Synthesis of Organic–Inorganic Hybrids Based on Perovskite-like Bismuth Titanate H₂K_0.5Bi_2.5Ti₄O₁₃·H₂O and n-Alkylamines

Abstract

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 H2K0.5Bi2.5Ti4O13·H2O (HKBT4·H2O). 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 HKBT4×RNH2 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.

A Review on the Synthesis and Modification of Functional Inorganic‐Organic‐Hybrid Materials via Microwave‐Assisted Method

“…al has also synthesized new IOH's by n-alkylamines (methylamine, ethylamine, n-propylamine, nbutylamine, n-hexylamine, and n-octylamine) intercalation in protonated anhydrous and hydrated H 2 K 0.5 Bi 2.5 Ti 4 O 13 .H 2 O (HKBT 4 ⋅ H 2 O) perovskite-based layered titenates for the first time. [88] This recent study has shown that PXRD patterns of products obtained by the treatment of HKBT 4 .H 2 O with nalkylamines, cause a reasonable shift in (00 l) reflections towards lower 2θ, which stands the enlargement of interlayer space between perovskite slabs (Figure 6(a)). The broadening in reflections with lower intensities results from weak bonding interactions between the layers that provide turbostratic stacking disorder in the structure.…”

“…(a) PXRD patterns oftheprotonated form of HKBT 4 , HKBT 4 .0.5H 2 O, HKBT 4 .H 2 O and their inorganic-organic hybrids HKBT 4 × MeNH 2 , HKBT 4 × EtNH 2 , HKBT 4 × PrNH 2 , HKBT 4 × BuNH 2 , HKBT 4 × HxNH 2 and HKBT 4 × OcNH 2 . Their respective Raman and FT-IR spectra has been presented in (b) and (c).Reproduced with permission from Ref [88],. Copyright 2020, American Chemical Society.…”

Physical–Chemical Exfoliation of n-Alkylamine Derivatives of Layered Perovskite-like Oxide H2K0.5Bi2.5Ti4O13 into Nanosheets

“…The reactions were performed in optimized conditions reported earlier. [49] Namely, hybrids with methylamine, ethylamine, n-propylamine, and n-butylamine were obtained via the 24 h reaction at 60 • C using 38% (for methylamine) and 50% aqueous solutions. The reaction with n-hexylamine was performed at 80 • C in 50% solution in n-heptane.…”

“…The H 2 K 0.5 Bi 2.5 Ti 4 O 13 •H 2 O (HKBT 4 •H 2 O) structure can be described as an alternation of perovskite slabs (K 0.5 Bi 2.5 Ti 4 O 13 ) with interlayer protons and water molecules. It was shown that this protonated derivative is capable of intercalation of n-alkylamines [49] and grafting of n-alcohols in the interlayer space [50]. This work reports on exfoliating HKBT 4 •H 2 O and its n-alkylamine derivatives in a tetrabutylammonium hydroxide (TBAOH) aqueous solution to obtain stable suspensions of perovskite nanolayers and their coatings.…”

Protonated Forms of Layered Perovskite-Like Titanate NaNdTiO4: Neutron and X-ray Diffraction Structural Analysis

“…Over past decades, great attention has been paid to ion-exchangeable layered perovskitelike oxides as promising ionic conductors [1][2][3][4][5], catalysts [6], photocatalysts [7][8][9], multipurpose precursors for the creation of hybrid inorganic-organic materials [10][11][12][13][14][15][16][17][18], nanoelectronic [19], ferroelectric [20], piezoelectric [21], luminescent [22] and photovoltaic devices [23], chemical sensors [24] as well as fuel cells [25].…”