Efficient Microwave-Assisted Functionalization of the Aurivillius-Phase Bi₂SrTa₂O₉

Abstract

A new method of acidification and subsequent functionalization of the Aurivillius-phase Bi2SrTa2O9 (BST), using microwave irradiation, was developed. This method enables to obtain hybridized phases from layered BST. Functionalization of BST by various kinds of amines and diamines can be achieved in a few hours only, compared to much longer time (over a week) using conventional heating. Good crystallinity of the compounds is kept. In addition, a microwave-assisted preintercalation strategy was developed, allowing inserting new amines (bearing cyclic or aromatic groups) between the oxide layers previously unseen in this type of compound. This work opens new perspectives for the fast and easy functionalization of layered oxides with more elaborated molecules.

Rapid Exfoliation and Surface Tailoring of Perovskite Nanosheets via Microwave‐Assisted Reactions

“…Organic modification was first carried out using linear n‐alkyl alcohols and n‐alkylamines, C n H 2n+1 OH ( n =3, 5 and 10) and C n H 2n+1 NH 2 ( n =3, 4, 6 and 10), respectively, and then further extended to saturated and unsaturated cyclic and linear alcohols. Even though only linear amines were studied here, the future scope of surface modifications could be very wide especially considering the high reactivity of layered perovskites with a variety of amines (linear and cyclic) . The XRD patterns of these hybrids are presented in Figure , which suggests a restacking behavior when the organic surface groups are moderately long; sharper peaks are observed for C n H 2 n +1 OH ( n =5 and 10), C n H 2 n +1 NH 2 ( n =4, 6 and 10), 6‐chloro‐1‐hexanol, and 3‐phenoxybenzyl alcohol.…”

“…Even though only linear amines were studied here, the future scope of surface modificationsc ould be very wide especially considering the high reactivity of layered perovskitesw ith av ariety of amines (linear and cyclic). [135,138] The XRD patterns of these hybrids are presented in Figure 8, which suggestsarestacking behavior when the organic surface groups are moderatelyl ong;s harper peaks are observed for C n H 2n + 1 OH (n = 5a nd 10), C n H 2n + 1 NH 2 (n = 4, 6a nd 10), 6chloro-1-hexanol, and 3-phenoxybenzyl alcohol. In case of shorter substituents( n-propylammonium-, n-propoxy-, benzyl alcoxy-, and phenylphosphonic-), as well as very long ones (such as PEG-400), the XRD patterns appear noisier with broader first reflections, which is consistent with poor restacking order within reassembled samples.…”

“…Rapid microwave‐assisted (MA) methods have been found to be effective for organic modification of bulk layered perovskites . Herein we extend microwave methods to both the rapid exfoliation and post‐exfoliation surface‐modification of perovskite nanosheets.…”

“…[70,71,134,135] Rapid microwave-assisted (MA) methods have been found to be effective for organicm odification of bulk layered perovskites. [136][137][138][139] Herein we extend microwave methods to both the rapid exfoliation and post-exfoliation surface-modification of perovskite nanosheets. MA reactions allow exfoliations and subsequents urfacem odifications to be carried out in as little as 1h,r espectively.E xfoliation utilizes the protonated doublelayered Dion-Jacobson perovskite (HLnNb 2 O 7 ;L n = La, Pr) where reactions with TBAOH quickly lead to dispersed materials.…”

Layered Simple Hydroxides Functionalized by Fluorene‐Phosphonic Acids: Synthesis, Interface Theoretical Insights, and Magnetoelectric Effect

“…[26][27][28][29][30] Such kind of preintercalation strategy is often used for the functionalization of layered materials, hexathiohypodiphosphates (MPS 3 ), [52,53] zirconium phosphate, [54][55][56] layered double hydroxides (LDH), [57] or layered oxides. [58][59][60] It consists in prefunctionalizing the starting compound by a molecule which is further removed to allow the insertion of the desired species. In the case of LSH, we have developed the prefunctionalization by dodecylsulfate or dodecylsulfonate, which is very efficient to allow the insertion-grafting of bulky or fragile molecules.…”