Novel POSS-based organic–inorganic hybrid porous materials by low cost strategies

Wang, Shaolei; Tan, Liangxiao; Zhang, Chengxin; Hussain, Irshad; Tan, Bien

doi:10.1039/c4ta06963c

Cited by 83 publications

(39 citation statements)

References 60 publications

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“…The presence of strongly polar Si-OH groups in the pores of MOFs could potentially lead to enhanced non-covalent interactions with gas molecules giving rise to attractive adsorption properties. 24,25 In some situations, polycarboxylic acids have been shown to form porous frameworks on crystallisation through hydrogen bonding. 26 Moreover, some of these materials have demonstrated potential for gas storage and separation applications.…”

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confidence: 99%

Siloxane-based linkers in the construction of hydrogen bonded assemblies and porous 3D MOFs

et al. 2017

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mentioning

confidence: 99%

Siloxane-based linkers in the construction of hydrogen bonded assemblies and porous 3D MOFs

et al. 2017

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“…Solid state 29 Si CP/ MAS NMR spectrum was recorded in support of this successful Friedel-Crafts reaction. The 29 Si MAS NMR of TPAIE-2 shows three major peaks at 81.6, 70.3 and 66.8 ppm. The signal at À 81.6 ppm is attributed to Si with unreacted vinyl groups.…”

Section: Fabrication and Characterization Of Nir Porous Compositesmentioning

confidence: 99%

“…[28] Increasing OVS content provides more reactive sites and enhances crosslink densities while coincidentally increasing unreacted vinyl contents and reducing S BET . [29] Hence, tunable porosities are afforded.…”

Section: Fabrication and Characterization Of Nir Porous Compositesmentioning

confidence: 99%

In Situ Methylation Transforms Aggregation‐Caused Quenching into Aggregation‐Induced Emission: Functional Porous Silsesquioxane‐Based Composites with Enhanced Near‐Infrared Emission

2019

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Methylation of TPA‐DCM (2‐(2,6‐bis‐4‐(diphenylamino)stryryl‐4H‐pyranylidene)malononitrile) that exhibits aggregation‐caused quenching (ACQ) results in the fluorophore M‐TPA‐DCM (2‐(2,6‐bis((E)‐4‐(di‐p‐tolylamino)‐styryl)‐4H‐pyran‐4‐ylidene]malononitrile) that shows aggregation‐induced emission (AIE) and NIR fluorescence and has a conjugated “D‐π‐A‐π‐D” electronic configuration. Friedel‐Crafts reaction of TPA‐DCM and octavinylsilsesquioxane (OVS) resulted in a family of porous materials (TPAIEs) that contain the M‐TPA‐DCM motif and show large Stokes shifts (180 nm), NIR emission (670 nm), tunable porosity (SBET from 160 to 720 m2 g−1, pore volumes of 0.13–0.55 cm3 g−1), as well as high thermal stability (400 °C, 5 % mass loss, N2). As a simple test case, one of TPAIE materials was used to sense Ru3+ ions with high selectivity and sensitivity.

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“…Although historically these types of porous materials have focused on using bridged alkoxysilanes synthesized by acid or base catalysis in a random structural formation, there are many advances in controlling the reactivity that give more focused pore sizes and overall reaction control [7][8][9][10][11][12][13][14]. There have been a few strategies implemented for this, including extensive processing and templation methodologies to maximize porosity and pore-structure stability [10,12,[15][16][17][18][19][20][21]. The advancements and mechanistic understanding of fluoride catalysis (non-stoichiometric) as a technique to synthesize these types of structures has enabled vast improvements in these materials from a structural and synthetic control standpoint [22,23].…”

Section: Introductionmentioning

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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Novel POSS-based organic–inorganic hybrid porous materials by low cost strategies

Cited by 83 publications

References 60 publications

Siloxane-based linkers in the construction of hydrogen bonded assemblies and porous 3D MOFs

Siloxane-based linkers in the construction of hydrogen bonded assemblies and porous 3D MOFs

In Situ Methylation Transforms Aggregation‐Caused Quenching into Aggregation‐Induced Emission: Functional Porous Silsesquioxane‐Based Composites with Enhanced Near‐Infrared Emission

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

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