Oleyl-phosphate-modified TiO2 nanoparticles (OP_TiO2) were prepared via phase transfer from an aqueous phase containing dispersed TiO2 nanoparticles to a toluene phase containing oleyl phosphate (OP, a mixture of monoester and diester), and employed for the preparation of OP_TiO2/cyclo-olefin polymer (COP) hybrid films with high-refractive indices. The modification of TiO2 by OP was essentially completed by reaction at room temperature for 8 h, and essentially all the TiO2 nanoparticles in the aqueous phase were transferred to the toluene phase. The infrared and solid-state 13C cross-polarization and magic-angle spinning (CP/MAS) NMR spectrum of OP_TiO2 showed the presence of oleyl groups originating from oleyl phosphate. The solid-state 31P MAS NMR spectrum of OP_TiO2 exhibited new signals at −1.4, 2.1, and 4.8 ppm, indicating the formation of Ti–O–P bonds. CHN and inductively coupled plasma analyses revealed that the major species bound to the TiO2 surface was tridentate CH3(CH2)7CH═CH(CH2)8P(OTi)3. These results clearly indicate that the surfaces of the TiO2 nanoparticles were modified by OP moieties via phase transfer. OP_TiO2/COP hybrid films exhibited excellent optical transparency up to 19.1 vol % TiO2 loading, and the light transmittance of the hybrid films with 19.1 vol % TiO2 loading was 99.8% at 633 nm. The refractive index of these hybrid films rose to 1.83.Keywords: cyclo-olefin polymer; oleyl phosphate; organic−inorganic hybrid; phase transfer; refractive index; surface modification; TiO2 nanoparticle;

Crystallization behavior of cubic boron nitride (c-BN) from amorphous boron nitride (a-BN) by high-pressure, high-temperature (HP-HT) treatment with the intentional addition of a controlled amount of water was studied. The a-BN precursor was prepared by pyrolysis of a boric acid-urea complex with urea/boric acid = 2 at 1000 °C for 3 h under an ammonia atmosphere. Hexagonal BN (h-BN) were initially crystallized from a-BN containing 2 mass% of water after HP-HT treatment at 7.7 GPa and 1200 °C, and the formation of c-BN was observed after 5 min. The crystallization of c-BN from a-BN containing 8 mass% of water after HP-HT treatment at 7.7 GPa and 1200 °C was observed even after 1 min, indicating that the crystallization of c-BN was promoted by increasing the amount of water added. In addition, since neither h-BN nor c-BN was crystallized from a-BN without intentional water addition after the same HP-HT treatment, the addition of water promoted the crystallization of both h-BN and c-BN from a-BN. Since no transformation from h-BN to c-BN was observed during HP-HT treatment at 7.7 GPa and 1200 °C, it was concluded that c-BN was directly crystallized from a-BN. After HP-HT treatment at 7.7 GPa and 1650 °C for 1 min, both h-BN and c-BN were crystallized from a-BN containing 8 mass% of water. These results clearly indicate that the addition of water has a positive effect on crystallization of c-BN from a-BN.

Transparent TiO2/PMMA hybrids with a thickness of 5 mm and improved refractive indices were prepared by in situ polymerization of methyl methacrylate (MMA) in the presence of TiO2 nanoparticles bearing poly(methyl methacrylate) (PMMA) chains grown using surface-initiated atom transfer radical polymerization (SI-ATRP), and the effect of the chain length of modified PMMA on the dispersibility of modified TiO2 nanoparticles in the bulk hybrids was investigated. The surfaces of TiO2 nanoparticles were modified with both m-(chloromethyl)phenylmethanoyloxymethylphosphonic acid bearing a terminal ATRP initiator and isodecyl phosphate with a high affinity for common organic solvents, leading to sufficient dispersibility of the surface-modified particles in toluene. Subsequently, SI-ATRP of MMA was achieved from the modified surfaces of the TiO2 nanoparticles without aggregation of the nanoparticles in toluene. The molecular weights of the PMMA chains cleaved from the modified TiO2 nanoparticles increased with increases in the prolonging of the polymerization period, and these exhibited a narrow distribution, indicating chain growth controlled by SI-ATRP. The nanoparticles bearing PMMA chains were well-dispersed in MMA regardless of the polymerization period. Bulk PMMA hybrids containing modified TiO2 nanoparticles with a thickness of 5 mm were prepared by in situ polymerization of the MMA dispersion. The transparency of the hybrids depended significantly on the chain length of the modified PMMA on the nanoparticles, because the modified PMMA of low molecular weight induced aggregation of the TiO2 nanoparticles during the in situ polymerization process. The refractive indices of the bulk hybrids could be controlled by adjusting the TiO2 content and could be increased up to 1.566 for 6.3 vol % TiO2 content (1.492 for pristine PMMA).Keywords: dispersibility; surface-initiated atom transfer radical polymerization; TiO2/PMMA hybrids; transparency;

Triethylphosphine oxide [(C2H5)3PO; TEPO] was intercalated into protonated Dion–Jacobson-type ion-exchangeable layered perovskites, HLaNb2O7·xH2O (HLaNb) and HCa2Nb3O10·xH2O (HCaNb), by hydrolysis of their n-decoxy derivatives (C10O-HLaNb or C10O-HCaNb) in the presence of TEPO. The interlayer distances of the products (TEPO/C10O-HLaNb and TEPO/C10O-HCaNb) were smaller than those of the corresponding n-decoxy derivatives, but still larger than those of anhydrous protonated forms of HLaNb and HCaNb. The solid-state 31P NMR signals of the products observed at 94 ppm (TEPO/C10O-HLaNb) and 93 ppm (TEPO/C10O-HCaNb) exhibited large downfield shifts from that of the physisorbed TEPO. IR spectroscopy also showed decreases in the ν(PO) band wavenumbers upon the reactions. These results clearly indicate that TEPO is intercalated and interacted with Brønsted acid sites, the surface hydroxyl groups generated via hydrolysis of n-decoxy groups. The difference in ν(PO) band wavenumbers as well as that in gallery heights suggests that TEPO exhibited different orientations with respect to the inorganic layers. The chemical shifts of solid-state 31P NMR signals suggested high Brønsted acidity of HLaNb and HCaNb.

Nanosheets bearing CF3(CF2)7C2H4O groups on their surface were prepared from a CF3(CF2)7C2H4O derivative of ion-exchangeable layered perovskite HLaNb2O7·xH2O (HLaNb) via exfoliation, and were further utilized to prepare epoxy-based hybrids. The CF3(CF2)7C2H4O derivative of HLaNb (C10F_HLaNb) was prepared by reacting the n-decoxy derivative of HLaNb with 1H,1H,2H,2H-perfluorodecanol, CF3(CF2)7C2H4OH. TEM and AFM observations revealed that the C10F_HLaNb was exfoliated into individual nanosheets bearing surfaces covered with CF3(CF2)7C2H4O groups after ultrasonication in acetonitrile. The nanosheet dispersion in acetonitrile was employed to prepare epoxy-based hybrids, and the FE-TEM image of the epoxy-based hybrid with 5 mass% of the nanosheets (C10F_HLaNb/epoxy_5) showed that the nanosheets were dispersed in the epoxy matrix. Thermogravimetry of C10F_HLaNb/epoxy_5 and neat epoxy resin indicated that the initial mass loss due to water decreased and the thermal decomposition retarded by introducing C10F_HLaNb nanosheets. Dynamic mechanical thermal analysis revealed that the glass transition temperature of C10F_HLaNb/epoxy_5 (161 °C) was higher than that of neat epoxy resin (110 °C). These results clearly exhibit that thermal properties were improved by incorporating nanosheets bearing hydrophobic CF3(CF2)7C2H4O groups in the epoxy resin most likely due to a decrease in water content. A water uptake test demonstrated that the water uptake rate of C10F_HLaNb/epoxy_5 was lower than that of the neat epoxy.

Organically modified niobate nanosheets are promising building blocks for the design of advanced hybrid materials. Nanosheets with controlled thickness and surface composition are important for precise structural design of the nanosheet-based materials. In this work, single-layered and double-layered niobate nanosheets functionalized by phenylphosphonate moieties were selectively prepared by interlayer grafting of A-type and B-type intercalation derivatives of potassium hexaniobate (K4Nb6O17·3H2O) with phenylphosphonic acid (PPA), followed by exfoliation by ultrasonication in acetonitrile. The interlayer grafting of PPA was monitored using X-ray diffraction (XRD), Fourier transform infrared (FTIR), and solid-state NMR spectroscopy, and the thicknesses of the exfoliated nanosheets were measured by atomic force microscopy (AFM). Transparent hybrid films were obtained by incorporating the single- and double-layered nanosheets into an epoxy matrix.

TiO2 nanoparticles were prepared from titanium tetrachloride (TiCl4) in CH2Cl2 at 80 °C for 30 h, 42 h and 70 h using urea hydrogen peroxide (UHP) as an oxygen donor with a TiCl4:UHP molar ratio of 1:2. The XRD patterns and Raman spectroscopy results showed that the products consisted of anatase TiO2. IR and solid-state 13C NMR with cross polarization and magic angle spinning techniques revealed the presence of urea. TEM observation revealed that the products prepared by the reactions for 30 and 42 h consisted of water-dispersible spheroid nanoparticles with a long axis of ~5 nm, while an aggregation of nanoparticles was evident upon reaction for 70 h. Thermogravimetry, inductively-coupled plasma emission spectrometry and CHN analysis showed that the amount of urea increases in the following order: TiO2_42h, TiO2_70h, TiO2_30h. The photocatalytic activity of the products dispersible in water (TiO2_30h and TiO2_42h) was estimated based on the degradation behaviour of methylene blue, and TiO2_42h showed higher photocatalytic activity than TiO2_30h. It is proposed that TiCl4 was directly oxidized by UHP to form anatase TiO2 in the early stage of the process.

Microstructural behavior of γ-Fe2O3 formation in reactions between FeOCl and n-C5H11ONa was thoroughly investigated. Reactions were conducted at 50–150 °C for 3 days in an autoclave using n-C5H11OH as a solvent. X-ray diffraction (XRD) patterns and infrared (IR) spectra of the products suggested the crystallization of γ-Fe2O3 besides the formation of n-pentoxy derivatives of FeOCl. Scanning electron microscopic observation revealed that the FeOCl particles were divided into thin sheets upon reaction. The selected area electron diffractions (SAED) of the sheets revealed the crystallization of γ-Fe2O3 at even 80 °C, apparently due to the fact that the γ-Fe2O3 crystallization process involved a collapse from n-pentoxide derivatives with large separations between two adjacent layers. In the reaction at 150 °C, a part of the sheets was converted into highly oriented polycrystalline γ-Fe2O3 in improved crystallinity, and the SAED clearly showed that an oriented transformation with a crystallographic relationship of FeOCl (010)//γ-Fe2O3 (110) occurred. The reaction at 120 °C, on the contrary, led to the formation of randomly oriented γ-Fe2O3 crystallites within a sheet.Graphical abstractHighlights► Formation of n-pentoxide derivatives of FeOCl in all the reactions. ► γ-Fe2O3 crystallites formation in the reactions at 80 and 120 °C. ► Highly oriented polycrystalline γ-Fe2O3 formation of in the reaction at 150 °C. ► γ-Fe2O3 crystallized from the n-pentoxide derivatives of FeOCl. ► Crystallographic FeOCl (010)//γ-Fe2O3 (110) relationship in the reaction at 150 °C.

The hydrolysis behavior of 1,4-bis(triethoxysilyl)benzene (BTB), a precursor of bridged polysilsesquioxane, was investigated with high-resolution 29Si nuclear magnetic resonance (29Si NMR) spectroscopy at ambient temperature in a system with BTB:ethanol:water:HCl = 1:10:x:0.8 × 10−4 (x = 3, 6 or 9). Signals due to hydrolyzed triethoxysilyl groups as well as unhydrolyzed triethoxysilyl groups [−Si(OEt)3, −Si(OEt)2(OH), −Si(OEt)(OH)2 and −Si(OH)3 (OEt = OCH2CH3)] formed four sub-regions based on the number of hydroxyl groups bound to a silicon atom. In addition, one silicon environment influenced the other silicon environment by an intra-molecular interaction between two silicon atoms, and each sub-region for monomeric species thus contained four signals. Based on the development of signal intensity, it is revealed that one of the two triethoxysilyl groups in BTB is hydrolyzed preferentially. Thus, when a triethoxysilyl group is hydrolyzed, the −Si(OH)x(OEt)3−x (x = 1, 2) groups formed undergo further hydrolysis, which is opposite to the tendency expected from the hydrolysis behavior of organotrialkoxysilanes under acidic conditions.

The interlayer surface of a protonated form of the Dion−Jacobson-type ion-exchangeable layered perovskite, HLaNb2O7·xH2O (HLaNb), has been successfully modified with various organophosphonic acids [phenylphosphonic acid (PhPO(OH)2, PPA) and n-alkylphosphonic acids (n-CnH2n+1PO(OH)2 with n = 4−18, APAs)] to produce graft-type organic derivatives using an n-decoxy derivative of HLaNb (C10O-HLaNb) as an intermediate. The interlayer distances of the products are changed from that of the intermediate, 2.73 nm, to 2.31 (PPA/C10O-HLaNb) and 2.31−5.26 (APAs/C10O-HLaNb) nm. IR and solid-state 13C CP/MAS NMR spectra of the products reveal that n-decoxy groups are removed and phenyl (PPA/C10O-HLaNb) or n-alkyl groups (APA/C10O-HLaNb) are introduced. Elemental analysis reveals that the amounts of PPA- and APA-moieties are 0.88−0.99 per [LaNb2O7], corresponding approximately to the amount of the n-decoxy groups in C10O-HLaNb. The environment of interlayer species in PPA/C10O-HLaNb is assumed to be monodentate PhPO(OH)(ONb) based on the IR results (the P−O stretching and P−OH stretching bands at ∼1030 and ∼950 cm−1) and the reaction between PPA/C10O-HLaNb and n-butylamine (−NH2/POH = 1.0). Scanning electron micrographs of the products reveal that the morphology is clearly preserved during the reactions with PPA or APAs, indicating that they are graft-type rather than dissolution−recrystallization-type reactions. Because water is required for the reaction between PPA and C10O-HLaNb, this reaction is assumed to proceed via the formation of an (HO)NbO5 site and its subsequent reaction with PPA. A linear relationship is clearly observed between the number of carbon atoms in the n-alkyl chains and the interlayer distances of APAs/C10O-HLaNb, and a structural model of APAs/C10O-HLaNb with a n-alkyl chain tilt angle of 57° is proposed.

Polyether chains have been successfully grafted onto the interlayer surface of a Dion–Jacobson-type layered perovskite, HLaNb2O7·xH2O, by a reaction between an n-decoxy-derivative of HLaNb2O7·xH2O and CH3(OCH2CH2)mOH (1 ≤ m ≤ 4). After the reaction, the interlayer distance decreases from 2.73 nm to 1.58 (m = 1), 2.07 (m = 2), 2.28 (m = 3), and 2.69 (m = 4) nm. Solid-state 13C CP/MAS NMR spectroscopy indicates that the CH3(OCH2CH2)mO– groups are bound to the interlayer surface of HLaNb2O7·xH2O. The n-decoxy groups are completely removed by the reaction with CH3(OCH2CH2)mOH (m = 2 and 3), while a part of the n-decoxy groups remain after the reaction with CH3(OCH2CH2)mOH (m = 1 and 4). Upon treatment of the CH3(OCH2CH2)mO-grafted HLaNb2O7·xH2O (m = 2 or 3) with a CH3(OCH2CH2)mOH solution of LiClO4, the interlayer distance decreases further to 1.78 (m = 2) and 2.01 (m = 3) nm. Inductively coupled plasma emission spectrometry reveals the presence of lithium (0.22 (m = 2) and 0.24 (m = 3) per [LaNb2O7]). The presence of ClO4− ions is demonstrated by Raman spectroscopy, and the position of the ν1(A1) band indicates the presence of isolated ClO4− ions in the interlayer space. After treatment with a LiClO4 solution, CH3(OCH2CH2)mO-grafted HLaNb2O7·xH2O (m = 2 and 3) exhibits ionic conductivity, and no clear temperature dependence is observed.

The structure of Bi5Nb3O15 was investigated by refinement of the powder neutron diffraction pattern as well as by structural change through acid treatment and subsequent treatments of an acid-treated product with n-alkylamines. Rietveld refinement suggests that Bi5Nb3O15 adopts a mixed-layer Aurivillius-related phase structure, [Bi2O2]+[NbO4]+[Bi2O2]+[BiNb2O7] [Pnc  2 (space group No. 30)] with a=2.1011(4)a=2.1011(4), b=0.5473(1)b=0.5473(1) and c=0.5463(1)c=0.5463(1) nm. After the acid treatment of Bi5Nb3O15 with 3 mol/L HCl, a new reflection (at 2.25 nm after drying at room temperature or at 1.89 nm after drying at 120 °C) appeared in the X-ray diffraction (XRD) pattern in addition to the reflections due to Bi5Nb3O15. Upon acid treatment, a part of the Bi ions were lost and essentially no Nb ions were dissolved during acid treatment to give a Bi/Nb molar ratio of 1.4. The TG curves of the acid-treated product showed mass loss (ca. 4 mass%) in the range of 300–600 °C. It was also demonstrated that the particle shapes did not change upon acid treatment. The reaction of the acid-treated product (after drying at room temperature) with n-alkylamines led to a shift of the newly appearing reflection to a lower angle, and the d-value of the low-angle reflection increased linearly in accordance with the increment of the number of carbon atoms in n-alkylamines. These results indicate that the [Bi2O2] sheet in Bi5Nb3O15 was partially leached by acid treatment to form a layered compound H4BiNb3O11·xH2O, capable of accommodating n-alkylamines in the interlayer space, and its anhydrous form, H4BiNb3O11, upon drying. Based on the variation in the interlayer distance upon intercalation of n-alkylamines into the acid-treated product, the structure of the acid-treated product can be suggested to comprise alternately stacked protonated [BiNb2O7] and [NbO4] sheets, a result consistent with the Rietveld refinement of Bi5Nb3O15.Crystal structure of Bi5Nb3O15 is investigated by refinement of neutron diffraction pattern as well as by structural change through acid treatment of Bi5Nb3O15 and subsequent treatment of an acid-treated product with n-alkylamine.

The local environments and dynamics of hydrogen atoms in five samples of protonated forms of ion-exchangeable layered perovskites, Dion–Jacobson-type H[LaNb2O7] and H[LaTa2O7], Ruddlesden–Popper-type H2[SrTa2O7] and H2[La2Ti3O10], and H1.8[(Sr0.8Bi0.2)Ta2O7] derived from an Aurivillius phase, Bi2Sr2Ta2O9, have been investigated by solid-state 1H nuclear magnetic resonance spectroscopy (NMR). Solid-state 1H NMR with a magic-angle spinning technique conducted at room temperature reveals that the mean electron densities around the 1H nuclei in these protonated forms are relatively low, and that they decrease in the following order: H1.8[(Sr0.8Bi0.2)Ta2O7]>H[LaNb2O7]>H2[SrTa2O7]>H[LaTa2O7]>H2[La2Ti3O10]. The temperature-dependent solid-state 1H broad-line NMR spectra measured at 140–400 K reveal a decrease in the signal width for all of these five samples upon heating due to motional narrowing. The NMR spectra of H[LaNb2O7] and H[LaTa2O7] are different from the other three protonated forms due to the weaker dipole–dipole interactions at low temperatures and lower mobility of the hydrogen atoms at high temperatures.Solid-state 1H MAS NMR spectra of protonated forms of ion-exchangeable layered perovskites: (a) H[LaNb2O7]; (b) H[LaTa2O7]; (c) H1.8[(Sr0.8Bi0.2)Ta2O7]; (d) H2[SrTa2O7]; and (e) H2[La2Ti3O10]. The spinning side bands are marked with asterisks.

The structures of sol–gel derived hybrid gels prepared by co-hydrolysis of tetraethoxysilane (TEOS)-organotrialkoxysilane (RTES, RSi(OC2H5)3, R = CH3, C5H11, C8H17 and C6H5) mixtures (TEOS : RTES : CH3CH2OH : H2O : HNO3 = 0.5 : 0.5 : 10 : x : 0.3; x = 2, 5, 10 and 20) were characterized based on signal intensities of 29Si CP/MAS NMR as a function of the contact time. The contact time dependencies of the signals for Q4 (Si(OSi)4) units were successfully simulated by assuming distributed cross relaxation times (TSiH) and an intrinsic 1H spin-lattice relaxation time in the rotating frame (T1ρH); the latter was different from the apparent T1ρH value estimated by assuming single TSiH. The distribution ranges of TSiH for the TEOS–RTES gels broadened as the water content increased, suggesting that the Q4 units tended to be separated from the T units and that the local concentration of 1H spins around the Q4 unit tended to decrease.

The CC bonds immobilized in the interlayer space of layered perovskite, HLaNb2O7·xH2O, have undergone hydrosilylation reactions with chlorohydrosilanes. The CC bonds are immobilized by the reaction between an n-propoxyl derivative of HLaNb2O7·xH2O and 4-penten-1-ol to form a CH2CH(CH2)3O derivative of HLaNb2O7·xH2O, and a corresponding increase in the interlayer distance from 1.54 to 1.85 nm is observed. The CH2CH(CH2)3O derivative is further treated with dichloromethylsilane or trichlorosilane, and the interlayer distance increases to 2.41 (dichloromethylsilane) or 2.07 (trichlorosilane) nm. Solid-state 13C-CP/MAS-NMR spectroscopy and infra-red (IR) spectroscopy reveal that the CC groups disappear after the treatment with dichloromethylsilane or trichlorosilane, and 13C-NMR signals assignable to the hydrosilylated products are clearly observed. Besides hydrosilylation reactions, siloxane formation involving hydrolysis of the SiCl groups also proceeds. The structure of the perovskite-like slabs in HLaNb2O7·xH2O is preserved throughout the process, indicating the successful modification of immobilized CC groups via hydrosilylation with no structural change in the inorganic host layers.The CC bonds immobilized in the interlayer space of layered perovskite, HLaNb2O7·xH2O, have undergone hydrosilylation reactions with chlorohydrosilanes, dichloromethylsilane or trichlorosilane. The treatment of the CH2CH(CH2)3O- derivative of HLaNb2O7·xH2O with dichloromethylsilane or trichlorosilane leads to the interlayer distance increase to 2.41 (dichloromethylsilane) or 2.07 (trichlorosilane) nm. Solid-state 13C-CP/MAS-NMR and IR spectroscopies reveal the occurrence of hydrosilylation.

Triethylphosphine oxide [(C2H5)3PO; TEPO] was intercalated into protonated Dion–Jacobson-type ion-exchangeable layered perovskites, HLaNb2O7·xH2O (HLaNb) and HCa2Nb3O10·xH2O (HCaNb), by hydrolysis of their n-decoxy derivatives (C10O-HLaNb or C10O-HCaNb) in the presence of TEPO. The interlayer distances of the products (TEPO/C10O-HLaNb and TEPO/C10O-HCaNb) were smaller than those of the corresponding n-decoxy derivatives, but still larger than those of anhydrous protonated forms of HLaNb and HCaNb. The solid-state 31P NMR signals of the products observed at 94 ppm (TEPO/C10O-HLaNb) and 93 ppm (TEPO/C10O-HCaNb) exhibited large downfield shifts from that of the physisorbed TEPO. IR spectroscopy also showed decreases in the ν(PO) band wavenumbers upon the reactions. These results clearly indicate that TEPO is intercalated and interacted with Brønsted acid sites, the surface hydroxyl groups generated via hydrolysis of n-decoxy groups. The difference in ν(PO) band wavenumbers as well as that in gallery heights suggests that TEPO exhibited different orientations with respect to the inorganic layers. The chemical shifts of solid-state 31P NMR signals suggested high Brønsted acidity of HLaNb and HCaNb.

Polyether chains have been successfully grafted onto the interlayer surface of a Dion–Jacobson-type layered perovskite, HLaNb2O7·xH2O, by a reaction between an n-decoxy-derivative of HLaNb2O7·xH2O and CH3(OCH2CH2)mOH (1 ≤ m ≤ 4). After the reaction, the interlayer distance decreases from 2.73 nm to 1.58 (m = 1), 2.07 (m = 2), 2.28 (m = 3), and 2.69 (m = 4) nm. Solid-state 13C CP/MAS NMR spectroscopy indicates that the CH3(OCH2CH2)mO– groups are bound to the interlayer surface of HLaNb2O7·xH2O. The n-decoxy groups are completely removed by the reaction with CH3(OCH2CH2)mOH (m = 2 and 3), while a part of the n-decoxy groups remain after the reaction with CH3(OCH2CH2)mOH (m = 1 and 4). Upon treatment of the CH3(OCH2CH2)mO-grafted HLaNb2O7·xH2O (m = 2 or 3) with a CH3(OCH2CH2)mOH solution of LiClO4, the interlayer distance decreases further to 1.78 (m = 2) and 2.01 (m = 3) nm. Inductively coupled plasma emission spectrometry reveals the presence of lithium (0.22 (m = 2) and 0.24 (m = 3) per [LaNb2O7]). The presence of ClO4− ions is demonstrated by Raman spectroscopy, and the position of the ν1(A1) band indicates the presence of isolated ClO4− ions in the interlayer space. After treatment with a LiClO4 solution, CH3(OCH2CH2)mO-grafted HLaNb2O7·xH2O (m = 2 and 3) exhibits ionic conductivity, and no clear temperature dependence is observed.