Microporous inorganic/organic hybrids via oxysilylation of a cubic symmetry nanobuilding block [(HMe&lt;sub&gt;2&lt;/sub&gt;SiOSiO&lt;sub&gt;1.5&lt;/sub&gt;)&lt;sub&gt;8&lt;/sub&gt;] with R&lt;i&gt;&lt;sub&gt;x&lt;/sub&gt;&lt;/i&gt;Si(OEt)&lt;sub&gt;4&amp;minus;&lt;/sub&gt;&lt;i&gt;&lt;sub&gt;x&lt;/sub&gt;&lt;/i&gt;

Pan, David; Yi, Eongyu; Doan, Phi; Furgal, Joseph C.; Schwartz, Matthew; Clark, Sarah; Laine, Richard M.

doi:10.2109/jcersj2.123.756

Cited by 16 publications

(16 citation statements)

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“…Although research into this reaction type is strongly focused on the polymer science, the first examples of the preparation of porous silica-based hybrid materials [131] and mixed Si-O-B oxides [54] have been reported. This strongly exothermic reaction is based on the condensation of Si-H and EtO-Si units (Scheme 7).…”

Section: Siloxanes By Nhsg Condensations Piers-rubinsztajn Reactionmentioning

confidence: 99%

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: Siloxanes By Nhsg Condensations Piers-rubinsztajn Reactionmentioning

confidence: 99%

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

et al. 2017

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“…Specific surface area (SSA) and porosity analyses: A Micromeritics 3FLEX surface and catalyst characterization analyzer (Micromeritics Inc., Norcross, GA, USA) was used to analyze the surface area and porosity of all samples [29,52]. Samples were degassed at room temperature for 2 h with an N 2 flush.…”

Section: Methodsmentioning

confidence: 99%

R-Silsesquioxane-Based Network Polymers by Fluoride Catalyzed Synthesis: An Investigation of Cross-Linker Structure and Its Influence on Porosity

Furgal

2020

Materials

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Silsesquioxane-based networks are an important class of materials that have many applications where high thermal/oxidative stability and porosity are needed simultaneously. However, there is a great desire to be able to design these materials for specialized applications in environmental remediation and medicine. To do so requires a simple synthesis method to make materials with expanded functionalities. In this article, we explore the synthesis of R-silsesquioxane-based porous networks by fluoride catalysis containing methyl, phenyl and vinyl corners (R-Si(OEt) 3 ) combined with four different bis-triethoxysilyl cross-linkers (ethyl, ethylene, acetylene and hexyl). Synthesized materials were then analyzed for their porosity, surface area, thermal stability and general structure. We found that when a specified cage corner (i.e., methyl) is compared across all cross-linkers in two different solvent systems (dichloromethane and acetonitrile), pore size distributions are consistent with cross-linker length, pore sizes tended to be larger and π-bond-containing cross-linkers reduced overall microporosity. Changing to larger cage corners for each of the cross-linkers tended to show decreases in overall surface area, except when both corners and cross-linkers contained π-bonds. These studies will enable further understanding of post-synthesis modifiable silsesquioxane networks.Materials 2020, 13, 1849 2 of 13 of reaction solvent and water content in modifying the overall pore size distributions of a single cross-linker system [29]. Though many reports speculate that the pore sizes obtained in sol-gel reactions are directly related to the bridging groups used, especially for rigid spacers [2,26,[30][31][32], we found that multiple pore size distributions (0.5 to 100 nm) could be obtained by simply changing the reaction solvent for the same bridge. For example, dichloromethane (DCM) favored micropores on the order of 1.2 nm and gel particles, while changing the reaction solvent to acetonitrile (ACN) gave pores centered around 3 nm and favored global gelation of the entire system. All the synthesized materials favored non-polar solvents as expected for organogels based on networked silsesquioxanes.Though high porosity materials with static or non-functionalizable pores are useful in many applications [33][34][35][36], it is often desirable to impart additional functionality to these materials for many specialized uses. such as in biology or environmental remediation. as capture and release agents [2,17,[37][38][39]. These functionalities may include hydrophilic groups, amino-acids and reversible chemistries such as "click" or complexation ligands [40][41][42][43][44]. Many researchers have been working on methods to synthesize active silsesquioxane-based networks, albeit primarily through preformed cage methods. In terms of preformed cage systems, Ervithayasuporn et al. have developed a recyclable methacrylate-POSS (polyhedral oligomeric silsesquioxanes) porous network which can efficiently bind Pd and acts as a catalyst f...

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“…Functionalization of each of the anionic oxygens can be achieved by reaction with any mono-chlorosilanes (i.e. chloro-dimethylsilane) to instill reactive functionalities to make a variety of materials ( Figure 18B) (Pan et al 2015). One of the unique features of OA is that it only reacts with silanes and not carbon based electrophiles (Laine 2005).…”

Section: From Rha To Silsesquioxane Derivativesmentioning

confidence: 99%

“…Porous inorganic/organic hybrid materials can also be made from green processes. The octasilicates made from RHA and discussed in Section 2.3 are excellent building blocks for porous materials, especially in the form of [(HMe 2 SiOSiO 1.5 ) 8 ], (OHS) (Pan et al 2015). Oxysilylation can be used to react Si-H groups with alkoxysilanes in the presence of B(C 6 F 5 ) 3 catalysts.…”

Section: Inorganic Copolymers and Compositesmentioning

confidence: 99%

Green routes to silicon-based materials and their environmental implications

Furgal

Lenora

2019

Physical Sciences Reviews

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Abstract The “greening” of silicon chemistry is fundamentally important for the future of the field. Traditional methods used to make silicon-based materials rely on carbon rich processes that are highly energy intensive, cause pollution, and are unsustainable. Researchers have taken up the challenge of developing new chemistries to circumvent the difficulties associated with traditional silicon material synthesis. Most of this work has been in the conversion of the “green” carbon neutral biogenic silica source rice hull ash (RHA, ~85 % silica) into useful silicon building blocks such as silica’s, silicon, and alkoxysilanes by using the inherently higher surface area and reactivity of RHA to sidestep the low reactivity of mined silica sources. This is a review of the work that has been done in the area of developing more environmentally benign methods for the synthesis and use of silicon containing materials to eliminate the negative impact on the environment.

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Microporous inorganic/organic hybrids via oxysilylation of a cubic symmetry nanobuilding block [(HMe<sub>2</sub>SiOSiO<sub>1.5</sub>)<sub>8</sub>] with R<i><sub>x</sub></i>Si(OEt)<sub>4−</sub><i><sub>x</sub></i>

Cited by 16 publications

References 61 publications

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

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

R-Silsesquioxane-Based Network Polymers by Fluoride Catalyzed Synthesis: An Investigation of Cross-Linker Structure and Its Influence on Porosity

Green routes to silicon-based materials and their environmental implications

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