The metallic C6S monolayer with high specific capacity for K-ion batteries

K-ion batteries (KIBs) attract considerable attention due to the abundance of K, high-working voltages, and chemical similarity with Li, enabling the utilization of mature Li-ion technology. However, shortage of high-performance anode materials is a critical obstacle for the development of KIBs. Through first-principles swarm-intelligence structural search, we identify a potential anode material, the C₆S monolayer, which provides not only a remarkably high specific capacity of 1546 mAh/g but also a low diffusion barrier of 0.11 eV and a low open-circuit voltage of 0.21 V. Inherent metallicity originates from delocalized π electrons.     

Superb thermal stability purple-blue phosphor through synergistic effect of emission compensation and nonradiative transition restriction of Eu2+

Phosphors with outstanding luminescence thermal stability are desirable for high-power phosphor-converted light-emitting diode (pc-LED) lightings. High structural rigidity and large bandgap of phosphor hosts are helpful to suppress nonradiative relaxation of optical centers and realize excellent thermal stability. Unfortunately, few host materials simultaneously possess aforementioned structural features. Herein, we confirm that Sr₃(PO₄)₂ (SPO) phosphate possesses high structural rigidity (Debye temperature, Θ_D = 559 K) and large bandgap (E_g = 8.313 eV) by density functional theory calculations. As expected, Eu²⁺-doped SPO purple-blue phosphors show extraordinary thermal stability. At 150/300 °C, SPO:5%Eu²⁺ presents emission loss of only 4%/8% and a predicated ultrahigh thermal quenching temperature of 973 °C. The most strikingly discoveries here are that thermal-induced emission compensation appears within two distinct Eu²⁺ sites of SPO host. The outstanding thermal stability, on one hand, is attributed to rigid structure and large bandgap of host that inhibits nonradiative relaxation of Eu²⁺ and on the other hand, the emission self-compensation of Eu²⁺. Benefiting from synergistic effect of emission compensation and nonradiative transition restriction of Eu²⁺, as-prepared SPO:5%Eu²⁺ purple-blue phosphor not only presents superior thermal stability but also high internal quantum efficiency of 95.1% and excellent hydrolysis resistant. Some advanced applications are explored including white LED lighting and wide-color-gamut display. Our work provides in-deep insights into structure-property relationships of thermally stable phosphors.     

容器壁厚度对光栅衍射法测量液体折射率的影响

利用光栅衍射法测量了NaCl溶液的折射率,并分析了容器壁厚度引起的附加光程对折射率的影响.采用折射率修正公式运用一级衍射得到的溶液的折射率更可靠.     

弹簧参与的微小振动一定是简谐运动吗

振动和波动是生活中的一种非常普遍而重要的运动形式,其中简谐振动是最简单、最基本的运动,弹簧振子是研究简谐运动的最基本模型.在研究弹簧参与的微小振动时,部分学生不能很好的判定弹簧参与的微小振动是否为简谐运动.本文讨论了系统作简谐运动的充要条件,并通过4个具体例子详细分析了弹簧参与的微小振动.     

Pd(Ⅱ)催化的芳基次膦酸衍生物C-H键活化芳基化反应及衍生化反应

通过对钯催化的不同次膦酸衍生物芳基偶联反应的深入探索,发现在Pd(OAc)2作催化剂,Ag2CO3作氧化剂,对苯醌(BQ)作添加剂的反应条件下,可以高效地实现芳基次膦酰胺邻位C—H键的直接芳基化。机理研究表明,芳基次膦酰胺邻位C—H键活化芳基偶联反应经历了Pd(0)到Pd(Ⅱ)的催化循环。在对偶联产物衍生化的研究过程中,发现芳基次膦酰胺化合物可以高效地转化为芳基次膦酸酯和芳基膦化氢,收率分别为98%和82%。因此,本文报道的实验结果可以为多芳基膦化合物的合成提供一个新的方法。     

新型锌铝水滑石紫外吸收剂的制备及其紫外吸收性能

以有机紫外吸收剂2-苯基苯并咪唑-5-磺酸(PBSA)、N,N-二甲氨基苯甲酸(DABA)为有机原料,采用共沉淀法,合成了有机紫外吸收剂插层水滑石Zn2Al-LDH/PBSA和Zn2Al-LDH/DABA,并测定了所得到的样品的XRD、FT IR、薄膜紫外吸收性质和氧化催化活性。结果表明,当有机紫外吸收剂以阴离子的形式进入水滑石层间后,仍有良好的紫外吸收性能并在可见光区有很好的透光性;通过测定插层水滑石的氧化催化活性,与纯有机物相比,Zn2Al-LDH/PBSA和Zn2Al-LDH/DABA的氧化催化活性明显降低。合成的新型的插层水滑石有望在防晒产品中得到应用。     

A flexible chelate ligand in dodecatungstoborate-based supramolecular compounds

Two new dodecatungstoborate-based supramolecular compounds, [Cu₄(H₂EGTA)₂(H₂O)₄(HBW₁₂O₄₀)]·18H₂O (1) and [Na₃(H₂O)₆Ca₃(H₂O)₆(HEGTA)₂] [H₂BW₁₂O₄₀]·21H₂O (2) (EGTA = ethyleneglycol-bis-(2-aminoethylether)-tetra acetate anion), were synthesized in aqua solution and characterized by element analysis, infrared spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction technique. The results show that in 1 two H₂EGTA^2? anions bond to four Cu²⁺ ions forming a four-nuclear cyclic cation, Cu₄(H₂EGTA)₂(H₂O) ₄ ⁴⁺ ; and dodecatungstoborate anion HBW₁₂O₄₀ ^4? acting as a bidentate ligand links two four-nuclear cations, leading to one-dimensional chain extending along [101] direction, [Cu₄(H₂EGTA)₂(H₂O)₄(HBW₁₂O₄₀)] _n (Cu–EGTA–BW₁₂). In 2 two HEGTA^3? anions coordinate to four Ca²⁺ ions in different modes, forming a Ca-EGTA polymeric chain. The building blocks (Cu–EGTA–BW₁₂ chains in 1, Ca–HEGTA chains and BW₁₂ anions in 2) are fused into three-dimensional architectures by hydrogen bonds. Variable temperature magnetic susceptibilities of 1 were determined and the results show that in 1 there is a weak ferromagnetic interaction.     

Exploring the Limits of Transition-Metal Fluorination at High Pressures

Fluorination is a proven method for challenging the limits of chemistry, both structurally and electronically. Here we explore computationally how pressures below 300 GPa affect the fluorination of several transition metals. A plethora of new structural phases are predicted along with the possibility for synthesizing four unobserved compounds: TcF₇, CdF₃, OsF₈, and IrF₈. The Ir and Os octaflourides are both predicted to be stable as quasi-molecular phases with an unusual cubic ligand coordination, and both compounds formally correspond to a high oxidation state of +8. Electronic-structure analysis reveals that otherwise unoccupied 6p levels are brought down in energy by the combined effects of pressure and a strong ligand field. The valence expansion of Os and Ir enables ligand-to-metal F 2p→M 6p charge transfer that strengthens M−F bonds and decreases the overall bond polarity. The lower stability of IrF₈, and the instability of PtF₈ and several other compounds below 300 GPa, is explained by the occupation of M−F antibonding orbitals in octafluorides with a metal-valence-electron count exceeding 8.     

Mechanistic details of metal-free cyclization reaction of organophosphorus oxide with alkynes mediated by 2,6-lutidine and Tf2O

Theoretical investigations have elucidated the mechanism of metal-free electrophilic phosphinative cyclization of alkynes reaction reported by Miura and coworkers. Two competitive mechanisms I and II were explored without or with 2,6-lutidine. Both of I and II involve transformation of P(V) to P(III), electrophilic addition, ring opening and cyclization/cyclization, hydrogen-transfer, and oxidation. The rate-determining step of mechanism I and competitive less-step II is electrophilic [2 + 1] cycloaddition and electrophilic addition via single C P bond formation with activation barrier of 13.5 and 10.6 kcal/mol, respectively. Our calculation results suggested that the cumulative effect of the isomer of 2,6-lutidine and Tf₂O as well as TfO⁻ affects the title reaction to some extent, and simultaneously activates key reaction sites and reverses the polarities of them via the formation of abundant noncovalent interactions to decrease activation barriers of TSs. In addition, the effects of two series substituents on reactivity of phosphine oxide were investigated. Therefore, our study will serve as useful guidance for more efficient metal-free synthesis of organophosphorus compounds mediated by pyridine reagents.     

CuS/Ag2S纳米复合物的制备及类过氧化物酶性质

采用水热法合成了一种微球状的CuS/Ag₂S纳米复合物. 通过透射电子显微镜、 紫外-可见吸收光谱和拉曼光谱等对其形貌及光学性质进行了表征; 考察了其类过氧化物酶性质, 并通过表面增强拉曼散射原位监测了类过氧化物酶催化反应. 以3,3',5,5'-四甲基联苯胺(TMB)为底物进行显色反应, 结果表明, 在H₂O₂存在下CuS/Ag₂S 纳米复合物具有类过氧化物酶的性质, 可以将无色的TMB氧化成蓝色的oxTMB. 基于此实现了对微量H₂O₂的检测.