Solid state chemical transformations through ring-opening polymerization of ferrocene-based conjugated microporous polymers in host–guest complexes with benzoxazine-linked cyclodextrin

Samy, Maha Mohamed; Mohamed, Mohamed Gamal; Mansoure, Tharwat Hassan; Meng, Tso Shiuan; Khan, Mo Aqib Raza; Liaw, Chih‐Chuang; Kuo, Shiao‐Wei

doi:10.1016/j.jtice.2021.10.010

Cited by 42 publications

(44 citation statements)

References 82 publications

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“…Because strong inter- and intramolecular hydrogen bonds exist after the thermal ROP of BZ units, formed among the tertiary amino and phenolic units in the Mannich bridges, the polymerization products can possess low dielectric constants, low surface free energies, low degrees of shrinkage, and high thermal stabilities and char yields [ 14 , 15 , 16 , 17 , 18 , 19 , 20 ]. Flexibility in molecular design—by varying the structures of the phenolic and amino groups—has allowed the introduction of a range of functional groups (e.g., allyl, propargyl, crown ether) [ 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 ] or inorganic nanomaterials (such as polyhedral oligomeric silsesquioxane, graphene, carbon nanotube) [ 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ] into the BZ matrix.…”

Section: Introductionmentioning

confidence: 99%

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine

et al. 2022

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New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on 1H and 13C NMR and FTIR spectroscopic analyses through the reduction of Schiff base formed from tetrakis(4-aminophenyl)porphyrin (TAPP) and salicylaldehyde and the subsequent reaction with CH2O. Thermal properties of the product formed through ring-opening polymerization (ROP) of Por-BZ were measured using DSC, TGA and FTIR spectroscopy. Because of the rigid structure of the porphyrin moiety appended to the benzoxazine unit, the temperature required for ROP (314 °C) was higher than the typical Pa-type benzoxazine monomer (ca. 260 °C); furthermore, poly(Por-BZ) possessed a high thermal decomposition temperature (Td10 = 478 °C) and char yield (66 wt%) after thermal polymerization at 240 °C. An investigation of the thermal and luminescence properties of metal–porphyrin complexes revealed that the insertion of Ni and Zn ions decreased the thermal ROP temperatures of the Por-BZ/Ni and Por-BZ/Zn complexes significantly, to 241 and 231 °C, respectively. The metal ions acted as the effective promoter and catalyst for the thermal polymerization of the Por-BZ monomer, and also improved the thermal stabilities after thermal polymerization.

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Section: Introductionmentioning

confidence: 99%

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine

et al. 2022

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“…Furthermore, the maximum exothermic curing peak of the oxazine ring of the AP-BZ POP appeared at 257 °C in the DSC thermograms Figure 4 c). The semicrystalline character of the PA-BZ POP was evidenced by three major diffraction peaks appearing at 10.18, 20.79, and 40.79° in the X-ray diffraction (XRD) pattern as presented in Figure 4 d [ 12 , 45 , 58 ]. We also investigated the ROP of PA-BZ POP through in situ FTIR spectroscopic analyses at temperatures from 25 to 250 °C ( Figure S3 ).…”

Section: Resultsmentioning

confidence: 99%

“…The PA-BZ POP, PA-BZ POP/metal composite, MCP, and PCMC samples displayed good cycling stability, with 87.5, 88.6, 91.0, and 95.0% retention, respectively, of their original capacitances after 2000 cycles, indicating excellent cycling stability in 1 M KOH as the electrolyte. Recently, we prepared ferrocene-derived conjugated microporous polymers (FFC-CMPs) and then formed an inclusion complex with a BZ-linked β-cyclodextrin (Py-FFC-CMP/CD-BZ) [ 12 ]; this material exhibited capacitance of only 46 F g –1 at 0.5 A g –1 . In addition, we have previously prepared a series of CMPs through Sonogashira–Hagihara cross-couplings of a tetrabenzonaphthalene (TBN) monomer with tetraphenylethylene (TPE), pyrene (Py), and carbazole (Car) units; we then mixed them with highly conductive single-walled carbon nanotubes (SWCNTs) to improve their conductivity [ 45 ], with the TBN-Py-CMP/SWCNT composite exhibiting high capacitance (430 F g –1 ) at a current density of 0.5 A g –1 because of strong π-stacking of the SWCNTs with the CMPs [ 45 ].…”

Section: Resultsmentioning

confidence: 99%

“…Nevertheless, the application of PBZ materials has been restricted industrially because the ROP of BZ resins to afford PBZs generally occurs at temperatures between 220 and 280 °C [ 10 , 11 , 12 , 13 , 14 ]. As a result, lowering the exothermic curing temperatures of BZ precursors has become desirable to encourage the use of these materials in industrial applications and academic settings [ 1 , 2 , 3 , 4 , 5 ].…”

Section: Introductionmentioning

confidence: 99%

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Microporous Carbon and Carbon/Metal Composite Materials Derived from Bio-Benzoxazine-Linked Precursor for CO2 Capture and Energy Storage Applications

Mohamed

Samy

Mansoure

et al. 2021

IJMS

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There is currently a pursuit of synthetic approaches for designing porous carbon materials with selective CO2 capture and/or excellent energy storage performance that significantly impacts the environment and the sustainable development of circular economy. In this study we prepared a new bio-based benzoxazine (AP-BZ) in high yield through Mannich condensation of apigenin, a naturally occurring phenol, with 4-bromoaniline and paraformaldehyde. We then prepared a PA-BZ porous organic polymer (POP) through Sonogashira coupling of AP-BZ with 1,3,6,8-tetraethynylpyrene (P-T) in the presence of Pd(PPh3)4. In situ Fourier transform infrared spectroscopy and differential scanning calorimetry revealed details of the thermal polymerization of the oxazine rings in the AP-BZ monomer and in the PA-BZ POP. Next, we prepared a microporous carbon/metal composite (PCMC) in three steps: Sonogashira coupling of AP-BZ with P-T in the presence of a zeolitic imidazolate framework (ZIF-67) as a directing hard template, affording a PA-BZ POP/ZIF-67 composite; etching in acetic acid; and pyrolysis of the resulting PA-BZ POP/metal composite at 500 °C. Powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller (BET) measurements revealed the properties of the as-prepared PCMC. The PCMC material exhibited outstanding thermal stability (Td10 = 660 °C and char yield = 75 wt%), a high BET surface area (1110 m2 g–1), high CO2 adsorption (5.40 mmol g–1 at 273 K), excellent capacitance (735 F g–1), and a capacitance retention of up to 95% after 2000 galvanostatic charge–discharge (GCD) cycles; these characteristics were excellent when compared with those of the corresponding microporous carbon (MPC) prepared through pyrolysis of the PA-BZ POP precursors with a ZIF-67 template at 500 °C.

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“…The ELDC of the materials can be attributed to their surface areas. The materials that have high surface areas, such as carbonaceous materials, conjugated microporous polymers (CMPs), and covalent organic frameworks (COFs), usually have high EDLC [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 ]. It is, therefore, important to explore new electrode materials that synergize both EDLC and PC.…”

Section: Introductionmentioning

confidence: 99%

Ultrastable Conjugated Microporous Polymers Containing Benzobisthiadiazole and Pyrene Building Blocks for Energy Storage Applications

et al. 2022

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In recent years, conjugated microporous polymers (CMPs) have become important precursors for environmental and energy applications, compared with inorganic electrode materials, due to their ease of preparation, facile charge storage process, π-conjugated structures, relatively high thermal and chemical stability, abundance in nature, and high surface areas. Therefore, in this study, we designed and prepared new benzobisthiadiazole (BBT)-linked CMPs (BBT–CMPs) using a simple Sonogashira couplings reaction by reaction of 4,8-dibromobenzo(1,2-c;4,5-c′)bis(1,2,5)thiadiazole (BBT–Br2) with ethynyl derivatives of triphenylamine (TPA-T), pyrene (Py-T), and tetraphenylethene (TPE-T), respectively, to afford TPA–BBT–CMP, Py–BBT–CMP, and TPE–BBT–CMP. The chemical structure and properties of BBT–CMPs such as surface areas, pore size, surface morphologies, and thermal stability using different measurements were discussed in detail. Among the studied BBT–CMPs, we revealed that TPE–BBT–CMP displayed high degradation temperature, up to 340 °C, with high char yield and regular, aggregated sphere based on thermogravimetric analysis (TGA) and scanning electron microscopy (SEM), respectively. Furthermore, the Py–BBT–CMP as organic electrode showed an outstanding specific capacitance of 228 F g–1 and superior capacitance stability of 93.2% (over 2000 cycles). Based on theoretical results, an important role of BBT–CMPs, due to their electronic structure, was revealed to be enhancing the charge storage. Furthermore, all three CMP polymers featured a high conjugation system, leading to improved electron conduction and small bandgaps.

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Solid state chemical transformations through ring-opening polymerization of ferrocene-based conjugated microporous polymers in host–guest complexes with benzoxazine-linked cyclodextrin

Cited by 42 publications

References 82 publications

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine

Microporous Carbon and Carbon/Metal Composite Materials Derived from Bio-Benzoxazine-Linked Precursor for CO2 Capture and Energy Storage Applications

Ultrastable Conjugated Microporous Polymers Containing Benzobisthiadiazole and Pyrene Building Blocks for Energy Storage Applications

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