Co-reporter:Dengxu Wang, Ruixue Sun, Shengyu Feng, Wensi Li, Hongzhi Liu
Polymer 2017 Volume 130(Volume 130) pp:
Publication Date(Web):9 November 2017
DOI:10.1016/j.polymer.2017.10.021
•The original appearance of POSS-based porous polymers has been retrieved.•The fluorescence of the polymers is largely dependent on their appearance.•Potential applications as sensing agents for detecting nitroaromatic explosives.A class of polyhedral oligomeric silsesquioxane (POSS)-based porous polymers containing typical π-conjugated units, including biphenyl, tetrahedral silicon-centered units and tetraphenylethene, have been prepared by Heck reactions of octavinylsilsesquioxane (OVS) with the corresponding brominated monomers. Two sets of reaction conditions were employed to retrieve their original appearance. These materials exhibit tunable appearance with the colors from dark colors to various colors and the physical forms from coarse powders with irregular shape particles to fine powders with relatively uniform solid spheres by altering the reaction conditions from method A to method B. It is found that the variation of appearance leads to the alteration of the fluorescence from nearly no fluorescence to bright fluorescence. Considering the conjugated feature of these polymers, we speculate that these polymers were afforded as their original appearance by method B. This finding could explain the unexpected phenomenon that many conjugated porous polymers exhibit no or very low fluorescence despite of their π-conjugated structures, that is, their real appearance may be covered by the residuals in the networks. Thus, researchers should deliberately consider the material's appearance when preparing fluorescent porous polymers. Additionally, samples with fine powders show excellent dispersion stability in solvents, which is beneficial for the use of these materials in solution processable methodologies such as spin-coating. Furthermore, these materials show efficient fluorescence quenching for nitrobenzene vapour in thin films, thereby indicating their potential application as sensing agents for the detection of explosives.Download high-res image (268KB)Download full-size image
Co-reporter:Huanhuan Liu
Journal of Materials Chemistry A 2017 vol. 5(Issue 19) pp:9156-9162
Publication Date(Web):2017/05/16
DOI:10.1039/C7TA01255A
Multifunctional hybrid fluorescent porous materials have been prepared by the Friedel–Crafts reaction of octavinylsilsesquioxane (OVS) with tetraphenylethene (TPE). These hybrid porous polymers possess high surface areas of up to 1910 cm2 g−1, and bimodal pore structures with micropores centered at ≈1.4 nm and mesopores centered at ≈4.5 nm. They show a moderate CO2 adsorption capacity of 6.25 wt% (1.42 mmol g−1) at 273 K/101 kPa. Remarkably, they exhibit highly size-selective adsorption of dye of 1666 mg g−1 for rhodamine B (RB), 1040 mg g−1 for congo red (CR) and 862 mg g−1 for crystal violet (CV). Furthermore, the incorporation of a tetraphenylethene unit induces higher fluorescence (λem = 490 nm) and high sensitivity for Fe3+, Cu2+ and Ru3+, especially for Fe3+ with KSV = 140 K M−1. They are very promising for multiple applications in dye separation, sensors, etc.
Co-reporter:Dengxu Wang, Wenyan Yang, Shengyu Feng and Hongzhi Liu
RSC Advances 2016 vol. 6(Issue 17) pp:13749-13756
Publication Date(Web):28 Jan 2016
DOI:10.1039/C5RA26617C
A novel hybrid porous polymer (HPP-1) is synthesized using octavinylsilsequioxane and 2,7-dibromo-9-fluorenone as monomers via Heck reaction. Subsequently, HPP-1 is post-functionalized by the conversion of deliberately introduced free ketone moieties into amine functionalities. Compared with HPP-1, the resulting material, HPP-1-amine, showed enhanced CO2 uptake from 0.63 mmol g−1 (HPP-1) to 1.01 mmol g−1 (HPP-1-EDA, EDA = ethylenediamine) and 0.72 mmol g−1 (HPP-1-HDA, HDA = hexamethylenediamine) at 298 K and 1 bar. Furthermore, the porosity of HPP-1-amine is not compromised, but enhanced with the BET specific surface area increasing from 529 m2 g−1 (HPP-1) to 651 m2 g−1 (HPP-1-EDA) and 615 m2 g−1 (HPP-1-HDA). Compared with HPP-1, the selectivity of CO2 over N2 of HPP-1-EDA increases nearly twice while that of HPP-1-HDA slightly decreases, indicating their potential applications in CO2 storage and capture. Although the enhanced extent of CO2/N2 selectivity is not as high as other analogues, we provide a new possibility for post-synthetic amine functionalization of porous polymers for simultaneously enhancing porosity and CO2 adsorption properties. The retained porosity won't limit their applications in other areas, such as heavy metal ion adsorption, ion channels and catalysis, etc.
Co-reporter:Rong Shen, Shengyu Feng and Hongzhi Liu
RSC Advances 2016 vol. 6(Issue 64) pp:59305-59312
Publication Date(Web):15 Jun 2016
DOI:10.1039/C6RA10165H
Multi-methacrylate functionalized cage silsesquioxane is a highly polymerizable monomer that can also act as a ligand coordinating agent to form luminescent hybrid complex with rare earth ions. This hybrid complex with terbium was incorporated into methyl methacrylate (MMA) monomers to form a hybrid luminescent PMMA nanocomposite via in situ polymerization. The resulting hybrid nanocomposite was highly optically transparent and exhibited photoluminescence, monochromaticity, relatively low surface energy and high thermal stability.
Co-reporter:Rong Shen and Hongzhi Liu
RSC Advances 2016 vol. 6(Issue 44) pp:37731-37739
Publication Date(Web):11 Apr 2016
DOI:10.1039/C6RA02963A
Two novel hybrid porous polymers were easily prepared by the Friedel–Crafts reaction of octavinylsilsesquioxane with triphenylphosphine and triphenylphosphine oxide, respectively. They possessed unique bimodal pores with uniform micropores and mesopores centered at 1.5 nm and 3.7 nm, respectively, high surface areas up to 1105 m2 g−1, high thermal stability and an excellent size-selective adsorption for dyes. These hybrid porous polymers are very promising in dye separation, water purification and treatment.
Co-reporter:Liguo Li; Hongzhi Liu
Chemistry - A European Journal 2016 Volume 22( Issue 14) pp:4713-4716
Publication Date(Web):
DOI:10.1002/chem.201600186
Abstract
Three new hybrid ionic liquids (ILs) based on cage silsesquioxane (SQ) were rapidly prepared in high yields from octa(mercaptopropyl)silsesquioxane and 1-allyl-3-methylimidazolium salts (Br−, BF4−, PF6−) through the photochemical thiol–ene reaction. These SQ-based ILs exhibited low glass transition temperatures and good thermal stability. The unique amphiphilic nature of these hybrid ILs cause them to self-assemble into perfect vesicles with “yolk–shell” structures, in which cages formed the “yolk” due to their aggregation and outer anions formed the “shell”.
Co-reporter:Yue Wu, Liguo Li, Wenyan Yang, Shengyu Feng and Hongzhi Liu
RSC Advances 2015 vol. 5(Issue 17) pp:12987-12993
Publication Date(Web):16 Jan 2015
DOI:10.1039/C4RA14830D
A series of hybrid nanoporous polystyrenes were synthesized from commercial polystyrene (PS) and cubic octavinylsilsesquioxane (OVS) via the Friedel–Crafts reaction. The porosity of the resulting hybrid polymers could be fine-tuned by varying the ratio of PS and OVS. The resulting polymers, HCP-1 to HCP-9 had apparent Brunauer–Emmett–Teller surface areas (SBET) in a range of 2.6 to 767 m2 g−1, with total pore volumes in the range of 0.36 to 0.90 cm3 g−1. The SBET was maximum when OVS loading was 9.1 wt%; it then decreased to almost no porosity before increasing again with the increase of OVS loading. The thermal decomposition temperatures of the hybrid polymers were close to pure PS under a N2 atmosphere, but the residues increased with the increase of OVS loading. The gas sorption applications revealed that HCP-3 possessed H2 uptake of 3.01 mmol g−1 (0.60 wt%) at 77 K and 1.01 bar and CO2 uptake of 1.12 mmol g−1 (4.93 wt%) at 298 K and 1.01 bar.
Co-reporter:Chundong Jiang;Wenyan Yang;Liguo Li;Yuqi Hou;Xiaoling Zhao
European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 23) pp:3835-3842
Publication Date(Web):
DOI:10.1002/ejic.201500462
Abstract
Octabromophenylethyl-functionalized silsesquioxane (BrPh-SQ) was synthesized by the Friedel–Crafts alkylation of octavinylsilsesquioxane (OVS) with bromobenzene, which acted as both the solvent and reactant and, furthermore, could be recycled after the reaction. The approach possesses the advantages of being mild, economic, and highly efficient. Further, BrPh-SQ was used as a building block in Heck reactions with OVS and tetrakis(4-vinylphenyl)silane to form two hybrid network polymers, that is, cage polymers 1 and 2, respectively. Cage polymer 1 showed moderate porosity with a Brunauer–Emmett–Teller specific surface area of 334 m2 g–1 and a total pore volume of 0.208 cm3 g–1. For gas-sorption applications, the CO2 uptake of cage polymer 1 was 2.44 wt.-% (0.55 mmol g–1) at 273 K and 101 kPa.
Co-reporter:Wenyan Yang, Xuesong Jiang and Hongzhi Liu
RSC Advances 2015 vol. 5(Issue 17) pp:12800-12806
Publication Date(Web):16 Jan 2015
DOI:10.1039/C4RA13628D
For the first time, a novel pH-responsive porous material based on POSS was easily prepared from the cubic octavinylsilsesquioxane (OVS) and brominated distyrylpyridine (Br-DSP) via the Heck coupling reaction. The resulting material possessed high porosity with Brunauer–Emmett–Teller specific surface area of 600 m2 g−1 and total pore volume of 0.58 cm3 g−1. It also exhibited high CO2 storage capability of 0.82 mmol g−1 (3.62 wt%) at 298 K/760 Torr. The porous polymer was luminescent with the maximum emission at ca. 530 nm in the solid state, due to the incorporation of the conjugated structures of distyrylpyridine. Owing to the protonated nitrogen centers in the porous material, an excellent pH-responsive property was observed and a linear relation was established between the maximum luminescent emission wavelengths (λem) of the turbid liquid in buffer solutions and the corresponding pH values in the pH range from 1 to 4. This porous material is very promising as a fluorescent probe in the rapid test systems.
Co-reporter:Wenyan Yang;Yanchang Gan;Xuesong Jiang
European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 1) pp:99-103
Publication Date(Web):
DOI:10.1002/ejic.201402920
Abstract
Starting from potassium cinnamate, photoreactive mono-, octa-, and deca(propyl cinnamate)-functionalized cage silsesquioxanes were synthesized by simple nucleophilic substitution reactions with chloropropyl-substituted octasilsesquioxanes. Among them, octa(propyl cinnamate)silsesquioxane exhibited some remarkable behavior, including high photopolymerization conversion of double bonds under UV irradiation and thermal stability. These compounds can act as pure photoreactive nanobuilding blocks for the preparation of hybrid nanocomposites with specific properties.
Co-reporter:Lei Xue, Liguo Li, Shengyu Feng, Hongzhi Liu
Journal of Organometallic Chemistry 2015 Volume 783() pp:49-54
Publication Date(Web):1 May 2015
DOI:10.1016/j.jorganchem.2015.01.028
•One step to multifunctional cage precursors.•A highly efficient photochemical thiol–ene reaction.•Commercially available multifunctional thiols.•Versatile octavinylsilsesquioxane.Starting from octavinylsilsesquioxane (OVS), several multifunctional cage silsesquioxanes were successfully prepared by the photo–induced thiol–ene reaction with the corresponding commercially available thiols. These cage compounds were fully characterized by FTIR, NMR, ESI–MS and element analysis.Octavinylsilsesquioxane (OVS) was selected as the starting material to react with a series of commercially available thiols bearing hydroxyl, carboxyl, amino and bi–/tri–alkoxysilane groups to produce the corresponding functionalized cage monomers via the photochemical thiol–ene reaction.
Co-reporter:Yun Liu;Wenyan Yang; Hongzhi Liu
Chemistry - A European Journal 2015 Volume 21( Issue 12) pp:4731-4738
Publication Date(Web):
DOI:10.1002/chem.201406142
Abstract
Mono- and octa-azobenzene-functionalized cage silsesquioxanes were easily synthesized by the reaction of 4-bromoazobenzene with monovinyl-substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited-state energies obtained from time-dependent density functional theory (TDDFT) and the CAM-B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene-functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue-light emission.
Co-reporter:Yue Wu, Dengxu Wang, Liguo Li, Wenyan Yang, Shengyu Feng and Hongzhi Liu
Journal of Materials Chemistry A 2014 vol. 2(Issue 7) pp:2160-2167
Publication Date(Web):29 Nov 2013
DOI:10.1039/C3TA14746K
Friedel–Crafts reaction of cubic octavinylsilsesquioxane (OVS) and benzene results in a series of hybrid porous polymers (HPPs). The resulting materials, HPP-1 to HPP-4, show relatively high porosity with apparent Brunauer–Emmett–Teller surface areas in a range of 400 m2 g−1 to 904 m2 g−1, with total pore volumes in the range of 0.24 cm3 g−1 to 0.99 cm3 g−1. Their porosities can be fine tuned by adjusting the mole ratios of OVS and benzene. They feature both micro- and mesopores (HPP-1 and HPP-2) to almost mesopores (HPP-3 and HPP-4) in the networks. The ratios of micropore volume to total pore volume for HPP-1 to HPP-4 were 0.58, 0.42, 0.10, and 0.11, respectively. These materials exhibit comparable surface area and high thermal stability in a N2 atmosphere. The gas sorption applications reveal that HPP-3 possesses a H2 uptake of 3.47 mmol g−1 (0.70 wt%) at 77 K and 760 mmHg and a CO2 uptake of 0.62 mmol g−1 (2.73 wt%) at 298 K and 760 mmHg. These results indicate these materials are promising candidates for storing H2 and CO2. In addition, HPP-4 has been successfully postfunctionalized with 3-mercaptopropionic acid via thiol–ene “click” reaction.
Co-reporter:Dengxu Wang, Wenyan Yang, Shengyu Feng and Hongzhi Liu
Polymer Chemistry 2014 vol. 5(Issue 11) pp:3634-3642
Publication Date(Web):17 Feb 2014
DOI:10.1039/C3PY01688A
Heck coupling of cubic octavinylsilsequioxane (OVS) with planar di-/tri-halogenated benzene (1–5) results in a series of inorganic–organic hybrid porous polymers (HPPs). These materials show high thermal stability and tunable porosities with Brunauer–Emmett–Teller surface areas ranging from 479 m2 g−1 to 805 m2 g−1 and with the total pore volume ranging from 0.33 cm3 g−1 to 0.59 cm3 g−1. Porosity comparison reveals that monomer species and reaction conditions strongly affect the surface area, pore volume and microporosity. For the monomer species, monomers with high reactivity, long strut length and more connectable sites are beneficial to enhance the surface area and pore volume. For the reaction conditions, the conditions which can result in high levels of coupling degrees and the choice of N,N-dimethylformamide (DMF) as the solvent can also enhance the porosity. However, long monomer strut length may also lead to lower surface area and pore volume. DMF tends to increase the level of microporosity and increasing connectable sites may afford more mesopores. These results suggest that these comprehensive factors should be carefully considered when preparing new porous polymers with controllable porosity. In the application, HPP-3 possesses a moderate carbon dioxide uptake of 1.38 mmol g−1 (6.1 wt%) at 273 K and 0.68 mmol g−1 (2.99 wt%) at 298 K when measured up to 1 bar. HPP-3 shows a high binding ability with CO2 with an isosteric heat of 35 kJ mol−1 at low coverage, making these materials become promising candidates for storing and capturing CO2.
Co-reporter:Liguo Li and Hongzhi Liu
RSC Advances 2014 vol. 4(Issue 87) pp:46710-46717
Publication Date(Web):12 Sep 2014
DOI:10.1039/C4RA05370B
Hybrid polystyrene was easily prepared from monovinyl-substituted POSS and commercial polystyrene (PS) via a straightforward Friedel–Crafts reaction. The resulting hybrid polystyrene was thoroughly investigated by a series of characterization methods, such as FTIR, NMR, XRD, SAXS, DLS, POM, DSC, TGA, SEM, TEM and an Abbe refractometer. Results showed that POSS was well dispersed in the polystyrene matrix at a nearly molecular level and no macrophase separation was observed; these hybrid polystyrenes exhibited different properties from pristine polystyrene, for example, solubility, crystalline and thermal properties etc. Considering the strong aggregation tendency of POSS in nonsolvents, it was interesting to study the self-assembly behaviors of these hybrid polystyrenes modified by POSS. The morphology of these hybrid polystyrenes in ethanol was investigated by dynamic lighting scattering, and transmission electron microscopy. The studies illustrated that these hybrid polystyrenes could self-assemble into a series of spheres in ethanol; the diameters of these spheres decreased with increasing POSS loading.
Co-reporter:Liguo Li, Shengyu Feng and Hongzhi Liu
RSC Advances 2014 vol. 4(Issue 74) pp:39132-39139
Publication Date(Web):19 Aug 2014
DOI:10.1039/C4RA05577B
A novel β-diketone-functionalized POSS dendrimer was initially prepared from octamercaptopropyl-substituted polyhedral oligomeric silsesquioxane (POSS) and diethyl allylmalonate by a photochemical thiol–ene reaction. The POSS dendrimer was used as a ligand to coordinate with lanthanide ions (Eu3+ and Tb3+) to form hybrid luminescent complexes. The resulting hybrid lanthanide complexes were incorporated into the PMMA matrix via in situ polymerization. Morphology study suggested that these hybrid complexes assembled into spherical particles with a diameter of approximately 100 nm and could be well dispersed in PMMA matrix. The resultant hybrid luminescent PMMA based on POSS exhibited highly saturated color and good thermal stability.
Co-reporter:Wenyan Yang;Dengxu Wang;Liguo Li
European Journal of Inorganic Chemistry 2014 Volume 2014( Issue 18) pp:2976-2982
Publication Date(Web):
DOI:10.1002/ejic.201402156
Abstract
A series of novel hybrid porous polymers (HPPs), derived from cubic octavinylsilsesquioxane (OVS; [(C2H3SiO1.5)8]) and tetraphenylsilane (TPS), were successfully synthesized through Friedel–Crafts alkylation reaction. The porosities of the HPPs could be tuned by modulating the molar ratio of OVS and TPS. The HPPs showed high porosity, with Brunauer–Emmett–Teller specific surface areas of 518–989 m2 g–1, and total pore volumes of 0.35–0.76 cm3 g–1, as well as narrow pore-size distributions. For gas sorption application, HPP-5 possessed a hydrogen uptake of 0.80 wt.-% at 760 Torr/77 K and a carbon dioxide uptake of 3.31 wt.-% at 760 Torr/298 K.
Co-reporter:Dengxu Wang, Liguo Li, Wenyan Yang, Yujing Zuo, Shengyu Feng and Hongzhi Liu
RSC Advances 2014 vol. 4(Issue 104) pp:59877-59884
Publication Date(Web):27 Oct 2014
DOI:10.1039/C4RA11069B
Luminescent hybrid porous polymers (LHPPs) have been synthesized by the Heck coupling reactions of cubic octavinylsilsequioxane (OVS) and halogenated triphenylamine (TPA). The resulting materials show high thermal stability, and their porous and luminescent properties could be tuned by altering TPA species and reaction condition. The optimized polymer LHPP-3 exhibits high porosity with a Brunauer–Emmett–Teller surface area of 680 m2 g−1 and total pore volume of 0.41 cm3 g−1, and emits high yellow luminescence. LHPP-3 possesses a moderate CO2 uptake of 1.44 mmol g−1 at 273 K and 0.77 mmol g−1 at 298 K at 1.01 bar, suggesting these polymers could be utilized as adsorbents for CO2 storage and capture. Significantly, the luminescence of LHPP-3 could be quenched efficiently by nitroaromatic explosives such as 4-nitrotoluene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene, thereby indicating that the polymers could be utilized as chemical sensors for explosives detection.
Co-reporter:Dengxu Wang, Wenyan Yang, Liguo Li, Xian Zhao, Shengyu Feng and Hongzhi Liu
Journal of Materials Chemistry A 2013 vol. 1(Issue 43) pp:13549-13558
Publication Date(Web):04 Sep 2013
DOI:10.1039/C3TA12324C
Cubic octavinylsilsesquioxane successively reacts with different tetrahedral silicon-centered precursors containing di-, tri-, or tetrabromophenyl groups to prepare hybrid porous polymers (HPPs) via Heck reaction. The resulting materials possess high porosities with Brunauer–Emmett–Teller specific surface areas of up to 875 m2 g−1. Their porosities can be tuned by altering the number of the connecting sites of silicon-centered units. For gas storage applications, HPP-5 exhibits the following properties: a high H2 uptake of 7.76 mmol g−1 (1.56 wt%) at 77 K and 1.01 bar; a moderate CO2 uptake of 1.04 mmol g−1 (4.58 wt%) at 298 K and 1.04 bar; and a low CH4 uptake of 0.28 mmol g−1 (0.45 wt%) at 298 K and 1 bar. These results suggest that these polymers can be applied as promising materials for H2 and CO2 storage as well as the selective adsorbents of CO2 rather than CH4. These polymers are also luminescent with the maximum emission at ca. 420 nm in the solid state; therefore, they could be potentially applied as blue light-emitting materials.
Co-reporter:Dengxu Wang;Lei Xue;Liguo Li;Bei Deng;Shengyu Feng;Xian Zhao
Macromolecular Rapid Communications 2013 Volume 34( Issue 10) pp:861-866
Publication Date(Web):
DOI:10.1002/marc.201200835
Co-reporter:Yue Wu;Liguo Li;Shengyu Feng
Polymer Bulletin 2013 Volume 70( Issue 12) pp:3261-3277
Publication Date(Web):2013 December
DOI:10.1007/s00289-013-1019-8
Hybrid nanocomposites were prepared via solution blending of octaphenethyl POSS into novolac resin. The resulted hybrid blends were investigated by Fourier-transformed infrared spectra (FTIR), polarized optical microscopy (POM), wide X-ray diffraction and differential scanning calorimetry (DSC). FTIR results showed that there existed intermolecular hydrogen bond between the hydroxyl groups of the phenolic resin and POSS siloxane groups, which could promote POSS to disperse well in the polymer matrix up to 20 wt% POSS loading. At higher POSS loading, POSS would aggregate and lead to macrophase separation, which was demonstrated by POM, DSC and WXRD. Finally, hexamethylene tetramine was used to cure the novolac blends to form hybrid network phenolic nanocomposites. Dynamic mechanical analysis results showed that the storage modulus of the hybrid networks was improved up to 20 wt% POSS loading; the Tg was increased with increasing POSS content and higher than that of the control phenolic resin except that 5 wt% POSS loading. Thermo gravimetric analysis showed that the thermal stability of hybrid networks was also enhanced with the incorporation of POSS.
Co-reporter:Mingtao Ge and Hongzhi Liu
Journal of Materials Chemistry A 2016 - vol. 4(Issue 42) pp:NaN16722-16722
Publication Date(Web):2016/09/27
DOI:10.1039/C6TA06656A
A novel hybrid nanoporous network was easily fabricated by the one-step Heck reaction of octavinylsilsesquioxane with dibromothiophene. FTIR, solid state CP-MAS-NMR (13C and 29Si), and elemental analysis indicate that a thiophene unit has been successfully introduced into the silsesquioxane-based network. The Brunauer–Emmett–Teller (BET) measurement shows that this hybrid network possesses a high surface area of 915 m2 g−1, a large pore volume of 1.61 cm3 g−1, and unique hierarchical pores, i.e. uniform micropores and continuous multimodal mesopores. Remarkably, it displays an ultrahigh adsorption capability of 1402 mg g−1 for Rhodamine B, and 862 mg g−1 for Methylene Blue, which are among the highest values compared with other reported adsorbents. It also shows a good removal capability of toxic heavy metal ions from wastewater. More importantly, it could remove multiple pollutants efficiently from wastewater by simple filtration and possesses excellent regeneration performance.
Co-reporter:Huanhuan Liu and Hongzhi Liu
Journal of Materials Chemistry A 2017 - vol. 5(Issue 19) pp:NaN9162-9162
Publication Date(Web):2017/04/12
DOI:10.1039/C7TA01255A
Multifunctional hybrid fluorescent porous materials have been prepared by the Friedel–Crafts reaction of octavinylsilsesquioxane (OVS) with tetraphenylethene (TPE). These hybrid porous polymers possess high surface areas of up to 1910 cm2 g−1, and bimodal pore structures with micropores centered at ≈1.4 nm and mesopores centered at ≈4.5 nm. They show a moderate CO2 adsorption capacity of 6.25 wt% (1.42 mmol g−1) at 273 K/101 kPa. Remarkably, they exhibit highly size-selective adsorption of dye of 1666 mg g−1 for rhodamine B (RB), 1040 mg g−1 for congo red (CR) and 862 mg g−1 for crystal violet (CV). Furthermore, the incorporation of a tetraphenylethene unit induces higher fluorescence (λem = 490 nm) and high sensitivity for Fe3+, Cu2+ and Ru3+, especially for Fe3+ with KSV = 140 K M−1. They are very promising for multiple applications in dye separation, sensors, etc.
Co-reporter:Yue Wu, Dengxu Wang, Liguo Li, Wenyan Yang, Shengyu Feng and Hongzhi Liu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 7) pp:NaN2167-2167
Publication Date(Web):2013/11/29
DOI:10.1039/C3TA14746K
Friedel–Crafts reaction of cubic octavinylsilsesquioxane (OVS) and benzene results in a series of hybrid porous polymers (HPPs). The resulting materials, HPP-1 to HPP-4, show relatively high porosity with apparent Brunauer–Emmett–Teller surface areas in a range of 400 m2 g−1 to 904 m2 g−1, with total pore volumes in the range of 0.24 cm3 g−1 to 0.99 cm3 g−1. Their porosities can be fine tuned by adjusting the mole ratios of OVS and benzene. They feature both micro- and mesopores (HPP-1 and HPP-2) to almost mesopores (HPP-3 and HPP-4) in the networks. The ratios of micropore volume to total pore volume for HPP-1 to HPP-4 were 0.58, 0.42, 0.10, and 0.11, respectively. These materials exhibit comparable surface area and high thermal stability in a N2 atmosphere. The gas sorption applications reveal that HPP-3 possesses a H2 uptake of 3.47 mmol g−1 (0.70 wt%) at 77 K and 760 mmHg and a CO2 uptake of 0.62 mmol g−1 (2.73 wt%) at 298 K and 760 mmHg. These results indicate these materials are promising candidates for storing H2 and CO2. In addition, HPP-4 has been successfully postfunctionalized with 3-mercaptopropionic acid via thiol–ene “click” reaction.
Co-reporter:Dengxu Wang, Wenyan Yang, Liguo Li, Xian Zhao, Shengyu Feng and Hongzhi Liu
Journal of Materials Chemistry A 2013 - vol. 1(Issue 43) pp:NaN13558-13558
Publication Date(Web):2013/09/04
DOI:10.1039/C3TA12324C
Cubic octavinylsilsesquioxane successively reacts with different tetrahedral silicon-centered precursors containing di-, tri-, or tetrabromophenyl groups to prepare hybrid porous polymers (HPPs) via Heck reaction. The resulting materials possess high porosities with Brunauer–Emmett–Teller specific surface areas of up to 875 m2 g−1. Their porosities can be tuned by altering the number of the connecting sites of silicon-centered units. For gas storage applications, HPP-5 exhibits the following properties: a high H2 uptake of 7.76 mmol g−1 (1.56 wt%) at 77 K and 1.01 bar; a moderate CO2 uptake of 1.04 mmol g−1 (4.58 wt%) at 298 K and 1.04 bar; and a low CH4 uptake of 0.28 mmol g−1 (0.45 wt%) at 298 K and 1 bar. These results suggest that these polymers can be applied as promising materials for H2 and CO2 storage as well as the selective adsorbents of CO2 rather than CH4. These polymers are also luminescent with the maximum emission at ca. 420 nm in the solid state; therefore, they could be potentially applied as blue light-emitting materials.
![Pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane, 1-ethenyl-3,5,7,9,11,13,15-heptakis(2-methylpropyl)-](/data/chemimg/65400/444315-18-8.png)
![Pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane, 1-ethenyl-3,5,7,9,11,13,15-heptakis(2-methylpropyl)-](/data/chemimg/65400/444315-18-8_b.png)
![2-Propenoic acid, 1,1',1'',1''',1'''',1''''',1'''''',1'''''''-(pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane-1,3,5,7,9,11,13,15-octaylocta-3,1-propanediyl) ester](/data/chemimg/3783300/1204591-17-2.png)
![2-Propenoic acid, 1,1',1'',1''',1'''',1''''',1'''''',1'''''''-(pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane-1,3,5,7,9,11,13,15-octaylocta-3,1-propanediyl) ester](/data/chemimg/3783300/1204591-17-2_b.png)
![Pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane, 1,3,5,7,9,11,13,15-octakis(3-chloropropyl)-](/data/chemimg/130100/161678-38-2.png)
![Pentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane, 1,3,5,7,9,11,13,15-octakis(3-chloropropyl)-](/data/chemimg/130100/161678-38-2_b.png)
