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Nanosheets of layered perovskite-like oxides attract researchers as building blocks for the creation of a wide range of demanded nanomaterials. However, Ruddlesden–Popper phases are difficult to separate into nanosheets quantitatively via the conventional liquid-phase exfoliation procedure in aqueous solutions of bulky organic bases. The present study has considered systematically a relatively novel and efficient approach to a high-yield preparation of concentrated suspensions of perovskite nanosheets. For this, the Ruddlesden–Popper titanates HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd) have been intercalated by n-alkylamines with various chain lengths, exposed to sonication in aqueous tetrabutylammonium hydroxide (TBAOH) and centrifuged to separate the nanosheet-containing supernatant. The experiments included variations of a wide range of conditions, which allowed for the achievement of impressive nanosheet concentrations in suspensions up to 2.1 g/L and yields up to 95%. The latter were found to strongly depend on the length of intercalated n-alkylamines. Despite the less expanded interlayer space, the titanates modified with short-chain amines demonstrated a much higher completeness of liquid-phase exfoliation as compared to those with long-chain ones. It was also shown that the exfoliation efficiency depends more on the sample stirring time in the TBAOH solution than on the sonication duration. Analysis of the titanate nanosheets obtained by means of dynamic light scattering, electron and atomic force microscopy revealed their lateral sizes of 30–250 nm and thickness of 2–4 nm. The investigated exfoliation strategy appears to be convenient for the high-yield production of perovskite nanosheet-based materials for photocatalytic hydrogen production, environmental remediation and other applications. [ABSTRACT FROM AUTHOR]

Structures of partially and completely protonated Ruddlesden-Popper phases, H0.7Na0.3NdTiO4·0.3H2O and HNdTiO4, have been established by means of neutron and X-ray diffraction analysis and compared among themselves as well as with that of the initial titanate NaNdTiO4. It was shown that while interlayer sodium cations in the partially protonated form are coordinated by nine oxygen atoms, including one related to intercalated water, in the fully protonated compound the ninth oxygen proves to be an axial anion belonging to the opposite slab of titanium-oxygen octahedra. Moreover, the partially protonated titanate was found to significantly differ from the other two in the octahedron distortion pattern. It is characterized by a weakly pronounced elongation of the octahedra towards the Nd-containing interlayer space making Ti4+ cations practically equidistant from both axial oxygen atoms, which is accompanied by a low-frequency shift of the bands relating to the asymmetric stretching mode of axial Ti-O bonds observed in the Raman spectra. [ABSTRACT FROM AUTHOR]

Two series of hybrid inorganic-organic derivatives, obtained via the modification of protonated Ruddlesden–Popper phases H2Ln2Ti3O10 (Ln = La, Nd) with intercalated n-alkylamines and grafted n-alkoxy groups, have been systematically investigated in relation to photocatalytic hydrogen production from a model of 1 mol % aqueous solution of methanol for the first time. Photocatalytic measurements were performed both for bare samples and for their composites with Pt nanoparticles as a cocatalyst using an advanced scheme, including dark stages, monitoring of the volume concentration of the sample in the reaction suspension during the experiment, shifts of its pH and possible exfoliation of layered compounds into nanolayers. It was found that the incorporation of organic components into the interlayer space of the titanates increases their photocatalytic activity up to 117 times compared with that of the initial compounds. Additional platinization of the hybrid samples' surface allowed for achieving apparent quantum efficiency of hydrogen evolution of more than 40%. It was established that the photocatalytic activity of the hybrid samples correlates with the hydration degree of their interlayer space, which is considered a separate reaction zone in photocatalysis, and that hydrogen indeed generates from the aqueous methanol solution rather than from organic components of the derivatives. [ABSTRACT FROM AUTHOR]

In the present work, we report the results on exfoliation and coating formation of inorganic–organic hybrids based on the layered perovskite-like bismuth titanate H2K0.5Bi2.5Ti4O13·H2O that could be prepared by a simple ion exchange reaction from a Ruddlesden–Popper phase K2.5Bi2.5Ti4O13. The inorganic–organic hybrids were synthesized by intercalation reactions. Exfoliation into nanosheets was performed for the starting hydrated protonated titanate and for the derivatives intercalated by n-alkylamines to study the influence of preliminary intercalation on exfoliation efficiency. The selected precursors were exfoliated in aqueous solutions of tetrabutylammonium hydroxide using facile stirring and ultrasonication. The suspensions of nanosheets obtained were characterized using UV–vis spectrophotometry, dynamic light scattering, inductively coupled plasma spectroscopy, and gravimetry. Nanosheets were coated on preliminarily polyethyleneimine-covered Si substrates using a self-assembly procedure and studied using atomic force and scanning electron microscopy. [ABSTRACT FROM AUTHOR]

A series of hybrid inorganic–organic niobates HCa2Nb3O10×ROH, containing n-alkoxy groups of primary alcohols (R = Me, Et, Pr, Bu, Hx, and Dc) grafted in the interlayer space, has been studied for the first time in relation to photocatalytic hydrogen generation from a model 1 mol % aqueous solution of methanol under ultraviolet irradiation. Photocatalytic activity was measured both for bare samples and for their composites with Pt nanoparticles as a cocatalyst. The advanced measurement scheme allowed monitoring the volume concentration of a sample in a suspension during the experiment, its pH, and possible exfoliation of layered compounds into nanolayers. In the series of n-alkoxy derivatives, the maximum rate of hydrogen evolution was achieved over a Pt-loaded ethoxy derivative HCa2Nb3O10×EtOH/Pt. Its apparent quantum efficiency of 20.6% in the 220–350 nm range was found not to be caused by changes in the light absorption region or specific surface area upon ethanol grafting. Moreover, the amounts of hydrogen released during the measurements significantly exceeded those of interlayer organic components, indicating that hydrogen is generated from the reaction solution rather than from the hybrid material. [ABSTRACT FROM AUTHOR]

A series of hybrid niobates HCa 2 Nb 3 O 10 ×RNH 2 , containing n -alkylamines (R = Me, Et, Pr, Bu, Hx, Oc) intercalated into the interlayer space, has been thoroughly studied concerning the photocatalytic hydrogen production from a model aqueous solution of methanol for the first time. All the hybrid photocatalysts were synthesized by the conventional ceramic technique followed by protonation and intercalation of n -alkylamines. The products were characterized using XRD, Raman, IR and diffuse reflectance spectroscopy, TGA, CHN-analysis and SEM. Photocatalytic measurements were conducted according to an advanced scheme taking into account possible changes in the photocatalyst concentration because of sedimentation, pH shifts and exfoliation of the samples into nanoplatelets. Special attention was also paid to the feasible improvement of the photocatalytic activity of the samples via their modification with Pt nanoparticles as a cocatalyst. In the series of amine derivatives, the highest rate of hydrogen generation was demonstrated by the Pt-loaded HCa 2 Nb 3 O 10 ×BuNH 2 reaching apparent quantum efficiency of 13% in the 220-340 nm range. The initial HCa 2 Nb 3 O 10 showed comparable efficiency of 8.3% that is greater than for other amine derivatives. It was demonstrated that for the investigated samples the photocatalytic activity correlates with their ability of water intercalation., (Copyright © 2020 Voytovich, Kurnosenko, Silyukov, Rodionov, Minich and Zvereva.)

New organic-inorganic hybrids have been synthesized by the intercalation of n -alkylamines (methylamine, ethylamine, n -propylamine, n -butylamine, n -hexylamine, and n -octylamine) into the structure of the protonated and hydrated form of the perovskite-like layered titanate H 2 K 0.5 Bi 2.5 Ti 4 O 13 ·H 2 O (HKBT 4 ·H 2 O). The possibility of the synthesis of the hybrid materials was studied in a wide range of conditions. It was found that interlayer water plays a crucial role in the formation of intercalated hybrids. The obtained compounds were characterized with powder X-ray diffraction analysis; Raman, IR, and NMR spectroscopies; thermogravimetry (TG), TG coupled with mass spectrometry, and CHN analyses; and scanning electron microscopy. It was suggested that the intercalated n -alkylamines exist in the form of alkylammonium ions forming a paraffin-like bilayer with an average tilting angle of ∼77.5°. The obtained HKBT 4 ×RNH 2 compounds contain 0.4-0.7 n -alkylamine molecules per formula unit as well as the varied amount of intercalated water. By gentle heating, they can be obtained as dehydrated forms, which are thermally stable up to 250 °C., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)