TY - JOUR

T1 - Highly Efficient Liquid-Phase Exfoliation of Layered Perovskite-like Titanates HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd) into Nanosheets

AU - Курносенко, Сергей Алексеевич

AU - Минич, Яна Андреевна

AU - Силюков, Олег Игоревич

AU - Зверева, Ирина Алексеевна

PY - 2023/11/29

Y1 - 2023/11/29

N2 - Nanosheets of layered perovskite-like oxides attract researchers as building blocks forthe creation of a wide range of demanded nanomaterials. However, Ruddlesden–Popper phasesare difficult to separate into nanosheets quantitatively via the conventional liquid-phase exfoliationprocedure in aqueous solutions of bulky organic bases. The present study has consideredsystematically a relatively novel and efficient approach to a high-yield preparation of concentratedsuspensions of perovskite nanosheets. For this, the Ruddlesden–Popper titanates HLnTiO4 andH2Ln2Ti3O10 (Ln = La, Nd) have been intercalated by n-alkylamines with various chain lengths,exposed to sonication in aqueous tetrabutylammonium hydroxide (TBAOH) and centrifuged toseparate the nanosheet-containing supernatant. The experiments included variations of a wide rangeof conditions, which allowed for the achievement of impressive nanosheet concentrations in suspensionsup to 2.1 g/L and yields up to 95%. The latter were found to strongly depend on the lengthof intercalated n-alkylamines. Despite the less expanded interlayer space, the titanates modifiedwith short-chain amines demonstrated a much higher completeness of liquid-phase exfoliation ascompared to those with long-chain ones. It was also shown that the exfoliation efficiency dependsmore on the sample stirring time in the TBAOH solution than on the sonication duration. Analysisof the titanate nanosheets obtained by means of dynamic light scattering, electron and atomic forcemicroscopy revealed their lateral sizes of 30–250 nm and thickness of 2–4 nm. The investigated exfoliationstrategy appears to be convenient for the high-yield production of perovskite nanosheet-basedmaterials for photocatalytic hydrogen production, environmental remediation and other applications.

AB - Nanosheets of layered perovskite-like oxides attract researchers as building blocks forthe creation of a wide range of demanded nanomaterials. However, Ruddlesden–Popper phasesare difficult to separate into nanosheets quantitatively via the conventional liquid-phase exfoliationprocedure in aqueous solutions of bulky organic bases. The present study has consideredsystematically a relatively novel and efficient approach to a high-yield preparation of concentratedsuspensions of perovskite nanosheets. For this, the Ruddlesden–Popper titanates HLnTiO4 andH2Ln2Ti3O10 (Ln = La, Nd) have been intercalated by n-alkylamines with various chain lengths,exposed to sonication in aqueous tetrabutylammonium hydroxide (TBAOH) and centrifuged toseparate the nanosheet-containing supernatant. The experiments included variations of a wide rangeof conditions, which allowed for the achievement of impressive nanosheet concentrations in suspensionsup to 2.1 g/L and yields up to 95%. The latter were found to strongly depend on the lengthof intercalated n-alkylamines. Despite the less expanded interlayer space, the titanates modifiedwith short-chain amines demonstrated a much higher completeness of liquid-phase exfoliation ascompared to those with long-chain ones. It was also shown that the exfoliation efficiency dependsmore on the sample stirring time in the TBAOH solution than on the sonication duration. Analysisof the titanate nanosheets obtained by means of dynamic light scattering, electron and atomic forcemicroscopy revealed their lateral sizes of 30–250 nm and thickness of 2–4 nm. The investigated exfoliationstrategy appears to be convenient for the high-yield production of perovskite nanosheet-basedmaterials for photocatalytic hydrogen production, environmental remediation and other applications.

KW - Layered perovskite

KW - titanate

KW - suspension stability

KW - intercalation

KW - amine

KW - exfoliation

KW - intercalation

KW - layered perovskite

KW - nanosheets

KW - suspension stability

KW - titanate

UR - https://www.mendeley.com/catalogue/340ac879-90f3-3dd9-bd53-533a7960da4e/

U2 - 10.3390/nano13233052

DO - 10.3390/nano13233052

M3 - Article

VL - 13

JO - Nanomaterials

JF - Nanomaterials

SN - 2079-4991

IS - 23

M1 - 3052

ER -