Organophosphorus modified hollow bimetallic organic frameworks: Effective adsorption and catalytic charring of pyrolytic volatiles

Wang, Xiu; Wu, Tong; Hong, Jing; Dai, Juguo; Lu, Zhenwu; Yang, Chang‐Fa; Yuan, Conghui; Dai, Lizong

doi:10.1016/j.cej.2021.129697

Cited by 50 publications

(38 citation statements)

References 38 publications

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“…Interestingly, the residues of 4B-LDH@APP/EP are composed of dense cobweb-like microstructures (Figure d″), which can provide a better physical barrier to decrease the heat exchange obviously. Additionally, the Raman curves of these char residues (Figure a‴–d‴) show two representative peaks at 1350 and 1570 cm –1 , which are assigned to the D band (disordered graphite or glassy carbons) and G band (graphitized carbons), respectively, due to sp 2 -hybridized carbon’s vibration. , The ratio of integrated intensities of D and G bands ( I G / I D ) is usually applied to assess the graphitization degree of the char residual. , A lower ratio of I G / I D corresponds to a higher graphitization degree of the char residue, which can provide a better protective shielding effect for the underlying matrix . Here, 4B-LDH@APP/EP composite exhibits the lowest I D / I G value of 2.39 among the four samples (3.37 for pure EP, 3.02 for 4APP/EP, and 2.67 for 4LDH@APP/EP composites), revealing that the highest graphitization degree in the char residue and glassy-state boric oxide derived from the decomposition of boron acid plays a crucial part in promoting the charred quality of EPs.…”

Section: Resultsmentioning

confidence: 99%

Facile Construction of Inorganic Phosphorus/Boron-Layered Double Hydroxide Complexes for Highly Efficient Fire-Safety Epoxy Resin

Shao

Wang

Lin

et al. 2023

ACS Appl. Polym. Mater.

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For inorganic flame retardants, facile fabrication and high-efficiency fire safety without compromising the mechanical property of the matrix are still significant challenges. Here, nanolayered double hydroxide containing boron constructed on the surface of ammonium polyphosphate (APP) complexes (B-LDH@APP) is prepared by a simple in situ coprecipitation technology to reduce the fire hazard and improves the mechanical performances of epoxy resin (EP). The as-obtained 4B-LDH@APP/EP achieves the UL-94 V-0 rating and presents superior flame-safety performance. With respect to the 4APP/EP, the fire growth rate (FIGRA), the peak heat release rate (pHRR), and the peak smoke production rate (pSPR) of 4B-LDH@APP/EP decrease by 77.8, 57.3, and 52.6%, respectively. This is mainly attributed to the excellent synergistic flame-retardant effect among boron, LDH, and APP, which can accelerate the generation of compact charring residual with a good microstructure during combustion of B-LDH@APP/EP composites. Furthermore, B-LDH@APP slightly affects the mechanical performances of the EP matrix due to the upgraded interfacial interaction.

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Section: Resultsmentioning

confidence: 99%

Facile Construction of Inorganic Phosphorus/Boron-Layered Double Hydroxide Complexes for Highly Efficient Fire-Safety Epoxy Resin

Shao

Wang

Lin

et al. 2023

ACS Appl. Polym. Mater.

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“…More elaborate clues are provided with reference to the curves for aromatics at 1514 cm –1 and hydrocarbons at 2974 cm –1 (Figure d,e), which are considered as flame-supporting fuels. Compared with the above mentioned compounds, the earlier released phosphorus species promote the charring of organic molecular chains (Figure f), which is beneficial to retain more char compounds in the condensed phase. , Moreover, RPHN thermal decomposition yields phosphorus-containing compounds (e.g., PO • , PO 2 • , etc. ), which can trap essential reactive radicals such as H • , OH • , and R • , thus slowing down and preventing the combustion chain reaction process, conferring excellent flame retardancy and self-extinguishing properties for the sensor.…”

Section: Resultsmentioning

confidence: 99%

Hollow Nanospheres of Red Phosphorus for Fireproof Flexible Sensors Fabricated via 3D Printing

Song

Yuan

et al. 2022

ACS Appl. Nano Mater.

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High-power and high-temperature applications have brought increased demand for electrical sensing systems; however, conventional sensors have often been designed without consideration for stability in extreme environments (e.g., fire). Red phosphorus (RP) is a highly effective commercial flame retardant; however, its sensitive properties and large size predispose it to spontaneous combustion during shearing and make it difficult to combine with direct inkjet writing technology carrying micron-sized pinholes to fabricate sophisticated sensor devices. Here, bulk commercial red phosphorus (C-RP) is converted into red phosphorous hollow nanospheres (RPHNs). The ingeniously designed nanostructure effectively circumvents the flammability of C-RP extrusion processes and the risk of clogging the printing needle, and a fireproof pressure-sensitive sensor has been successfully fabricated. A load of RPHNs into a sensor matrix improves the moldability and fire safety properties. And with the assistance of the rapid charring mechanism, the peak of the heat release rate of the fireproof pressure-sensitive sensor is reduced by 58.9% compared to the pure matrix and withstands seven 2-s repetitive ignitions, thus allowing the sensor to respond continuously to flame stimulation. This work provides a broad perspective on the design of fireproof sensors and the application of red phosphorus hollow nanospheres.

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“…However, this premature phenomenon in organophosphorus-modified MOF composites is mostly absent during the flexural property evaluation but still present in tensile samples for lower weight fractions (≤0.2 wt %). Wang et al have demonstrated that the mechanical property of the epoxy composite was found to be improved in the presence of organophosphorus modified hollow bimetallic organic frameworks (W-Zr-MOF-DOPO) by virtue of the enhanced interaction between additives and the epoxy matrix . The study reveals that the presence of organophosphorus on the surface of MOF has a significant effect on the overall mechanical property of the composites.…”

Section: Resultsmentioning

confidence: 99%

“…Wang et al have demonstrated that the mechanical property of the epoxy composite was found to be improved in the presence of organophosphorus modified hollow bimetallic organic frameworks (W-Zr-MOF-DOPO) by virtue of the enhanced interaction between additives and the epoxy matrix. 54 The study reveals that the presence of organophosphorus on the surface of MOF has a significant effect on the overall mechanical property of the composites. Similarly, in the current study, it can be ascribed that the post-synthetic modification of MOF with the organophosphorus component acted decisively to enhance the mechanical property of the developed functionalized composites.…”

Section: Mechanical Propertiesmentioning

confidence: 90%

Organophosphorus-Functionalized Zirconium-Based Metal–Organic Framework Nanostructures for Improved Mechanical and Flame Retardant Polymer Nanocomposites

Unnikrishnan

Zabihi

et al. 2021

ACS Appl. Nano Mater.

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Metal−organic framework (MOF) nanostructures provide unique opportunities in the fabrication of multifunctional polymer nanocomposites. However, achieving both enhanced mechanical properties and fire safety using labile metal−organic framework (MOF) reinforced epoxy composites is usually challenging, calling for post-synthetic modification (PSM) of MOFs. In this study, we have synthesized an organophosphorus functionalized zirconium-based MOF, P-UiO-66 NH 2 (P-MOF). This as-synthesized modified MOF when reinforced with epoxy showcased improved mechanical and flame retardancy performance. Interestingly, the addition of 1 wt % of P-MOF in epoxy resin increases the tensile and flexural strength by 13.8 and 28.8% compared to the neat epoxy system. Similarly, in comparison with the pure epoxy nanocomposites, the tensile and flexural modulus of P-MOF reinforced nanocomposites was increased by 21.9 and 27.8%, respectively. Further, the flame retardancy properties of the P-MOF composites exhibited decreasing peak heat release rate (pHRR), smoke production rate (SPR), and carbon monoxide emission (CO) by 30, 42, and 43%, respectively, in parallel to the neat epoxy reinforced nanocomposites. This multifunctional property is primarily attributed to the enriched synergistic effects of the P-MOF with epoxy matrix, which promoted increased char layers on the epoxy surface, thus creating a carbonaceous layer to restrain the flame growth.

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Organophosphorus modified hollow bimetallic organic frameworks: Effective adsorption and catalytic charring of pyrolytic volatiles

Cited by 50 publications

References 38 publications

Facile Construction of Inorganic Phosphorus/Boron-Layered Double Hydroxide Complexes for Highly Efficient Fire-Safety Epoxy Resin

Facile Construction of Inorganic Phosphorus/Boron-Layered Double Hydroxide Complexes for Highly Efficient Fire-Safety Epoxy Resin

Hollow Nanospheres of Red Phosphorus for Fireproof Flexible Sensors Fabricated via 3D Printing

Organophosphorus-Functionalized Zirconium-Based Metal–Organic Framework Nanostructures for Improved Mechanical and Flame Retardant Polymer Nanocomposites

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