Engineering Lithium Ions Embedded in NiFe Layered Double Hydroxide Lattices To Activate Laminated Ni2+ Sites as High-Efficiency Oxygen Evolution Reaction Catalysts

NiFe layered double hydroxides (LDHs) have been denoted as benchmark non-noble-metal electrocatalysts for the oxygen evolution reaction (OER). However, for laminates of NiFe LDHs, the edge sites are active, but the basal plane is inert, leading to underutilization as catalysts for the OER. Herein, for the first time, light and electron-deficient Li ions are intercalated into the basal plane of NiFe LDHs. The results of theoretical calculations and experiments both showed that electrons would be transferred from near Ni²⁺ to the surroundings of Li⁺, resulting in electron-deficient properties of the Ni sites, which would function as “electron-hungry” sites, to enhance surface adsorption of electron-rich oxygen-containing groups, which would enhance the effective activity for the OER. As demonstrated by the catalytic performance, the Li−NiFe LDH electrodes showed an ultralow overpotential of only 298 mV at 50 mA cm⁻², which was lower than that of 347 mV for initial NiFe LDHs and lower than that of 373 mV for RuO₂. Reasonable intercalation adjustment effectively activates laminated Ni²⁺ sites and constructs the electron-deficient structure to enhance its electrocatalytic activity, which sheds light on the functional treatment of catalytic materials.     

Reactivity of Diarylnitrenium Ions

Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar₂N⁺. Sequential H-atom abstraction reactions ensue. The first H-atom abstraction leads to intensely colored aminium radical cations, Ar₂NH^.+, some of which are quite stable. However, most undergo a second H-atom abstraction leading to ammonium ions, Ar₂NH₂⁺. In the absence of a ready source of H-atoms, a unique self-abstraction reaction occurs when Ar=Me₅C₆, leading to a novel iminium radical cation, Ar=N^.+Ar, which decays via a second self H-atom abstraction reaction to give a stable iminium ion, Ar=N⁺HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions.     

Boosting Conjugate Addition to Nitroolefins Using Lithium Tetraorganozincates: Synthetic Strategies and Structural Insights

We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R₄ZnLi₂) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R₄ZnLi₂ provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N’,N’-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N’,N’-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et₄ZnLi₂ into equimolar amounts of solvent-separated Et₃ZnLi and EtLi.     

Solution-Based,Anion-Doping of Li4Ti5O12 Nanoflowers for Lithium-Ion Battery Applications

Solution-based, anionic doping represents a convenient strategy with which to improve upon the conductivity of candidate anode materials such as Li₄Ti₅O₁₂ (LTO). As such, novel synthetic hydrothermally-inspired protocols have primarily been devised herein, aimed at the large-scale production of unique halogen-doped, micron-scale, three-dimensional, hierarchical LTO flower-like motifs. Although fluorine (F) doping has been explored, the use of chlorine (Cl) dopants is the primary focus here. Several experimental variables, such as dopant amount, lithium hydroxide concentration, and titanium butoxide purity, were probed and perfected. Furthermore, the Cl doping process did not damage the intrinsic LTO morphology. The analysis, based on interpreting a compilation of SEM, XRD, XPS, and TEM-EDS results, was used to determine an optimized dopant concentration of Cl. Electrochemical tests demonstrated an increased capacity via cycling of 12 % for a Cl-doped sample as compared with pristine LTO. Moreover, the Cl-doped LTO sample described in this study exhibited the highest discharge capacity yet reported at an observed rate of 2C for this material at 143mAh g⁻¹. Overall, these data suggest that the Cl dopant likely enhances not only the ion transport capabilities, but also the overall electrical conductivity of our as-prepared structures. To help explain these favorable findings, theoretical DFT calculations were used to postulate that the electronic conductivity and Li diffusion were likely improved by the presence of increased Ti³⁺ ion concentration coupled with widening of the Li migration channel.     

介孔碳材料抑制锂电池负极枝晶生长

为了解决锂电池负极表面锂枝晶生长带来的性能衰退和安全问题。 以沸石咪唑酯骨架-8(ZIF-8)为前驱体制得介孔碳材料(MCM),用于金属锂负极表面改性。 X射线粉末衍射(XRD)和拉曼光谱表明,退火制得的MCM具有一定的石墨化程度,N₂气吸脱附测试(BET)证明MCM具有典型的介孔特征。 对比不同温度退火样品的XRD、拉曼光谱和BET测试结果,确定900 ℃为最佳退火温度。 优化的MCM作为表面改性剂对金属锂负极进行改性研究。 电池充放电循环后,负极样品的XRD和扫描电子显微镜(SEM)测试表明,MCM能够通过均衡锂负极表面的电荷分布抑制金属锂的取向沉积和锂枝晶的生长。 本研究为制备抑制锂电池负极枝晶生长表面改性剂提供了一种简便而有效的合成方法,有利于锂电池循环寿命的延长和安全性能的提高。     

Effect of thickness variations of lithium niobate on insulator waveguide on the frequency spectrum of spontaneous parametric down-conversion

We study the effect of waveguide thickness variations on the frequency spectrum of spontaneous parametric down-conversion in the periodically-poled lithium niobate on insulator (LNOI) waveguide. We analyze several variation models and our simulation results show that thickness variations in several nanometers can induce distinct effects on the central peak of the spectrum, such as narrowing, broadening, and splitting. We also prove that the effects of positive and negative variations can be canceled and thus lead to a variation-robust feature and an ultra-broad bandwidth. Our study may promote the development of on-chip photon sources in the LNOI platform, as well as opens up a way to engineer photon frequency state.     

Ion transport in polymerized lyotropic liquid crystals containing ionic liquid

In this work, we investigate the effect of morphology and segmental dynamics on ion transport in polymerized lyotropic liquid crystals (polyLLCs) containing 1-butyl-3-methylimidazolium tetrafluoroborate as ionic liquid (IL). We demonstrate that two important factors, which affect ion conduction in polyLLCs, are grain size and chain density at the interface. The polyLLC with large grain size (70 nm) shows significant reduction in ion conductivity (one order of magnitude) compared to its homopolymer/IL mixture. However, the polyLLC with small grain size (20 nm) has little difference in ion conductivity compared to its homopolymer/IL mixture. It is observed that decreasing the chain density enhances the interaction of IL with polymer chains and consequently slows the relaxation of polymer chains. In addition, comparing the dynamics of polymer chains in mixtures of homopolymer/IL and templated LLC mesophases shows that the confinement in LLC structure prolongs the relaxation of polymer chains.     

单斜ZnP2负极材料的锂化机理及性能

过渡金属磷化物电位低且比容量高, 是有发展前景的锂离子电池(LIBs)负极材料. 其中, ZnP₂属于双活性负极材料, Zn与P都能与Li⁺发生反应, 储Li⁺性能更具有竞争力. 但是, 对于ZnP₂的锂化机理及产物尚不明确. 采用第一性原理计算和电化学测试方法研究了ZnP₂的电子性质和电化学性能, 通过理论计算和实验测试相结合阐述了ZnP₂的锂化机制. 首先, 以密度泛函理论(DFT)计算揭示了ZnP₂的锂化机理、Li⁺扩散路径、势垒和理论比容量(1477 mAh/g). 其次, 通过直流电弧等离子体法及固相烧结法合成ZnP₂, 并测试其首圈放电曲线, 显示放电容量为1439 mAh/g, 与理论计算结果相近. 此外, 薄膜X射线衍射(XRD)检测最终产物成分为LiZn和Li₃P, 与DFT计算结果一致.     

Emerging Trends in Fluorescence Bioimaging of Divalent Metal Cations Using Small-Molecule Indicators

Visualization of cation dynamics inside a living system represent a major breakthrough at the crossroad of chemistry and cellular physiology. Since the inception of BAPTA-based cellular calcium indicators in the 1980s, generations of chemical and genetically encoded ion indicators spanning the visible spectrum have been developed. In this article, we bring up three emerging concepts in this field: 1. red-shifting cation indicators towards far-red and near-infrared (NIR) channels; 2. directing the indicators to various subcellular localizations; 3. lowering the phototoxicity of indicators for long term recording. These initiatives collectively echo the advocate of 4D cellular physiology, where biological processes within living systems can be panoramically unveiled under 3D, long-term, and multi-channel imaging with unprecedented spatial and temporal resolution. This outlook poses exciting challenges and opportunities for chemists to upgrade the toolkit of fluorescent indicators as key enablers for a new era of imageomics.     

CoO纳米颗粒/石墨烯纳米纤维复合材料的制备及电化学性能

用石墨烯和Co(CH₃COO)₂·4H₂O作为原料,利用超声辅助法合成了锂离子电池的负极材料CoO纳米颗粒/中空石墨烯纳米纤维复合物.采用X射线衍射(XRD)确定材料的物相组成,采用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察材料的表面形貌和微观结构,采用X射线光电子能谱(XPS)确定材料的价态结构.采用循环伏安、恒电流充放电和交流阻抗谱表征材料的电化学性能.结果显示,在100 mA/g的电流密度下,循环了160次后,可逆容量仍超过800 mA/g,库仑效率保持在99%以上.该材料优异的电化学性能主要归因于石墨烯的中空纤维结构,中空内部可以容纳电解液,能直接将离子输送到颗粒表面,实现了离子的快速传输;二维中空纤维搭建成三维网络结构,实现了三维电子传导网络.