NMR Study of Intercalates and Grafted Organic Derivatives of H2La2Ti3O10

Shelyapina, Marina G.; Silyukov, Oleg I.; Lushpinskaia, Irina P.; Kurnosenko, Sergei A.; Mazur, Anton S.; Shenderovich, Ilya G.; Zvereva, Irina A.

doi:10.3390/molecules25225229

Cited by 15 publications

(4 citation statements)

References 76 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The main attention has been focused on water and water-alcohol mixtures [59][60][61][62][63][64][65]. Some other substances have been studies as well [66][67][68][69][70]. Interaction with the surface causes a change in the melting/freezing point of the adsorbate [71][72][73][74][75].…”

Section: H Nmrmentioning

confidence: 99%

Solid State NMR for Nonexperts: An Overview of Simple but General Practical Methods

Shenderovich

Limbach

2021

Solids

Self Cite

View full text Add to dashboard Cite

There are varieties of methods available for the exploration of solids using nuclear magnetic resonance (NMR) spectroscopy. Some of these methods are quite sophisticated, others require specialized equipment. This review is addressed to those for whom NMR is not the main research method. It discusses simple methods that can be applied to solids with little or no adaptation to a specific system. Despite their technical simplicity and ease of use, these methods are powerful analytical tools that provide unique insights into the structure, dynamics, and noncovalent interactions in homo- and heterogeneous systems. Particular attention is paid to the characterization of porous materials and solids containing phosphorus. 31P NMR of organometallic compounds has been used as an example of how theoretical calculations can help in deeper analysis of experimental data.

show abstract

Section: H Nmrmentioning

confidence: 99%

Solid State NMR for Nonexperts: An Overview of Simple but General Practical Methods

Shenderovich

Limbach

2021

Solids

Self Cite

View full text Add to dashboard Cite

show abstract

“…Functionalization of the interlayer space of the perovskite lamellar structures forms interstratified inorganic sheets and organic moieties, which in turn can be utilized to modify the interlayer spacing, and the properties of subsequent hybrid compounds. Grafting reactions typically utilize protonated forms of ion-exchangeable layered perovskites, where the protons are replaced with organic cations via an ion-exchange mechanism [ 14 , 15 ]. Interlayer organics can be replaced by other organics by treating the structure with a solution of the targeted compound.…”

Section: Introductionmentioning

confidence: 99%

The Grafting of Hydroxyaromatic Organics within Layered Perovskites via a Microwave-Assisted Method

Poduval,

Jones,

LeBan

et al. 2024

Molecules

View full text Add to dashboard Cite

A new series of inorganic–organic hybrid perovskite materials were prepared by microwave-assisted grafting reactions. Simple carboxylic acids, acetic acid, and propionic acid, as well as hydroxyaromatic carboxylic acids, 3,5-dihydroxy benzoic acid (DBA), 5-hydroxyisophthalic acid (HPA), 4-hydroxybenzoic acid (HBA), and 4-hydroxy-4-biphenyl carboxylic acid (HBCA), were reacted with the Dion–Jacobson double-layered perovskite, HLaNb2O7, and its alcoxy derivatives. Grafting was found to not occur with simple carboxylic acids, while those molecules with hydroxyls were all attached to the perovskite interlayers. Reactivity of the hydroxyaromatic carboxylic acids varied with the different layered perovskite hosts where reactions with HLaNb2O7 did not occur, and those with n-propoxy-LaNb2O7 were limited; the greatest extent of reactivity was seen with n-decoxy-LaNb2O7. This is attributed to the larger interlayer spacing available for the insertion of the various hydroxyaromatic carboxylic acid compounds. The loading exhibited by the grafting species was less than that seen with well-known long-chain alkoxy grafting groups. It is expected that the width of the molecules contributes to this where, due to the benzyl groups, the interlayer volume of the grafted moieties occupies a larger horizontal fraction, therefore minimizing the loading to the below half. X-ray powder diffraction and transmission electron microscopy studies found that grafting of the n-decoxy-LaNb2O7 intermediates with the series of hydroxyaromatics resulted in a reduction in crystallinity along with a disruption of the layer structure. Raman data on the series show little variation in local structure except for HBCA, where there appears to be a lengthening of the Nb-O apical linkage and a possible reduction in the distortion of inner-layer NbO6 octahedra. The optical properties of the hydroxyaromatic carboxylic acid grafted perovskites were also investigated using diffuse-reflectance UV-Vis spectroscopy. The band gaps of DBA, HPA, and HBA were found to be similar to the parent (Eg ≈ 3.4 eV), while the HBCA was significantly less by ca. 0.6 eV. This difference is attributed to electron withdrawal from the perovskite block to the HBCA ligand, leading to a lower band gap for the HBCA compound. The methods described herein allow for the formation of a new series of inorganic–organic hybrid materials where the products are of interest as precursors to more complex architectures as well as models for band gap modification of metal oxide photocatalysts.

show abstract

“…Perovskite-like oxides with a layered structure have been intensively studied both experimentally and theoretically due to the unique physicochemical properties exhibited by individual representatives of this class of compounds, such as high catalytic and photocatalytic activity [ 1 ], high-temperature superconductivity [ 2 ], and colossal magnetoresistance [ 3 ]. Most layered perovskite-like oxides capable of ion-exchange reactions [ 4 ] can be transformed into their protonated forms [ 5 , 6 ], which, on the one hand, are proton conductors [ 7 , 8 ] and photocatalysts for water splitting [ 1 , 9 ] and, on the other hand, exhibit the ability to intercalate water [ 10 , 11 ] and other molecules [ 12 , 13 ], give derivatives with grafted organic modifiers [ 14 , 15 , 16 , 17 ], and undergo exfoliation into nanolayers [ 18 , 19 ]. Materials based on layered oxides are promising objects for use as high-temperature ion conductors in fuel cells [ 20 ], catalysts in industrial reactions [ 21 ], as well as in devices for water and air purification [ 22 , 23 ], microelectronics [ 24 ], and photovoltaics [ 25 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Inorganic-Organic Derivatives of Layered Perovskite-like Niobate HSr2Nb3O10 with n-Amines and n-Alcohols

et al. 2023

Self Cite

View full text Add to dashboard Cite

A protonated and hydrated Dion-Jacobson-phase HSr2Nb3O10∙yH2O was used to prepare two series of inorganic–organic derivatives containing non-covalently intercalated n-alkylamines and covalently grafted n-alkoxy groups of different lengths, as they are promising hybrid materials for photocatalytic applications. Preparation of the derivatives was carried out both under the conditions of standard laboratory synthesis and by solvothermal methods. For all the hybrid compounds synthesized structure, quantitative composition, a type of bonding between inorganic and organic parts as well as light absorption range were discussed using powder XRD, Raman, IR and NMR spectroscopy, TG, elemental CHN analysis, and DRS. It was shown that the inorganic–organic samples obtained contain approximately one interlayer organic molecule or group per proton of the initial niobate, as well as some amount of intercalated water. In addition, the thermal stability of the hybrid compounds strongly depends on the nature of the organic component anchoring to the niobate matrix. Although non-covalent amine derivatives are stable only at low temperatures, covalent alkoxy ones can withstand heat up to 250 °C without perceptible decomposition. The fundamental absorption edge of both the initial niobate and the products of its organic modification lies in the near-ultraviolet region (370–385 nm).

show abstract

NMR Study of Intercalates and Grafted Organic Derivatives of H2La2Ti3O10

Cited by 15 publications

References 76 publications

Solid State NMR for Nonexperts: An Overview of Simple but General Practical Methods

Solid State NMR for Nonexperts: An Overview of Simple but General Practical Methods

The Grafting of Hydroxyaromatic Organics within Layered Perovskites via a Microwave-Assisted Method

Synthesis and Characterization of Inorganic-Organic Derivatives of Layered Perovskite-like Niobate HSr2Nb3O10 with n-Amines and n-Alcohols

Contact Info

Product

Resources

About