Novel electrospun polymer electrolytes incorporated with Keggin‐type hetero polyoxometalate fillers as solvent‐free electrolytes for lithium ion batteries

In this study, solvent‐free nanofibrous electrolytes were fabricated through an electrospinning method. Polyethylene oxide (PEO), lithium perchlorate and ethylene carbonate were used as polymer matrix, salt and plasticizer respectively in the electrolyte structures. Keggin‐type hetero polyoxometalate (Cu‐POM@Ru‐rGO, Ni‐POM@Ru‐rGO and Co‐POM@Ru‐rGO (POM, polyoxometalate; rGO, reduced graphene oxide)) nanoparticles were synthesized and inserted into the PEO‐based nanofibrous electrolytes. TEM and SEM analyses were carried out for further evaluation of the synthesized filler structures and the electrospun nanofibre morphologies. The fractions of free ions and crystalline phases of the as‐spun electrolytes were estimated by obtaining Fourier transform infrared and XRD spectra, respectively. The results showed a significant improvement in the ionic conductivity of the nanofibrous electrolytes by increasing filler concentrations. The highest ionic conductivity of 0.28 mS cm^?1 was obtained by the introduction of 0.49 wt% Co‐POM@Ru‐rGO into the electrospun electrolyte at ambient temperature. Compared with solution‐cast polymeric electrolytes, the electrospun electrolytes present superior ionic conductivity. Moreover, the cycle stability of the as‐spun electrolytes was clearly improved by the addition of fillers. Furthermore, the mechanical strength was enhanced with the insertion of 0.07 wt% fillers to the electrospun electrolytes. The results implied that the prepared nanofibres are good candidates as solvent‐free electrolytes for lithium ion batteries. © 2020 Society of Chemical Industry     

含稀土多金属氧酸盐的杂化)自组装膜的制备和光学性质研究

用自组装方法构建含稀土多金属氧酸盐和聚丙烯胺的有机-无机杂化多层膜.用紫外可见光谱、原子力显微镜、X射线衍射等测试手段表征了膜的结构.计算了此杂化多层膜上分子的密度和独特的排列状态,以及分子在膜上逐层按比例的增长,用荧光光谱检测了自组装膜发光性能.指出在杂化自组装膜上,稀土的发光特性依然得到保持.     

多酸化合物的药学应用进展

介绍了多金属氧酸盐化学的发展过程,综述了多酸化合物的药学应用进展,包括其在抗艾滋病（HIV）、抗肿瘤、抗病毒等方面的研究情况.同时,展望了未来多酸药学应用研究的主要领域及亟需解决的关键问题.     

Electrochemically Induced Crystalline-to-Amorphous Transition of Dinuclear Polyoxovanadate for High-Rate Lithium-Ion Batteries

Polyoxometalates are intriguing high-capacity anode materials for alkali-metal-ion storage due to their multi-electron redox capabilities and flexible structure. However, their poor electrical conductivity and high working voltage severely restrict their practical application. Herein, the dinuclear polyoxovanadate Sr₂V₂O₇·H₂O with unusually high electrical conductivity is reported as a promising anode material for lithium-ion batteries. During the initial lithiation process, the Sr₂V₂O₇·H₂O anode experiences an electrochemically induced crystalline-to-amorphous transition. The resulting amorphous structure provides high redox activity and fast reaction kinetics via reversible V^4.9+/V^2.8+ redox couple through the intercalation mechanism. Furthermore, when coupled with the LiFePO₄ cathode, the strong V O bonds of the amorphous anode provide excellent structural stability, with the full-cell capable of performing >12 000 cycles with a capacity retention of 72%. Another advantage of Sr_2xV₂O_7-δ·yH₂O (0.5 ≤ x ≤ 1.0) is its composition adjustability, which enables delicately regulating the Sr vacancy content without destroying the structure. The defect Sr_2xV₂O_7-δ·yH₂O (x = 0.5) electrodes show significantly improved specific capacity and rate capability without sacrificing other key properties, delivering a high specific capacity of 479 mAh g^-1 at 0.1 mA cm^-2 and 41.9% of its capacity in 2 min. Overall, the preliminary study points the way forward for the facile preparation of high-quality polyoxometalates for advanced energy storage applications and beyond.     

双-Keggin结构多金属氧酸盐对卤酸根离子的电催化还原

双-Keggin结构取代型稀土多金属氧酸盐K10H3[Eu（SiMo4W7O39）2].XH2O（简写为EuSiMo4W7）在水溶液中可进行一系列单电子和两电子的可逆还原过程,产生具有催化活性的杂多蓝,因此,该类化合物是良好的氧化剂和催化剂。采用循环伏安法研究EuSiMo4W7水溶液的电化学性质、扫描速度及溶液pH均对EuSiMo4W7的电化学性质有所影响,同时考察该物质对卤酸根离子还原反应的催化作用,结果表明：EuSiMo4W7对IO3-的催化作用强于对BrO3-的催化作用,而对ClO3-基本上不起催化作用,可见,EuSiMo4W7对3种卤酸根离子还原反应的催化作用按照ClO3-、BrO3-、IO3-的顺序依次增强。     

Keggin型多金属氧酸盐[Cu_2(phen)_4(SiMo_(12)O_(40))]的水热合成、晶体结构及表征

用硅酸钠和钼酸钠为原料,在水热条件下合成了一种新的Keggin型多金属氧酸盐[Cu2(phen)4(SiMo12O40)](phen=1,10-邻菲洛啉)(1).通过元素分析、红外光谱分析和X射线单晶衍射对化合物1进行了结构表征,结构表明该化合物属于三斜晶系,P21/c空间群,晶胞参数a=1.303 2(3)nm,b=1.152 2(2)nm,c=2.340 8(8)nm,β=108.29(3)°,V=3.337 3(15)nm3.同时也研究了化合物1的荧光性能.     

多酸化学课程改革与探索

针对我校多酸化学课程教学的实际,分析教学现状,探索多酸化学课程的改革与实践,为无机化学专业研究生教育改革提供参考。     

稀土对α-K7[SiFe3(OH2)3W9O37]多金属氧酸盐化学扩渗和导电性的影响

用改进方法合成了标题化合物。采用气相法通过固-气反应,研究多组分稀土对所合成多金属氧酸盐的化学热扩渗。经ICP、XPS、IR和XRD分析发现,微量的La、Ce、Sm、Gd等稀土元素可以渗入到多金属氧酸盐的体相。扩渗后化合物的电导率在室温下σ值达到1.59×10-3S·cm-1,比扩渗前多金属氧酸盐的电导率(σ=2.4×10-7S·cm-1)提高了几千倍;且渗后化合物导电性能的稳定温度显著增大,同导电性能最好的多金属氧酸盐H3PM12O40·29H2O(M=W,Mo)相比,其导电热稳定温度增大近200K,成为在523K以上依然保持高电导率的新型固体电解质。     

Synthesis and anticancer properties of tungstosilicic polyoxometalate containing 5-fluorouracil and neodymium

A novel tungstosilicic polyoxometalate containing 5-fluorouracil and Nd,K26(C4H4FN2O2)8Nd(SiW11O39)4·SH2O(FNSW)was synthesized and its structure was characterized by using elemental analysis,FT-IR spectra,X-ray powder diffraction,UV-vis spectra and TG.The results indicated that the compound FNSW had Keggin structure of heteropolyanion and ring structure of 5-fluorouracil,and it had a good thermal stability.With 5-fluorouracil for the positive control group,the cytotoxicity tests in human renal embryonic cell HEK293 and the antitumor activity tests in hepatocellular carcinoma cell HepG-2 were carried out by the methyl thiazolyl tetrazolium method.The toxicity of the compound FNSW was lower than that of 5-fluorouracil,and compared with 5-fluorouracil the compound FNSW could inhibit HepG-2cell in vitro with significant difference.The rare earth clement Nd increased the biological activity of polyoxometalate significantly.     

多磺酸官能化杂多酸离子杂化体的合成与催化性能研究

以四甲基乙二胺、五甲基二乙烯三胺、1,3-丙烷磺内酯、Keggin型杂多酸磷钨酸、硅钨酸为原料,经季铵化、酸化两步原子经济反应,合成了两种多磺酸基、多杂多酸阴离子官能化杂多酸离子杂化体8S3Si IH和6S2PIH。8S3Si IH、6S2PIH作为非均相催化剂,研究了柠檬酸与正丁醇的Fischer酯化反应,确定了最佳反应条件:n(酸)∶n(醇)∶n(杂化体)=1∶4∶0.001 5,无溶剂回流分水反应4 h,柠檬酸三丁酯产率分别为97.8%和95.7%。杂化体经过滤、乙醚洗涤、真空干燥即可再生循环使用,循环使用5次的催化活性保持不变。