Synthesis in Silica Nanoreactor: Copper Pyrophosphate Quantum Dots and Silver Oxide Nanocrystallites Inside Silica Mezochannels

Laskowski, Łukasz; Majtyka-Piłat, Anna; Cpałka, Krzysztof; Zubko, Maciej; Laskowska, Magdalena

doi:10.3390/ma13092009

Cited by 6 publications

(5 citation statements)

References 32 publications

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“…In the second region, weight loss was at a level of 11% (from 95% to 84%) and was connected with the chemically-bonded water abruption, thermal decomposition of methyl (trimethylsilane-) groups and anchored iron propilphosphonate chains. The last ones were decomposed with the formation of various phosphates, pyrophosphates and oxides, the formation of which was observed in similar systems [24,50,51]. Since, according to electron diffraction, at this region, no crystalline products were noticed, one can assume that those products were in a complex amorphous form spread on the inner surface of the silica mesopores.…”

Section: Thermogravimetric Analysismentioning

confidence: 83%

Synthesis, thermal evolution and magnetic investigations of SBA-15 silica functionalized with anchored iron phosphonate molecules

et al. 2023

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In the current work, we report on synthesizing a series of novel nanocomposite materials obtained by functionalizing the SBA-15 silica matrix with anchored iron phosphonate molecules and following thermal treatment. Obtained results reveal the formation of a unique amorphic layer of Fe-based compounds on the surface of silica walls of SBA-15 channels as a result of the organic groups' decomposition after the moderate thermal treatment. Due to their unique structure, represented in an active Fe-containing amorphous coating spread over a large surface area, these materials are of great interest for their potential applications in fields such as catalysis, adsorption, and non-linear optics. Obtained materials remain amorphous, preserving the SBA-15 mesoporous structure up to the temperatures of approximately 800 °C, after which the partial melting of the silica backbone is observed with simultaneous formation of nanocrystals inside the newly-formed glassy mass. All obtained materials were characterized using such techniques as thermogravimetry, transmission and scanning electron microscopy combined with energy dispersive X-ray spectroscopy mapping, Raman spectroscopy, N2 sorption analysis, X-ray diffraction, X-ray photoelectron spectroscopy, Mössbauer spectroscopy, and SQUID measurements.

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Section: Thermogravimetric Analysismentioning

confidence: 83%

Synthesis, thermal evolution and magnetic investigations of SBA-15 silica functionalized with anchored iron phosphonate molecules

et al. 2023

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“…Such molecules can be separated and placed precisely inside porous silica structures [12][13][14]. The materials obtained in such a way can be a starting point for the fabrication of nanocomposites composed of copper pyrophosphate and silver Materials 2022, 15, 842 2 of 9 oxide nanocrystals placed inside mesoporous silica of the SBA-15 type, as we showed in our previous works [15].…”

Section: Introductionmentioning

confidence: 81%

“…The preparation of the nanocrystalline copper pyrophosphate in silica nanoreactors is presented in our article [15]. The DFT studies were carried out using the Quantum Espresso code [24].…”

Section: Experimental and Computational Detailsmentioning

confidence: 99%

Structure and Properties of Copper Pyrophosphate by First-Principle Calculations

et al. 2022

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Investigated the structural, electronic, and magnetic properties of copper pyrophosphate dihydrate (CuPPD) by the first-principle calculations based on the density functional theory (DFT). Simulations were performed with the generalized gradient approximation (GGA) of the exchange-correlation functional (Exc) supplemented by an on-site Coulomb self-interaction (U–Hubbard term). It was confirmed that the GGA method did not provide a satisfactory result in predicting the electronic energy band gap width (Eg) of the CuPPD crystals. Simultaneously, we measured the Eg of CuPPD nanocrystal placed inside mesoporous silica using the ultraviolet–visible spectroscopy (UV–VIS) technique. The proposed Hubbard correction for Cu-3d and O-2p states at U = 4.64 eV reproduces the experimental value of Eg = 2.34 eV. The electronic properties presented in this study and the results of UV–VIS investigations likely identify the semiconductor character of CuPPD crystal, which raises the prospect of using it as a component determining functional properties of nanomaterials, including quantum dots.

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“…Using the mesoporous silica give the possibility for obtaining homogenously distributed nanocrystals, while maintaining its correct structure and functionality. The material was prepared according to the procedure described in [30]. In this procedure mesoporous silica was used as a nanoreactor, where nanocrystals were created as a result of thermal decomposition of internal copper phosphonate units (figure 1).…”

Section: Experimental Methodsmentioning

confidence: 99%

“…Our method applies precisely functionalized mesoporous silica [28,29] and treats it as a system of nanoreactors, in which nanocrystals are created as a result of thermal decomposition. Additionally, the significant spatial confinement of crystallites (diameters below 5 nm) give a possibility to consider them as nanocrystalline quantum dots [30]. The resulting composite materials can find numerous applications, mainly in photonics and nanoelectronics [31].…”

Section: Introductionmentioning

confidence: 99%

Ab initio studies for characterization and identification of nanocrystalline copper pyrophosphate confined in mesoporous silica

Pastukh¹,

Laskowska²,

Dulski³

et al. 2021

Nanotechnology

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Here we employ a novel method for preparing the homogeneous copper pyrophosphate nanocrystals inside silica mesopores. In order to characterize and identify synthesized nanocrystals we performed the ab initio studies of the α phase of Cu2P2O7. The electronic and crystal structure were optimized within the density functional theory with the strong electron interactions in the states on copper atoms and van der Waals corrections included in calculations. The relaxed lattice parameters and atomic positions agree very well with the results of the diffraction measurements for nanocrystalline copper pyrophosphates embedded inside SBA-15 silica pores. The obtained Mott insulating state with the energy gap of 3.17 eV exhibits the antiferromagnetic order with magnetic moments on copper atoms (0.8 ) that is compatible with the experimental studies. The phonon dispersion relations were obtained to study the dynamical properties of the Cu2P2O7 lattice and the element-specific atomic vibrations were analyzed using the partial phonon density of states. The calculated Raman spectrum revealed the consistency of typical bands of Cu2P2O7 with the experimental data. The investigation that combines a new synthesis of nanomaterials with the first-principles calculations is important for better characterization and understanding of the physical properties relevant for nanotechnological applications.

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Synthesis in Silica Nanoreactor: Copper Pyrophosphate Quantum Dots and Silver Oxide Nanocrystallites Inside Silica Mezochannels

Cited by 6 publications

References 32 publications

Synthesis, thermal evolution and magnetic investigations of SBA-15 silica functionalized with anchored iron phosphonate molecules

Synthesis, thermal evolution and magnetic investigations of SBA-15 silica functionalized with anchored iron phosphonate molecules

Structure and Properties of Copper Pyrophosphate by First-Principle Calculations

Ab initio studies for characterization and identification of nanocrystalline copper pyrophosphate confined in mesoporous silica

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