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1

Luminescent homo- and hetero-metallic hybrid molecular materials constructed by covalent grafting

Wang F. F., Yan B.

Materials Science Poland

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2013

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Vol. 31, No. 1

108-114

EN

In this paper, 3-(triethoxysilyl)-propyl isocyanate (abbreviated as TESPIC) was modified by ethylparaben (EPB) to produce corresponding organic-inorganic monomers (EPB-TESPIC) with two components equipped with covalent bonds, which not only can coordinate to RE ions (Tb3+ and Eu3+) but also act as a sol-gel precursor. Luminescent hybrid materials consisting of terbium-europium complex, covalently bonded to silica-based network, have been obtained in situ via a sol-gel approach. Proton nuclear magnetic resonance spectroscopy (1HNMR) and Fourier transform infrared spectroscopy (FT-IR) were applied to characterize the structure of EPB-TESPIC. UV-visible, phosphorescence, and luminescence spectra were obtained to characterize the photophysical properties of the obtained hybrid material. Through co-hydrolysis and polycondensation, Tb3+ and Eu3+ can be introduced into the same organic-inorganic hybrid monomer, forming Si-O backbones. The experimental results show that the strong luminescence of rare-earth ions substantiates the optimum energy match and effective intramolecular energy transfer between the triplet state energy of coordination complex and the emissive energy level of the rare-earth ions. The hybrid material systems are expected to have potential applications in photophysical sensors.

2

Photofunctional terbium centered inorganic/organic hybrid material with the functionalized 5-dihydroxybenzoate linkage

Li Y., Sui Y. L., Yan B.

Materials Science Poland

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2012

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Vol. 30, No. 1

39--44

EN

In this study, silica-based organic-inorganic hybrids were prepared using sol-gel methods. A new kind of monomer (DHBA-TESPI) was derived by modifying the double hydroxyl groups of 3, 5-dihydroxybenzoic acid (DHBA) with 3-(triethoxysilyl)-propyl isocyanate (TESPI) through the addition reaction. Then, the obtained compound and tetraethoxysilane (TEOS) were used as the inorganic and organic counterparts respectively. Coordination reaction between Tb3+ and the carboxylic groups of the monomer happen simultaneously. IR, NMR, UV/Vis absorption, low-temperature phosphorescence spectroscopy and fluorescence spectroscopy were used to characterize the hybrids. The final materials exhibited strong green-colored fluorescence (Tb3+), which can be explained by the intramolecular energy transfer caused by coordination of the organic counterpart. The spectroscopic data also revealed that the triplet state energy of the organic ligand matches the emissive energy level of Tb3+.

3

Degradability of organic-inorganic cellulose acetate butyrate hybrids in sea water

Wojciechowska P., Heimowska A., Foltynowicz Z., Rutkowska M.

Polish Journal of Chemical Technology

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2011

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Vol. 13, nr 2

29-34

EN

Environmental degradability of novel organic-inorganic cellulose acetate butyrate hybrids obtained via solgel process was investigated. The degradation of hybrids was studied under marine exposure conditions in the Baltic Sea for a period of 25 weeks. The influence of characteristic parameters of sea water on the degree of degradation monitored by changes of weight and optical microscopy was discussed. The degraded samples were also examined by FT-IR spectroscopy. It has been established that the CAB/silica hybrids are more susceptible to biodegradation in sea water environment than pure cellulose acetate butyrate.

4

Hybrid materials doped with lithium ions

Zelazowska E., Rysiakiewicz-Pasek E.

Optica Applicata

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2010

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Vol. 40, nr 2

383--396

EN

Sol–gel derived lithium-ion conducting organic–inorganic hybrid materials have been synthesized from tetraethyl orthosilicate (TEOS), propylene glycol, ethylene glycol dimethacrylate, poly(vinyl alcohol), vinyl acetate, ethyl acetoacetate, poly(methyl methacrylate), propylene carbonate and some other precursors and solvents. The mass fraction of the organic additions in the gels and the level of the lithium salt doping (LiClO4) were ~40 mass% and 0.01%, respectively. The morphological and structural properties of the gels were investigated by a scanning electron microscope equipped with energy dispersive X-ray spectroscopy (SEM/EDX), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR) and 29Si MAS Nuclear Magnetic Resonance (29Si MAS NMR). The hybrid gels obtained were amorphous and colourless transparent or slightly opalescent, with the room temperature ionic conductivities of the order of 10–3 Scm–1. The results of FTIR spectroscopy and 29Si MAS NMR investigations have revealed strong influence of the organic modification, resulting in the direct chemical bonding between organic and inorganic components of the gels. The WO3-based electrochromic cells with the hybrids obtained being applied as the electrolytes were able to be reversibly coloured and bleached in the optical transmittance range of ~58% to 5% at around 550 nm.

5

Synthesis of organic-inorganic hybrids based on cellulose acetate butyrate

Wojciechowska P.

Polimery

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2009

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T. 54, nr 11-12

845-848

EN

Novel organic-inorganic hybrids based on cellulose acetate butyrate (CAB) were synthesized applying sol-gel process. The inorganic phase was introduced into polymer matrix by hydrolysis and condensation using tetraethoxysilane (TEOS) as the precursor, under acidic conditions. The obtained organic-inorganic hybrids were characterized by different techniques such as IR spectroscopy, thermogravimetric analysis (TGA), solid state 29Si NMR and scanning electron microscopy (SEM). Organic-inorganic hybrids obtained with 20% of diethyl phthalate (DEP) as plasticizer exhibit good transparency in comparison with unmodified CAB.

PL

Nowe organiczno-nieorganiczne materiały hybrydowe na bazie octanomaślanu celulozy (CAB) otrzymano techniką zol-żel. Fazę nieorganiczną wprowadzano do matrycy polimeru w wyniku reakcji hydrolizy w środowisku kwaśnym i kondensacji stosując jako prekursor tetraetoksysilan (TEOS). Otrzymane materiały charakteryzowano za pomocą spektroskopii w podczerwieni (IR), analizy termograwimetrycznej (TGA), magnetycznego rezonansu jądrowego ciał stałych 29Si NMR oraz skaningowej mikroskopii elektronowej (SEM). Organiczno-nieorganiczne hybrydy otrzymane z udziałem 20% ftalanu dietylu jako plastyfikatora cechują się dobrą przejrzystością w porównaniu z polimerem niemodyfikowanym.

6

Organic-inorganic hybrid materials doped with lithium ions

Żelazowska E., Borczuch-Laczka M., Rysiakiewicz-Pasek E.

Optica Applicata

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2008

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Vol. 38, nr 1

137-146

EN

Organic-inorganic hybrid materials have been synthesized by the sol-gel method, using tetraethyl orthosilicate TEOS), poly(ethylene oxide) (PEO), net-polyacrylic-inter-net-polysiloxane, butyl acrylate, ethyl acetoacetate, tetrahydrofuran, acetonitrile and LiClO4 precursors and additives. Mass fractions of the organic additions in the gels were of ca 35-40 mass%. The hybrid materials obtained were amorphous, colourless, transparent or translucent, with room temperature ionic conductivities in a range of 10-4-10-3 omega-1cm-1. The results of scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX), Fourier transform infrared spectroscopy and 29Si MAS Nuclear Magnetic Resonance analysis have revealed [SiO4] tetrahedrons polycondensation strongly influenced by organic precursors and chemical bonding between organic and inorganic parts of the gels obtained.

7

Elektrolity hybrydowe organiczno-nieorganiczne dla cienkowarstwowych powłok elektrochromowych opartych na WO3.

Żelazowska E., Borczuch-Łączka M., Rysiakiewicz-Pasek E.

Szkło i Ceramika

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2007

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R. 58, nr 4

11-17

PL

Domieszkowane solą litu (LiClO4), elektrolity hybrydowe organiczno-nieorganiczne, przydatne dla cienkowarstwowych powłok elektrochromowych opartych na WO3, zostały otrzymane metodą zol-żel z prekursorów w postaci ortokrzemianu etylu (TEOS), politlenku etylenu (PEO), tlenku propylenu (PO), węglanu propylenu (PC). Badania morfologii i ocena właściwości strukturalnych na podstawie widm FTIR wykazały, że uzyskane elektrolity były amorficzne, porowate i miały charakter materiałów hybrydowych organiczno-nieorganicznych o właściwościach strukturalnych zależnych od stosowanych dodatków organicznych. Ich stosunkowo wysoka przewodność jonowa w zakresie temperatur pokojowych (najwyższa wartość 8,29 x 10 do -3 Scm do -1), którą można wiązać ze stanem amorficznym i modyfikacją struktury żeli hybrydowych w wyniku stosowania dodatków organicznych i soli litu, czyni uzyskane materiały obiecującymi do stosowania w charakterze stałych elektrolitów dla zastosowań niskotemperaturowych w układach elektrochemicznych optoelektronicznych.

EN

Sol-gel derived, doped with lithium salt (LiClO4) organic - inorganic hybrid electrolytes for WO3 - based thin film electrochromic coatings were obtained as amorphous materials from tetraethoxysilane (TEOS), poly(ethylene oxide) (PEO), propylene oxide (PO), propylene carbonate (PC) precursors and were investigated for morphology, structural properties and ionic conductivity. All materials obtained were porous with hybrid structure, influenced by organic components and preparing procedure, evident from FTIR spectra and have proved to be efficient as electrolytes in WO3 - based electrochromic thin film systems. The relatively high room-temperature conductivity (the highest value 8.29 x 10 to the -3 Scm to the -1) can be attributed to amorphous character and structural modification due to lithium salt and organic additions and makes the obtained materials to be promising as electrolytes for ambient temperature electrochemical and optoelectronic applications.

8

Li-ion conducting organic-inorganic hybrid electrolytes

Żelazowska E., Borczuch-Łączka M., Rysiakiewicz-Pasek E., Zduniewicz T.

Materials Science Poland

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2006

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Vol. 24, No. 1

133--140

EN

Lithium ion conducting, sol-gel derived, amorphous, organic-inorganic hybrid electrolytes were obtained from tetraethoxysilane, poly(ethylene oxide), propylene oxide, propylene carbonate, acetonitrile and LiClO4 precursors, and were investigated for their morphological and structural properties by scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX), X-ray diffraction (XRD), infrared spectroscopy, and nitrogen adsorption at 77 K. A room-temperature conductivity of ca. 10-4-10-3 Sźcm-1, attributed to an amorphous character and the organic addition, as well as results of testing in WO3-based electrochromic thin-film systems, make the hybrid materials obtained promising as electrolytes for ambient temperature electrochemical and optoelectronic applications.

9

Organic-inorganic hybrid electrolytes for thin film metal oxide electrochromic coatings

Żelazowska E., Borczuch-Łączka M., Rysiakiewicz-Pasek E., Lachman W.

Optica Applicata

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2005

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Vol. 35, nr 4

887-894

EN

Sol-gel derived lithium salt (LiClO4) doped organic-inorganic hybrid electrolytes have been obtained from the tetraethyl orthosilicate (TEOS) and poly(ethylene oxide) (PEO), propylene oxide (PO), ethyl acetoacetate (EAA), propylene carbonate (PC), polyvinyl alcohol (PVA) precursors and have been investigated for morphology and structural properties by SEM/EDS and FTIR spectroscopy. The hybrid materials obtained were amorphous, with structural properties influenced by organic ingredients which had been used, and with the ionic conductivities of 10-4-10-3 Scm-1. When used as electrolytes in the WO3-based thin-film electrochromic coatings, they have proved to be suitable for low-temperature electrochemical applications.