Control of micro/mesoporosity in non-hydrolytic hybrid silicophosphate xerogels

Stýskalík, Aleš; Škoda, David; Moravec, Zdeněk; Babiak, Michał; Barnes, Craig E.; Pinkas, Jiří

doi:10.1039/c4ta06823h

Cited by 27 publications

(59 citation statements)

References 66 publications

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“…Both C−Si and C−P bonds were stable under the reaction conditions no matter whether alkyl or aryl groups were used [47]. While the homogeneity of Si−O−P mixing was preserved in these hybrid derivatives, the porosity [47] and hydrolytic stability [94] were influenced by the incorporation of organic groups. The control over porosity in hybrid silicophosphate materials will be described in more detail in Section 3.1.1.…”

Section: New Materials By Ester Elimination: Silicophosphates and Thementioning

confidence: 89%

“…There are a few reports of the siloxane formation, which are described in Section 2.6, focusing on oligo-and polysiloxanes. Ester elimination has, however, recently been used in the synthesis of highly homogeneous and porous silicophosphate materials from silicon acetates and trimethylsilyl esters of phosphoric and phosphonic acids (Scheme 3) [39,47,94,95]. Skeletal Si−O−P bonds in silicophoshates are prone to hydrolysis and therefore it is highly desirable to use anhydrous conditions during synthesis.…”

Section: New Materials By Ester Elimination: Silicophosphates and Thementioning

confidence: 99%

“…Recently, it was discovered that acetoxysilanes react with trimethylsilyl esters of phosphoric and phosphonic acids in similar way providing highly homogeneous silicophosphates and acetic acid esters as organic products [39]. Mild reaction conditions have yielded a broad variety of hybrid derivatives [47].…”

Section: ≡M-oh + Cl-m≡ → ≡M-o-m≡ + Hcl (5)mentioning

confidence: 99%

“…This environment of the silicon atom was introduced together with the organic groups forming CSiO3 moieties, which built the silicophosphate structure [47]. Reproduced with permission from [47]. Copyright Royal Society of Chemistry, 2015.…”

Section: Without Templatesmentioning

confidence: 99%

“…While all microporous samples were built up predominantly from SiO 6 units, mesoporosity was typical for the samples with silicon atoms in the tetrahedral coordination. This environment of the silicon atom was introduced together with the organic groups forming CSiO 3 moieties, which built the silicophosphate structure [47].…”

Section: Without Templatesmentioning

confidence: 99%

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The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

et al. 2017

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This review is devoted to non-hydrolytic sol-gel chemistry. During the last 25 years, non-hydrolytic sol-gel (NHSG) techniques were found to be attractive and versatile methods for the preparation of oxide materials. Compared to conventional hydrolytic approaches, the NHSG route allows reaction control at the atomic scale resulting in homogeneous and well defined products. Due to these features and the ability to design specific materials, the products of NHSG reactions have been used in many fields of application. The aim of this review is to present an overview of NHSG research in recent years with an emphasis on the syntheses of mixed oxides, silicates and phosphates. The first part of the review highlights well known condensation reactions with some deeper insights into their mechanism and also presents novel condensation reactions established in NHSG chemistry in recent years. In the second section we discuss porosity control and novel compositions of selected materials. In the last part, the applications of NHSG derived materials as heterogeneous catalysts and supports, luminescent materials and electrode materials in Li-ion batteries are described.

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Section: New Materials By Ester Elimination: Silicophosphates and Thementioning

confidence: 89%

Section: New Materials By Ester Elimination: Silicophosphates and Thementioning

confidence: 99%

Section: ≡M-oh + Cl-m≡ → ≡M-o-m≡ + Hcl (5)mentioning

confidence: 99%

Section: Without Templatesmentioning

confidence: 99%

Section: Without Templatesmentioning

confidence: 99%

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The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

et al. 2017

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Hydrophobicity Boosts Catalytic Activity: The Tailoring of Aluminosilicates with Trimethylsilyl Groups**

et al. 2023

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Introducing organic groups into metal silicate catalysts and thus supposedly changing the surface hydrophobicity has been shown to enhance the catalyst performance in various reactions. However, the organic groups introduction does not unambiguously guarantee hydrophobicity control. Therefore, a thorough characterization is necessary to provide a complete view of the interaction between the catalyst surface, reactants, and products. Herein, an aluminosilicate catalyst with welldispersed Al atoms was prepared via the non-hydrolytic sol-gel method. This material was post-synthetically modified with trimethylsilyl groups; their number on the catalyst surface was controlled via a temperature-vacuum pretreatment. In such a way, aluminosilicate materials with similar porosity, structure, and acid site strength and quality were obtained. Notably, the water sorption measurements showed that trimethylsilylated aluminosilicates adsorb 2.5-3 times less water than the parent material (p/p 0 = 0.3). The turn-over-frequency in epoxide ring opening and ethanol dehydration scaled up with the number of trimethylsilyl groups grafted on the catalyst surface. Particularly, the heavily trimethylsilylated sample achieved three to five times higher turnover-frequency in styrene oxide aminolysis than the parent aluminosilicate material. To the best of the authors' knowledge, it exhibited the most active Al sites for epoxide aminolysis in the present literature.

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Structural Insight into Layered Silicon Hydrogen Phosphates Containing [SiO₆] Octahedra Prepared by Different Reaction Routes

et al. 2019

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The layered silicophosphate Si(HPO 4 ) 2 was prepared via a novel synthesis approach using silicon nanopowder and ortho-phosphoric acid at 150°C providing a polycrystalline product. Silicophosphate compounds with sixfold coordinated silicon atoms obtained from pyrophosphoric acid H 4 P 2 O 7 and tetraalkoxysilanes via a sol-gel route exhibit the same shortrange order. The solid products were analyzed with XRD, ele- IntroductionSilicophosphates, i.e. in narrower sense compounds in the element system Si/P/O/(H), can show in contrast to most naturally occurring silicates and related silicon-oxygen compounds a sixfold coordination of the silicon with oxygen. [1] Typically, this phenomenon is only known from several high pressure materials and minerals, e.g. stishovite. [2] Not only in phosphorus containing glasses [3][4][5][6] but also in a number of crystalline silicophosphates, e.g. SiP 2 O 7 , [7][8][9] Si 5 P 6 O 25 , [10] and Si(HPO 4 ) 2 ·xH 2 O (x = 0,1), [11,12] the silicon is present in [SiO 6 ] units at ambient pressure. Additionally, molecular compounds with [SiO 6 ] moieties are also known in literature. [13][14][15][16] Furthermore, a tris(imidodiphosphinato) silicon complex synthesized from bis(diphenyldiphosphinyl)imine and silicon(IV) chloride, offers [SiO 6 ] structures surrounded by phosphorus atoms. [17] The role of phosphorus for building up [SiO 6 ] octahedra in silicophosphates has been discussed in several theoretical investigations. [18,19] Furthermore, the optical [20] and material properties [21] of silicophosphates, which are partly different from silicate materials due to the phosphorus content, are of basic interest relating to applications in laser technique, [22,23] implants research, [24] or [a]

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Control of micro/mesoporosity in non-hydrolytic hybrid silicophosphate xerogels

Cited by 27 publications

References 66 publications

The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

Hydrophobicity Boosts Catalytic Activity: The Tailoring of Aluminosilicates with Trimethylsilyl Groups**

Structural Insight into Layered Silicon Hydrogen Phosphates Containing [SiO₆] Octahedra Prepared by Different Reaction Routes

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Control of micro/mesoporosity in non-hydrolytic hybrid silicophosphate xerogels

Cited by 27 publications

References 66 publications

The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

Hydrophobicity Boosts Catalytic Activity: The Tailoring of Aluminosilicates with Trimethylsilyl Groups**

Structural Insight into Layered Silicon Hydrogen Phosphates Containing [SiO6] Octahedra Prepared by Different Reaction Routes

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Structural Insight into Layered Silicon Hydrogen Phosphates Containing [SiO₆] Octahedra Prepared by Different Reaction Routes