaline medium was up to 30000 s. The excellent ORR performance of CD/CNTs can be attributed to the dominant role of amino-N, the synergistic effect of heterojunctions formed by CDs and CNTs, and the high Lewis basicity. The composite electrocatalyst synthesized by the CD-regulated CNT strategy is expected to be a reliable cathode candidate for future energy conversion devices. [ABSTRACT FROM AUTHOR]

We report the first highly selective kinetic resolution of racemic α‐chiral azides via Cu‐catalyzed azide‐alkyne cycloaddition (CuAAC). Newly developed pyridine‐bisoxazoline (PYBOX) ligands, bearing a C4 sulfonyl group, enable effective kinetic resolution of racemic azides derived from privileged scaffolds such as indanone, cyclopentenone, and oxindole, and their asymmetric CuAAC to afford α‐tertiary 1,2,3‐triazoles with high to excellent ee values. DFT calculations and control experiments reveal that the C4 sulfonyl group decreases the Lewis basicity of the ligand and increases the electrophilicity of the copper center for better recognition of azides, and functions as a shielding group to make the chiral pocket of the catalyst more effective. [ABSTRACT FROM AUTHOR]

Reverse water‐gas shift (RWGS) reaction is the initial and necessary step of CO2 hydrogenation to high value‐added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnNx@C‐N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four‐coordinate Zn‐N4 sites and low valence CuNx clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn‐N4 and N4 structures, which show strong Lewis basicity and has strong adsorption for *CO2 and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO2 conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO2 conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu‐ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO2. In the catalytic process, CuNx not only adsorbs and activates H2, but also cooperates with the adjacent Zn‐N4 and N4 structures to jointly activate CO2 molecules and further promotes the hydrogenation of CO2. This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts. [ABSTRACT FROM AUTHOR]

Reverse water‐gas shift (RWGS) reaction is the initial and necessary step of CO2 hydrogenation to high value‐added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnNx@C‐N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four‐coordinate Zn‐N4 sites and low valence CuNx clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn‐N4 and N4 structures, which show strong Lewis basicity and has strong adsorption for *CO2 and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO2 conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO2 conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu‐ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO2. In the catalytic process, CuNx not only adsorbs and activates H2, but also cooperates with the adjacent Zn‐N4 and N4 structures to jointly activate CO2 molecules and further promotes the hydrogenation of CO2. This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts. [ABSTRACT FROM AUTHOR]

Boron‐boron multiple bonds, such as those found in diborenes and diborynes, are typically stabilized by σ‐donor ligands that furnish electron density to these otherwise electron‐deficient species. These compounds are not only of fundamental importance in the study of chemical bonding, but can also activate small molecules in a chemistry reminiscent of that carried out by transition metals. In the pursuit of designing new and improved σ‐donor ligands to stabilize diborenes and diborynes suitable to activate small molecules, we performed density functional calculations to evaluate the Lewis basicity of a series of σ‐donor ligands. For this evaluation, we analysed the interaction between the boranes and the σ‐donor ligands in model systems L→BX3 (X=F and Me) using energy decomposition analyses. We found that electronic bond energies of the L→BX3 adducts correlate well with the ionization energies of the ligands and that ligands with high or medium basicity stabilize diborynes better than ligands with low basicity. We also learnt that beryllium‐based ligands are promising since they are able to stabilize L→B≡B←L diborynes without significantly reducing the triple bond character of the B≡B bond. [ABSTRACT FROM AUTHOR]

Starting with diboranes with two electron‐rich bridging bicyclic guanidinate substituents, we report in this work the rational synthesis of new dicationic symmetrically‐ and unsymmetrically‐substituted diboranes in SN1‐type substitution reactions in which triflato or bromo substituents are replaced by neutral Lewis bases. The scope of such substitution reactions and their rate are analyzed with different pyridine derivatives of variable Lewis basicity. The first substitution step, leading to a monocationic diborane with one anionic substituent (triflate or bromide) and one neutral Lewis base, proceeds much faster than the second substitution step leading to a dicationic diborane with two neutral Lewis bases. The different time scales for the substitution steps could be used to conveniently synthesize in one‐pot reactions several dicationic, unsymmetrically‐substituted diboranes with two different neutral Lewis bases. [ABSTRACT FROM AUTHOR]

Activation of the dinitrogen triple bond is a crucial step in the overall fixation of atmospheric nitrogen into usable forms for industrial and biological applications. Current synthetic catalysts incorporate metal ions to facilitate the activation and cleavage of dinitrogen. The high price of metal‐based catalysts and the challenge of catalyst recovery during industrial catalytic processes has led to increasing interest in metal‐free catalysts. One step toward metal‐free catalysis is the use of frustrated Lewis pairs (FLPs). In this study, we have examined 18 functionalized carbenes as FLPs to elucidate the influence of steric and electronic effects on the activation of dinitrogen. To test the effects of functionalization on dinitrogen activation, we have performed density functional theory (DFT), multireference, non and extended transition state‐natural orbital for chemical valence (ETS‐NOCV) calculations. Our results suggest that functional groups which introduce strong electron‐withdrawing effects and/or engage in extended π/π* systems lead to the lowering of the dissociation energy of the dinitrogen bond, which further contributes to greater nitrogen activation. We conjecture that these effects are due to enhanced back‐bonding capability of the p orbital of the carbene carbon atoms to the adjacent nitrogen atoms (increasing Lewis basicity of the carbene carbon atom) and enhanced stability of dissociated products. Our concluding remarks include opportunities to extend this activation study to explore the entire catalytic cycle with promising functionalized carbenes for experimental evaluation. [ABSTRACT FROM AUTHOR]

Li‐metal battery (LMB) suffers from the unexpected Li dendrite growth and unstable solid‐electrolyte interphase (SEI), especially in the extreme conditions, such as high rates and low temperatures (LT). Herein, a high‐rate and stable LT LMB is realized by regulating electrolyte chemistry. A weak Li+‐solvating solvent 2‐methyltetrahydrofuran is used as electrolyte solvent to mitigate the kinetic barrier for Li+ de‐solvation. Moreover, a co‐solvent tetrahydrofuran with a high donor number is incorporated to improve the LT solubility of Li salts, achieving an improved ionic conductivity while maintaining the weak Li+‐solvation effect. Furthermore, abundant FSI‐ anions in contact‐ion pairs are presented, facilitating the formation of a stable LiF‐enriched SEI. Consequently, the Li||Li battery can be operated at 10 mA cm‐2 with a small polarization of 154 mV at −40 °C. Meanwhile, an outstanding cumulative cycling capacity of 4000 mAh cm‐2 at 8.0 mA cm‐2 is achieved, reaching a record high level in LT alkali metal symmetric batteries. Also, rechargeable high‐rate and stable full batteries are achieved at −40 °C. This work demonstrates the superiority of electrolyte chemistry for synergistic regulation of both ion transfer kinetics and SEI toward ultrafast and stable rechargeable LMBs at LT. [ABSTRACT FROM AUTHOR]

Coupled electron-proton transfer dominates the activity and selectivity of electrochemical CO 2 reduction (CO 2 RR), still the concern on proton-feeding is far from satisfied especially in nitrogen-doped carbonaceous catalysts. Here, we report that pyridinic N cooperated with electron-donating BC 3 provides with strengthened Lewis basicity for favorably electrophilic attack of CO 2 and beneficial electron transfer, while implanted BC 3 trigger water activation for availably proton-feeding, conducting to superior CO production rate on two-step synthesized B and N co-doped porous graphene (t BNPG) over single N-doped reference. Inspired by such cognition, oxygen-containing groups applauded by their charge induced effect, were further decorated on t BNPG but elevating the competitive H 2 evolution (HER). Mechanistic studies illustrate that lateral oxygen functionalities, especially –COOH, deliver BC 3 sites much lower limiting potentials for H 2 O transition to *H, determining whose fate branches to HER versus CO 2 RR. The atomic-level insight paves the cornerstone for the catalysts design of proton-involved electrochemical reactions. [Display omitted] Pyridinic N cooperated with electron-deficient BC 3 is beneficial for accelerating the CEPT process of CO 2 RR by favorably electron-transfer and proton-feeding. [ABSTRACT FROM AUTHOR]

[Display omitted] • KCl-incorporated g-C 3 N 4 (CN11) was prepared via a one-step thermal polymerization for CO 2 adsorption. • CN11 exhibited the highest CO 2 adsorption per unit surface area (44.52 μmol m−2). • m-CO 3 2− and b-CO 3 2− were identified as the major intermediates formed on the CN sample. • KCl incorporation formed K–N bonds within the CN structure and improved electron transfer. In this study, we demonstrated the synthesis of potassium chloride (KCl)-incorporated graphitic carbon nitride, (g-C 3 N 4 , CN) with varying amounts of N -vacancies and pyridinic-N as well as enhanced Lewis basicity, via a single-step thermal polymerization by tailoring the precursors of melamine and urea for carbon oxide (CO 2) capture. Melamine, as a precursor, undergoes a phase transformation into melam and triazine-rich g-C 3 N 4 , whereas the addition of urea polymerizes the mixture to form melem and heptazine-rich g-C 3 N 4 (CN11). Owing to the abundance of pyridinic-N and the high surface area, CN11 adsorbed higher amounts of CO 2 (44.52 μmol m−2 at 25 °C and 1 bar of CO 2) than those reported for other template-free carbon materials. Spectroscopic analysis revealed that the enhanced CO 2 adsorption is due to the presence of pyridinic-N and Lewis basic sites on the surface. The intermediates of CO 2 adsorption, including carbonate and bicarbonate species, attached to the CN samples were identified using in-situ Fourier-transform infrared spectroscopy (FTIR). This work provides insights into the mechanism of CO 2 adsorption by comparing the structural features of the synthesized KCl-incorporated g-C 3 N 4 samples. CN11, with an excellent CO 2 uptake capacity, is viewed as a promising candidate for CO 2 capture and storage. [ABSTRACT FROM AUTHOR]

Conversion of CO 2 to chemicals and fuels has attracted considerable attention as CO 2 is a nontoxic, non-flammable, and cheap carbon-oxygen source. However, the kinetics of CO 2 conversion into other chemicals remains a challenge due to its thermodynamic stability. Herein, P and S co-doped graphitic-carbon nitride (PSCN) catalyst was synthesized through one-step thermal condensation to improve its Lewis acidity and basicity and investigate carbon dioxide/glycerol (CO 2 /GLY) conversion. The catalytic GLY conversion at 210 °C reached 60% and 85% using pristine g-C 3 N 4 (CN) and PSCN, respectively, with CO 2 as a carbon feedstock and CH 3 CN as a dehydrating agent. Density-functional theory (DFT) calculations revealed that the efficient charge transfer resulting from P and S doping could increase the catalytic activity for CO 2 /GLY conversion by lowering the activation barrier. This is the first study to demonstrate the catalytic activity of the PSCN catalyst for the CO 2 /GLY conversion and the computational work for the GLY carboxylation reaction. Moreover, the interaction site and adsorption energy were investigated for the adsorption of CO 2 and GLY on PSCN and CN to elucidate the reaction mechanism. Our results demonstrated that PSCN could serve as a superior catalyst and pave new light for CO 2 /GLY conversion. [Display omitted] • P and S co-doped g-C 3 N 4 (PSCN) catalyst was prepared for a catalytic CO 2 /glycerol reaction. • PSCN exhibited a conversion of 85% at 210 °C because of its enhanced Lewis acidity and basicity. • PSCN decreased the energy barrier and improved the co-adsorption and glycerol carboxylation. [ABSTRACT FROM AUTHOR]

We present a theoretical and numerical framework for the study of molecular attraction mechanisms between species in solution. The respective approach provides detailed insight into the enthalpic contributions of solvation and relies on molecular exchange reactions in combination with electronic perturbations. Associated values for chemical reactivity indices such as the electronegativity, the chemical hardness, and the electrophilicity are obtained from straightforward conceptual density functional theory calculations. Further analysis of corresponding reaction energies allows us to estimate the enthalpic stability of solvent–solute, solvent–ion, and ion–ion complexes. The validity of our approach is demonstrated by the calculation of donor numbers for distinct solvents. Our results reveal a reasonable agreement between calculated and experimental outcomes which highlights the applicability of our combined theoretical and computational approach. [ABSTRACT FROM AUTHOR]