层状钛硅酸盐化合物作为锂离子电池负极储能材料

锂离子二次电池是手提设备的重要电力来源。近年来, 人们为了寻找更新颖更好的锂离子电极材料, 开始研究晶形离子交换材料, 这种材料具有开放孔道, 能够让离子在多孔框架里自由的进出。一种具有层状结构的钛硅酸盐Na-JDF-L1(Na₄Ti₂Si₈O₂₂·4H₂O)经过离子交换后被用作锂离子负极材料。它在循环200次后放电容量保持在364 mAh·g^-1, 并且库伦效率约为100%。通过将TiO₂引入Li(Na)-JDF-L1中, 有效的提高了材料的首次库伦效率和倍率放电性能。     

An XPS study of microporous and mesoporous titanosilicates

In this contribution we report on an XPS study of microporous and mesoporous titanosilicates, in particular microporous titanium silicalite TS‐1, ordered mesoporous Ti‐MCM‐41 and [Ti]‐MCM‐41 and amorphous mesoporous silica–titania (MST) catalysts. Our aim was to obtain both photoemission and x‐ray‐excited Auger data for Ti species on these catalysts and use them in a Ti Wagner plot to rationalize the dependence of the local electronic structure on the atomic environment. Isolated Ti(IV) species coordinated to four and six oxygen anions and segregated TiO₂ clusters were detected on all catalysts by a curve‐fitting procedure of Ti 2p, O 1s and related peaks. The presence of the Si 2p peak excited by an O Kα ghost makes the detection of Ti LMM Auger transitions in mesoporous samples impossible due to the low Ti loadings and its homogeneous distribution in the silica matrix. Small TiO₂ clusters are eventually segregated within the mesopores of the catalysts and not at their external surface. On TS‐1 microporous catalysts with similar Ti loadings to the mesoporous catalysts we were able to detect Ti LMM Auger transitions, and by the Ti Wagner plot we clearly identify the presence of octahedrally coordinated Ti(IV) species. Thus, it is suggested that on TS‐1 the in‐framework (? O)₄Ti species are easily changed to (? O)₄(H₂O)₂Ti species by insertion of water molecules from the atmosphere. Small TiO₂ clusters (diameter <5 nm), eventually present on samples with Ti loading >2 wt.%, are segregated at their external surface and present spectroscopic features similar to (? O)₄(H₂O)₂Ti species. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis and Luminescence of Eu3+-Doped Narsarsukite Prepared by the Sol-Gel Process

The sol-gel synthesis and structural characterisation of narsarsukite powders are reported. Samples doped with different Eu³⁺ amounts (Ti/Eu = 20 and 200), calcined at 800°C, have been characterised by powder XRD, ²³Na, ²⁹Si MAS NMR, Raman and luminescence spectroscopies. Eu³⁺-doped narsarsukite displays a high and stable room-temperature luminescence. The presence in narsarsukite of two different Eu³⁺ local environments is inferred based both on the distinct ⁵D₀ ⁷F₀ lines observed and on the local field splitting of the ⁷F_1,2 levels. For low lanthanide contents, the Eu³⁺ ions are essentially localised in a centrosymmetric environment characterized by a low-energy ⁵D₀ ⁷F₀ line and a relatively long ⁵D₀ lifetime (3.56–3.96 ms). In contrast, at high lanthanide contents the Eu³⁺ ions are also present in a second local site with a less covalent first coordination shell. This corresponds to a high-energy ⁵D₀ ⁷F₀ line and a short ⁵D₀ lifetime (0.84–0.99 ms). Therefore, it is likely that Eu³⁺ ions substitute for both Ti⁴⁺ and Na⁺, although the former ions are preferentially replaced at low Eu³⁺ content.     

Metal Containing New Inorganic Ring Systems Based on Siloxane and Phosphazane Frameworks

High-field ³¹P NMR spectroscopy and single crystal X-ray diffraction studies have been used to study the ring opening and nucleophilic substitution reactions of the λ³-cyclotriphosphazane [EtNPCl]₃. The synthesis of the ring opened silicophosphonate [RSi(OH){OP(O)(H)(OH)}]₂O (R = (2,6-iPr₂C₆H₃)NSiMe₃) (1) represents the first ever molecular silicophosphonate to be isolated bearing free reactive hydroxyl groups. The structure and conformation of the bulky aryloxide substituted λ³-cyclotriphosphazane derivative [EtNP(OAr)]₃ (Ar = 2,6-iPr₂C₆H₃) (2) has also been investigated. Interaction of 2 with transition metal precursor complexes leads to the isolation of phosphazane metal complexes with different mode of co-ordination of 2. Further, the reaction of Cp Ti(OAr)Cl₂ (Ar = 2,6-(CH₃)₂C₆H₃OH) with O{SiPh₂(OH)}₂ gave the eight-membered trititanosiloxane [Cp Ti(Cl) (O(SiPh₂O)₂SiPh₂O) (3). Siloxane chain expansion effects, presumed to be a consequence of ring strain, have been observed in the product. The presence of reactive Ti-Cl bond in 3 offers opportunities for its reaction chemistry to be explored.     

Inorganic Ion Exchangers for Cesium Removal from Radioactive Wastewater

Ion exchange is a proven process for radioactive wastewater decontamination, where inorganic sorbents are ideal due to their thermal, chemical and radiation stability. This review focuses on the removal of Cs⁺ by inorganic exchangers, viz. zeolites, titanosilicates, hexacyanoferrates metal oxides and hydrous metal oxides, bentonite/clays and the key family of ammonium phosphomolybdates (AMPs). The design of new selective composites is also addressed focusing on those based on AMPs, hexacyanoferrates and titanosilicates/zeolites. Future inorganic Cs⁺ exchangers will encompass promising solids, like lanthanide silicates, sodium titanates and metal sulfides. The sensing ability derived from the photoluminescence properties of lanthanide silicates and the efficiency of layered gallium-antimony-sulfide materials in acidic and basic solutions disclose considerable potential for real applications. The ion exchange systems are discussed in terms of sorbent capacity and selectivity (with competitors), pH, temperature and solution salinity. The microscopic features of the exchangers and the associated mechanisms (e.g., pore size, counterions radii, dehydration energy of the ions, coordination environments in the solid exchanger, and site accessibility) are always used for interpreting the ion exchange behavior. On the whole, more than 250 publications were reviewed and a large compilation of data is provided in Supplemental Material.     

层状钛硅酸盐化合物作为锂离子电池负极储能材料

锂离子二次电池是手提设备的重要电力来源。近年来,人们为了寻找更新颖更好的锂离子电极材料,开始研究晶形离子交换材料,这种材料具有开放孔道,能够让离子在多孔框架里自由的进出。一种具有层状结构的钛硅酸盐Na-JDF-L1(Na₄Ti₂Si₈O₂₂·4H₂O)经过离子交换后被用作锂离子负极材料。它在循环200次后放电容量保持在364 mAh·g^-1,并且库伦效率约为100%。通过将TiO₂引入Li(Na)-JDF-L1中,有效的提高了材料的首次库伦效率和倍率放电性能。