Doping-induced memory effect in Li-ion batteries: the case of Al-doped Li4Ti5O12

In Li-ion batteries (LIBs), a memory effect has been revealed in two-phase electrode materials such as olivine LiFePO₄ and anatase TiO₂, which complicates the two-phase transition and influences the estimation of the state of charge. Practical electrode materials are usually optimized by the element doping strategy, however, its impact on the memory effect has not been reported yet. Here we firstly present the doping-induced memory effect in LIBs. Pristine Li₄Ti₅O₁₂ is free from the memory effect, while a distinct memory effect could be induced by Al-doping. After being discharged to a lower cutoff potential, Al-doped Li₄Ti₅O₁₂ exhibits poorer electrochemical kinetics, delivering a larger overpotential during the charging process. This dependence of the overpotential on the discharging cutoff leads to the memory effect in Al-doped Li₄Ti₅O₁₂. Our discovery emphasizes the impact of element doping on the memory effect of electrode materials, and thus has implications for battery design.     

Photocatalytic activity of R3MO7 and R2Ti2O7 (R=Y, Gd, La; M=Nb, Ta) for water splitting into H2 and O2

The photocatalytic activities of R3MO7 and R2Ti2O7 (R=Y, Gd, La; M=Nb, Ta) strongly depended on the crystal structure. Overall, photocatalytic water splitting into H2 and O2 proceeded over La3TaO7 and La3NbO7, which have an orthorhombic weberite structure, Y2Ti2O7 and Gd2Ti2O7, which have a cubic pyrochlore structure, and La2Ti2O7, which has a monoclinic perovskite structure. All of these materials are composed of a network of corner-shared octahedral units of metal cations (TaO6, NbO6, or TiO6); materials without such a network were inactive. The octahedral network certainly increased the mobility of electrons and holes, thereby enhancing photocatalytic activity.     

Revisiting the nature of Cu sites in the activated Cu-SSZ-13 catalyst for SCR reaction

Cu-SSZ-13 is a highly active NH₃-SCR catalyst for the abatement of harmful nitrogen oxides (NO_x, x = 1, 2) from the exhausts of lean-burn engines. The study of Cu-speciation occurring upon thermal dehydration is a key step for the understanding of the enhanced catalytic properties of this material and for identifying the SCR active sites and their redox capability. Herein, we combined FTIR, X-ray absorption (XAS) and emission (XES) spectroscopies with DFT computational analysis to elucidate the nature and location of the most abundant Cu sites in the activated catalyst. Different Cu species have been found to be dominant as a function of the dehydration temperature and conditions. Data analysis revealed that the dehydration process of Cu cations is essentially completed at 250 °C, with the formation of dehydrated [CuOH]⁺ species hosted in close proximity to 1-Al sites in both d6r and 8r units of the SSZ-13 matrix. These species persist at higher temperatures only if a certain amount of O₂ is present in the gas feed, while under inert conditions they undergo virtually total “self-reduction” as a consequence of an OH extra-ligand loss, resulting in bi-coordinated bare Cu⁺ cations. Synchrotron characterization supported by computational analysis allowed an unprecedented quantitative refinement of the local environment and structural parameters of these Cu(ii) and Cu(i) species.     

Reversible cation/anion extraction from K2La2Ti3O10: formation of new layered titanates, KLa2Ti3O9.5 and La2Ti3O9

A new soft-chemical transformation of layered perovskite oxides is described wherein K2O is sequentially extracted from the Ruddlesden-Popper (R-P) phase, K2La2Ti3O10 (I), yielding novel anion-deficient KLa2Ti3O(9.5) (II) and La2Ti3O9 (III). The transformation occurs in topochemical reactions of the R-P phase I with PPh4Br and PBu4Br (Ph = phenyl; Bu = n-butyl). The mechanism involves the elimination of KBr accompanied by decomposition of PR4+ (R = phenyl or n-butyl) that extracts oxygen from the titanate. Analysis of the organic products of decomposition reveals formation of Ph3PO, Ph3P, and Ph-Ph for R = phenyl, and Bu3PO, Bu3P along with butane, butene, and octane for R = butyl. The inorganic oxides II and III crystallize in tetragonal structures (II: P4/mmm, a = 3.8335(1) A, c = 14.334(1) A; III: I4/mmm, a = 3.8565(2) A, c = 24.645(2) A) that are related to the parent R-P phase. II is isotypic with the Dion-Jacobson phase, RbSr2Nb3O10, while III is a unique layered oxide consisting of charge-neutral La2Ti3O9 anion-deficient perovskite sheets stacked one over the other without interlayer cations. Interestingly, both II and III convert back to the parent R-P phase in a reaction with KNO3. While transformations of the R-P phases to other related layered/three-dimensional perovskite oxides in ion-exchange/metathesis/dehydration/reduction reactions are known, the simultaneous and reversible extraction of both cations and anions in the conversions K2La2Ti3O10 right harpoon over left harpoon KLa2Ti3O9.5 right harpoon over left harpoon La2Ti3O9 is reported here for the first time.     

Formation of the Compound La2BaCuO5 (La4Ba2Cu2O10)

Synthesis of the compound La₂BaCuO₅ (La₄Ba₂Cu₂O_{1 0}), whose X-ray diffraction pattern is identical to that available in the literature for the solid solution La_3.6Ba_2.4Cu_1.8O_9.6, was studied.     

Zur Kenntnis von Na5HI2O10 · 14 H2O

On Na₅HI₂O₁₀ · 14 H₂O Single crystals of Na₅HI₂O₁₀ · 14 H₂O were obtained for the first time. According to the results of an X-ray crystal structure determination (P1 , a = 8.450(7), b = 8.533(6), c = 9.066(6) Å, α = 76.96(6), β = 62.94(5), γ = 86.98(6°, Z = 1, 4970 diffractometer data) iodine is in a distorted octahedral coordination. Two IO₆ polyhedra are connected by a common edge forming dimeric anions H₂I₂O₁₀^4?, the site symmetry is 1 . Sodium exhibits C.N. 6 (mainly hydrate). A 3-d network is formed largely by H-bonds.     

NMR Study of Intercalates and Grafted Organic Derivatives of H2La2Ti3O10

The protonated perovskite-like titanate H₂La₂Ti₃O₁₀ has been used to produce organic-inorganic hybrids with simple organic molecules: methylamine, methanol, monoethanolamine, and n-butylamine. The optimal pathways for the preparation of such hybrids are summarized. Solid-state NMR, combined with thermal analysis, Raman, and IR spectroscopy, has been applied to determine the bonding type in the obtained organic-inorganic hybrids. It has been found that, in the methanolic hybrid, the organic residues are covalently bound to the inorganic matrix. In contrast, in the methylamine and n-butylamine hybrids, the organic molecules are intercalated into the inorganic matrix in cationic forms. The structure of the monoethanolamine hybrid is composite and includes both the covalently bound and intercalated organic species.     

Kristallstruktur von Na5P3O10 · 6 H2O

Crystal Structure of Na₅P₃O₁₀ · 6 H₂O Na₅P₃O₁₀ · 6 H₂O crystallizes triclinic in P1 with a = 1 037.0(2), b = 984.8(4), c = 761.5(3) pm; α = 92.24(7)°, β = 94.55(9), γ = 90.87(6)°; Z = 2. The structure has been determined from fourcycle diffractometer data (2 089 independent reflections, R = 0.053). All hydrogen positions have been taken from a weighted difference-fourier-syntheses. Na₅P₃O₁₀ · 6 H₂O forms colorless, plate-like crystals, which are twinned systematically parallel (001) and can be divided mechanically into single-crystalline portions.     

Aerosol-Gel Deposition of Optically Active Thin Films in the System Y2Ti2O7-Er2Ti2O7

Optically active thin films in the system Y₂Ti₂O₇-Er₂Ti₂O₇ (YETO) have been deposited using the Aerosol-gel process. Depending on the heat-treatment temperature, amorphous or crystalline films could be prepared in the range 600–950°C. The study shows that dilution of erbium ions within a Y₂Ti₂O₇ (YTO) matrix allows to prevent short range distance interactions between those ions and to promote good photoluminescence properties of YETO films. These properties are discussed and compared with those of sol-gel derived silica films doped with erbium.     

层状光催化材料H2La2Ti3O10/CdS的制备及其性质研究

通过改善酸交换过程,用分步柱撑法制备了一种新的层柱材料H2La2Ti3O10/CdS.用X射线粉末衍射（XRD）、红外光谱（IR）、比表面（BET）等方法对材料进行了表征;以光催化降解苯胺为探针对材料的活性进行了研究.结果表明： 通过柱撑CdS,H2La2Ti3O10的光催化性能得到明显提高;同时,对试验条件进行了优化,得到了最佳催化反应条件.     

Fractional precipitation synthesis and photoluminescence of La2Ti2O7:xEu3+ phosphors

Eu³⁺ ions activated La₂Ti₂O₇ (La₂Ti₂O₇:xEu³⁺) phosphors have been successfully synthesized by a fractional precipitation method from commercially available La₂O₃, Eu₂O₃, HNO₃, Ti(SO₄)₂·9H₂O and NH₃·H₂O as the starting materials. Detailed characterizations of the synthetic products were obtained by fourier transform infrared spectroscopy (FT-IR), X-ray diffractometry (XRD), differential thermal analysis, thermogravimetry and derivative thermogravimetry (DTA-TG-DTG), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy. The results show that the precursor is composed of amorphous particles with quasi-spherical in shape and about 50 nm in size. Moreover, the precursor could be converted into pure La₂Ti₂O₇ phase by calcining at 1000 °C for 2 h in air. The as-synthesized La₂Ti₂O₇ particles are approximate polyhedron in shape and about 100–200 nm in size. PL spectroscopy of La₂Ti₂O₇:xEu³⁺ phosphors reveals that the strongest emission peak is located at 616 nm under 275 nm ultraviolet (UV) light excitation, which corresponds to the ⁵D₀→⁷F₂ transition of Eu³⁺ ions. The quenching concentration of Eu³⁺ ions is 10.0 mol%, and its corresponding fluorescence lifetime was 1.82 ms according to the linear fitting result. Decay study reveals that the ⁵D₀→⁷F₂ transition of Eu³⁺ ions has a single exponential decay behavior.     

Photocatalytic degradation of azophloxine on porous La2Ti2O7 prepared by sol-gel method

Cetyltrimethyl ammonium bromide (CTAB) was used in a sol-gel route to synthesize porous lanthanum titanate. The materials are composed of perovskite La₂Ti₂O₇ in monoclinic system. The addition of CTAB does not cause phase transformation, but leads to a slight decreasing tendency of La₂Ti₂O₇ crystallite size. Both the pore volume and pore size distribution range are enlarged after using CTAB. The sample obtained with 4 g CTAB has the maximum BET specific surface area of 42.4 m²/g. When the amount of CTAB is less than 4 g, the increase in photocatalytic degradation efficiency is almost in linear relationship to the amount of CTAB. The reaction rate constants are 0.0032, 0.0116 and 0.0237 min⁻¹ on the La₂Ti₂O₇ samples obtained using 0, 2 and 4 g CTAB. The functional groups in azophloxine molecule are decomposed during photocatalytic oxidation with extending irradiation time.     

Preparation of Pt/K_2La_2Ti_3O_(10) and its photo-catalytic activity for hydrogen evolution from methanol water solution

1 Introduction Conventional energy resources, such as coal, petro-leum products, etc., which are fulfilling most of the world’s energy requirement have been depleted to a great extend. The human being is now facing exhaus-tion of fuel resources in a near…     

Mg2Na2V10O28·20H2O and Mg3V10O28·28H2O

The crystal structures of dimagnesium disodium decavanadate icosahydrate, Mg₂Na₂V₁₀O₂₈·20H₂O, (I), and trimagnesium decavanadate octacosahydrate, Mg₃V₁₀O₂₈·28H₂O, (II), have been determined by single‐crystal X‐ray diffraction. They crystallize with monoclinic (C2/c) and triclinic () symmetry, respectively. All the Mg²⁺ cations in (I) and (II) are octahedrally coordinated by six water mol­ecules. The Na⁺ cations in (I) are coordinated by three water mol­ecules and three O atoms of the decavanadate anions, and link the latter into a three‐dimensional network. The decavanadate anions in (II) are not linked to one another.     

Cu3V10O28·24H2O and CuNa4V10O28·23H2O

The crystal structures of tricopper decavanadate tetracosa­hydrate, (I), and copper tetra­sodium decavanadate tricosa­hydrate, (II), have been determined by single‐crystal X‐ray diffraction. Both compounds exhibit a catenary structure consisting of [V₁₀O₂₈]⁶⁻ anions linked by Cu²⁺ cations in (I) or by Na⁺ cations in (II). Compound (II) also contains a polymeric linear array of edge‐sharing [Na(OH₂)₆]⁺ and [Cu(OH₂)₆]²⁺ octahedra. In both compounds, the [V₁₀O₂₈]⁶⁻ ions lie about inversion centres and the Cu²⁺ ions in (I) also lie about inversion centers.     

Thermodynamic properties of calcium titanates: CaTiO3, Ca4Ti3O10, and Ca3Ti2O7

The chemical potentials of CaO in two-phase fields (TiO₂ + CaTiO₃), (CaTiO₃ + Ca₄Ti₃O₁₀), and (Ca₄Ti₃O₁₀ + Ca₃Ti₂O₇) of the pseudo-binary system (CaO + TiO₂) have been measured in the temperature range (900 to 1250) K, relative to pure CaO as the reference state, using solid-state galvanic cells incorporating single crystal CaF₂ as the solid electrolyte. The cells were operated under pure oxygen at ambient pressure. The standard Gibbs free energies of formation of calcium titanates, CaTiO₃, Ca₄Ti₃O₁₀, and Ca₃Ti₂O₇, from their component binary oxides were derived from the reversible e.m.f.s. The results can be summarised by the following equations: CaO(solid) + TiO₂(solid) → CaTiO₃(solid), ΔG° ± 85/(J · mol^?1) = ?80,140 ? 6.302(T/K); 4CaO(solid) + 3TiO₂(solid) → Ca₄Ti₃O₁₀(solid), ΔG° ± 275/(J · mol^?1) = ?243,473 ? 25.758(T/K); 3CaO(solid) + 2TiO₂(solid) → Ca₃Ti₂O₇(solid), ΔG° ± 185/(J · mol^?1) = ?164,217 ? 16.838(T/K).The reference state for solid TiO₂ is the rutile form. The results of this study are in good agreement with thermodynamic data for CaTiO₃ reported in the literature. For Ca₄Ti₃O₁₀ Gibbs free energy of formation obtained in this study differs significantly from that reported by Taylor and Schmalzried at T = 873 K. For Ca₃Ti₂O₇ experimental measurements are not available in the literature for direct comparison with the results obtained in this study. Nevertheless, the standard entropy for Ca₃Ti₂O₇ at T = 298.15 K estimated from the results of this study using the Neumann–Koop rule is in fair agreement with the value obtained from low-temperature heat capacity measurements.     

Syntheses, crystal structures, and physical properties of La5Cu6O4S7 and La5Cu6.33O4S7

Single crystal and bulk powder samples of the quaternary lanthanum copper oxysulfides La5Cu6.33O4S7 and La5Cu6O4S7 have been prepared by means of high-temperature sealed-tube reactions and spark plasma sintering, respectively. In the structure of La 5Cu6.33O4S7, Cu atoms tie together the fluorite-like (2)infinity[La5O4S(5+)] and antifluorite-like (2) infinity[Cu6S6(5-)] layers of La5Cu6O4S7. The optical band gap, E g, of 2.0 eV was deduced from both diffuse reflectance spectra on a bulk sample of La5Cu6O4S7 and for the (010) crystal face of a La 5Cu6.33O4S7 single crystal. Transport measurements at 298 K on a bulk sample of La 5Cu 6O 4S 7 indicated p-type metallic electrical conduction with sigma electrical =2.18 S cm(-1), whereas measurements on a La 5Cu6.33O4S7 single crystal led to sigma electrical =4.5 10(-3) S cm(-1) along [100] and to semiconducting behavior. In going from La 5Cu6O4S7 to La5Cu6.33O4S7, the disruption of the (2)infinity[Cu6S6(5-)] layer and the decrease in the overall Cu(2+)(3d(9)) concentration lead to a significant decrease in the electrical conductivity.