Panchromatic Light-Absorbing [70]Fullerene-Perylene-BODIPY Triad with Cascade of Energy Transfer as an Efficient Singlet Oxygen Sensitizer.

A panchromatic light-absorbing [70]fullerene-perylene-BODIPY triad (C70-P-B) was synthesized and applied as a heavy atom-free organic triplet photosensitizer for photooxidation. The photophysical processes were comprehensively investigated by the methods of steady-state spectroscopy, time-resolved spectroscopy, as well as theoretical calculations. C70-P-B shows a strong absorption ability from 300-620 nm. Efficient cascading intramolecular singlet-singlet energy transfer in C70-P-B was confirmed by the luminescence study. The backward triplet excited state energy transfer from C70 moiety to perylene then occurs to populate 3perylene*. Thus, the triplet excited states of C70-P-B are distributed on both C70 and perylene moiety with lifetimes of 23 ± 1 µs and 175 ± 17 µs, respectively. C70-P-B exhibits excellent photooxidation capacity, and its yield of singlet oxygen reaches 0.82. The photooxidation rate constant of C70-P-B is 3.70 times that of C70-Boc and 1.58 times that of MB, respectively. The results in this paper are useful for designing efficient heavy atom-free organic triplet photosensitizers for practical application in photovoltaics, photodynamic therapy, etc.

Recent Advances in Zinc Hydroxystannate-Based Flame Retardant Polymer Blends.

During the combustion of polymeric materials, plenty of heat, smoke, and toxic gases are produced that may cause serious harm to human health. Although the flame retardants such as halogen- and phosphorus-containing compounds can inhibit combustion, they cannot effectively reduce the release of toxic fumes. Zinc hydroxystannate (ZHS, ZnSn(OH)6) is an environmentally friendly flame retardant that has attracted extensive interest because of its high efficiency, safety, and smoke suppression properties. However, using ZHS itself may not contribute to the optimal flame retardant effect, which is commonly combined with other flame retardants to achieve more significant efficiency. Few articles systematically review the recent development of ZHS in the fire safety field. This review aims to deliver an insight towards further direction and advancement of ZHS in flame retardant and smoke suppression for multiple polymer blends. In addition, the fire retarded and smoke suppression mechanism of ZHS will be demonstrated and discussed in depth.

Three-Dimensional Superhydrophobic Hollow Hemispherical MXene for Efficient Water-in-Oil Emulsions Separation.

A superhydrophobic macroporous material composed of hollow hemispherical MXene (HSMX) was synthesized by the thermal annealing of MXene-wrapped cationic polystyrene spheres (CPS@MXene). Notably, the spherical MXene shells exhibited highly efficient catalysis of the carbonization of CPS into carbon nanoparticles. Their insertion into the interlayer of MXene increased the d-spacing and created hollow hemispheres. The as-prepared HSMX with nanoscale walls had a lower packing density than MXene, but higher porosity, total pore volume, and total pore area. Moreover, the stacking of hollow hemispheres promoted the formation of a highly undulating macroporous surface and significantly improved the surface roughness of the HSMX-based 3D membrane, resulting in superhydrophobicity with a water contact angle of 156.4° and a rolling angle of 6°. As a result, the membrane exhibited good separation efficiency and Flux for emulsifier-stabilized water-in-paraffin liquid emulsions, which was dependent on its superhydrophobic performance and strong demulsification ability derived from the razor effect originating from the ultrathin walls of HSMX. This work provides a facile approach for the transformation of highly hydrophilic 2D MXene into superhydrophobic 3D HSMX, and opens a new pathway for the development of advanced MXene-based materials for environmental remediation applications.

Broadband Visible Light-Absorbing [70]Fullerene-BODIPY-Triphenylamine Triad: Synthesis and Application as Heavy Atom-Free Organic Triplet Photosensitizer for Photooxidation.

A broadband visible light-absorbing [70]fullerene-BODIPY-triphenylamine triad (C70-B-T) has been synthesized and applied as a heavy atom-free organic triplet photosensitizer for photooxidation. By attaching two triphenylmethyl amine units (TPAs) to the π-core of BODIPY via ethynyl linkers, the absorption range of the antenna is extended to 700 nm with a peak at 600 nm. Thus, the absorption spectrum of C70-B-T almost covers the entire UV-visible region (270-700 nm). The photophysical processes are investigated by means of steady-state and transient spectroscopies. Upon photoexcitation at 339 nm, an efficient energy transfer (ET) from TPA to BODIPY occurs both in C70-B-T and B-T, resulting in the appearance of the BODIPY emission at 664 nm. Direct or indirect (via ET) excitation of the BODIPY-part of C70-B-T is followed by photoinduced ET from the antenna to C70, thus the singlet excited state of C70 (1C70*) is populated. Subsequently, the triplet excited state of C70 (3C70*) is produced via the intrinsic intersystem crossing of C70. The photooxidation ability of C70-B-T was studied using 1,5-dihydroxy naphthalene (DHN) as a chemical sensor. The photooxidation efficiency of C70-B-T is higher than that of the individual components of C70-1 and B-T, and even higher than that of methylene blue (MB). The photooxidation rate constant of C70-B-T is 1.47 and 1.51 times as that of C70-1 and MB, respectively. The results indicate that the C70-antenna systems can be used as another structure motif for a heavy atom-free organic triplet photosensitizer.

Engineering MXene surface with POSS for reducing fire hazards of polystyrene with enhanced thermal stability.

High-performance MXene-based polymer nanocomposites are highly desirable for diverse industry applications due to their exceptional mechanical, thermal and other properties. Nevertheless, it remains an intractable challenge to create flame retardant polymer/MXene nanocomposites due to the difficulty to achieve uniform dispersion of MXenes. Here, we reported a facile strategy for the surface manipulation of two-dimensional titanium carbide nanosheets (Ti3C2Tx) with 3-aminopropylheptaisobutyl-polyhedral oligomeric silsesquioxane (AP-POSS) (POSS-Ti3C2Tx) through electrostatic interactions. The POSS-Ti3C2Tx is steadily dispersed in many polar solvents. Upon incorporated into polystyrene (PS), the combined effect of AP-POSS and MXene makes the resultant PS nanocomposites exhibit significantly improved thermal and thermoxidative stability, e.g. 22 °C and 39 °C increases in the temperature at 5 wt% mass loss under nitrogen and air, respectively. Meanwhile, a 39.1 % reduction in the peak heat release rate, a respective 54.4 % and 35.6 % reduction in the peak CO production rate and the peak CO2 production rate was achieved, which are superior to those of its own and previous counterparts. This outstanding fire safety is attributed to the combination of adsorption, catalytic and barrier effects of POSS-Ti3C2Tx. Hence, as-designed functionalized MXenes can be effectively applied in PS to formulate multifunctional polymer nanocomposites attractive for wide potential applications.

MXene/chitosan nanocoating for flexible polyurethane foam towards remarkable fire hazards reductions.

MXene/chitosan nanocoating for flexible polyurethane foam (PUF) was prepared via layer-by-layer (LbL) approach. MXene (Ti3C2) ultra-thin nanosheets were obtained through etching process of Ti3AlC2 followed by exfoliation. The deposition of MXene/chitosan nanocoating was conducted by alternatingly immersing the PUF into a chitosan solution and a Ti3C2 aqueous dispersion, which resulted in different number of bilayers (BL) ranging from 2, 5 and 8. Owing to the utilization of ultra-thin Ti3C2 nanosheets, the weight gain was only 6.9% for 8 BL coating of PUF, which minimised the unfavourable impact on the intrinsic properties of PUF. The Ti3C2/chitosan coating significantly reduced the flammability and smoke releases of PUF. Compared with unmodified PUF, the 8 BL coating reduced the peak heat release rate by 57.2%, alongside with a 65.5% reduction in the total heat release. The 8 BL coating also showed outstanding smoke suppression ability with total smoke release decreased by 71.1% and peak smoke production rate reduced by 60.3%, respectively. The peak production of CO and CO2 gases also decreased by 70.8% and 68.6%, respectively. Furthermore, an outstanding char formation performance of 37.2 wt.% residue was obtained for 8 BL coated PUF, indicating the excellent barrier and carbonization property of the hybrid coating.

Robust, Lightweight, Hydrophobic, and Fire-Retarded Polyimide/MXene Aerogels for Effective Oil/Water Separation.

Polyimide (PI) aerogels have attracted great attention owing to their low density and excellent thermal stability. However, hydrophobic surface modification is required for PI aerogels to improve their ability in oil/water separation due to their amphiphilic characteristic. Two-dimensional MXenes (transition metal carbides/nitrides) can be utilized as nanofillers to enhance the properties of polymers because of their unique layered structure and versatile interface chemistry. Herein, the robust, lightweight, and hydrophobic PI/MXene three-dimensional architectures were fabricated via freeze-drying of polyamide acid/MXene suspensions and thermal imidization. Polyamide acid was synthesized using N-N-dimethylacetamide and 4,4'-oxydianiline. MXene (Ti3C2Tx) dispersion was obtained via the etching of Ti3AlC2 and ultrasonic exfoliation. Taking advantage of the strong interaction between PI chains and MXene nanosheets, the interconnected, highly porous, and hydrophobic PI/MXene aerogels with low density were fabricated, resulting in the improved compressive performance, remarkable oil absorption capacity, and efficient separation of oil and water. For the PI/MXene-3 aerogel (weight ratio, 5.2:1) without any surface modification, the water contact angle was 119° with a density of 23 mg/cm3. This aerogel can completely recover to its original height after 50 compression-release cycles, exhibiting superelasticity and exceptional fatigue-resistant ability. It also showed high absorption capacities to various organic liquids ranging from approximately 18 to 58 times of their own weight. This hybrid aerogel can rapidly separate the chloroform, soybean oil, and liquid paraffin from the water-oil system. The thermally stable hybrid aerogel also exhibited excellent fire safety properties and outstanding reusability under an extreme environment.

Functionalization of MXene Nanosheets for Polystyrene towards High Thermal Stability and Flame Retardant Properties.

Fabricating high-performance MXene-based polymer nanocomposites is a huge challenge because of the poor dispersion and interfacial interaction of MXene nanosheets in the polymer matrix. To address the issue, MXene nanosheets were successfully exfoliated and subsequently modified by long-chain cationic agents with different chain lengths, i.e., decyltrimethylammonium bromide (DTAB), octadecyltrimethylammonium bromide (OTAB), and dihexadecyldimethylammonium bromide (DDAB). With the long-chain groups on their surface, modified Ti3C2 (MXene) nanosheets were well dispersed in N,N-dimethylformamide (DMF), resulting in the formation of uniform dispersion and strong interfacial adhesion within a polystyrene (PS) matrix. The thermal stability properties of cationic modified Ti3C2/PS nanocomposites were improved considerably with the temperatures at 5% weight loss increasing by 20 °C for DTAB-Ti3C2/PS, 25 °C for OTAB-Ti3C2/PS and 23 °C for DDAB-Ti3C2/PS, respectively. The modified MXene nanosheets also enhanced the flame-retardant properties of PS. Compared to neat PS, the peak heat release rate (PHRR) was reduced by approximately 26.4%, 21.5% and 20.8% for PS/OTAB-Ti3C2, PS/DDAB-Ti3C2 and PS/DTAB-Ti3C2, respectively. Significant reductions in CO and CO2 productions were also obtained in the cone calorimeter test and generally lower pyrolysis volatile products were recorded by PS/OTAB-Ti3C2 compared to pristine PS. These property enhancements of PS nanocomposites are attributed to the superior dispersion, catalytic and barrier effects of Ti3C2 nanosheets.

Interface decoration of exfoliated MXene ultra-thin nanosheets for fire and smoke suppressions of thermoplastic polyurethane elastomer.

Thermoplastic polyurethane (TPU) has broad applications as lightweight materials due to its multiple advantages and unique properties. Nevertheless, toxicity emission under fire conditions remains a major concern, particularly in building fire scenarios. To circumvent the problem, it is imperative that an effective flame retardant is sought to suppress the flame and release of combustion/smoke products whilst maintaining the favorable material properties of TPU. In the current work, a simple method is proposed for the preparation and utilization of cetyltrimethyl ammonium bromide (CTAB) and tetrabutyl phosphine chloride (TBPC) modified Ti3C2 (MXene) ultra-thin nanosheets. During the cone calorimeter tests, significant reduction in peak heat release rate (51.2% and 52.2%), peak smoke production rate (57.1% and 57.4%), peak CO production (39.4% and 41.6%) and peak CO2 production (49.7% and 51.7%) were recorded by the mere introduction of 2 wt.% CTAB-Ti3C2 and TBPC-Ti3C2 to TPU. These superior fire safety properties resulting from the significant reduction of the fire, smoke and toxicity hazards are attributed to the excellent dispersion, catalytic and barrier effect of Ti3C2 ultra-thin nanosheets in TPU. Future applications of exfoliated MXene nanosheets as flame retardant appear to be very promising.

Novel 3D Network Architectured Hybrid Aerogel Comprising Epoxy, Graphene, and Hydroxylated Boron Nitride Nanosheets.

A novel three-dimensional (3D) epoxy/graphene nanosheet/hydroxylated boron nitride (EP/GNS/BNOH) hybrid aerogel was successfully fabricated in this study. This was uniquely achieved by constructing a well-defined and interconnected 3D network architecture. The manufacturing process of EP/GNS/BNOH involved a simple one-pot hydrothermal strategy, followed by the treatment of freeze-drying and high-temperature curing. In comparison with EP/GNS-3, EP/GNS/BNOH-3 demonstrated improvement of 97% for compressive strength at 70% strain. Through compression tests, fracture occurred for EP/GNS-3 at ninth compression cycles, whereas EP/GNS/BNOH-3 retained its original form after twenty compression cycles, with a residual height of 97% (i.e., only 3% reduction). By the addition of BNOH in the polymer matrix, the dynamic heat transfer and dissipation rates of EP/GNS/BNOH aerogels were also considerably reduced, indicating that the aerogel with BNOH additive possessed excellent thermal insulation properties. Thermogravimetric analysis results revealed that the thermal stabilities of EP/GNS and EP/GNS/BNOH aerogels were improved with increasing loading of EP, and EP/GNS/BNOH aerogels exhibited a better thermal stability at high temperatures. Through the elevated levels attained in the compressive strength, superelasticity, and thermal resistance, EP/GNS/BNOH aerogels has the great potential of being a very effective thermal insulation material to be utilized across a board range of applications in building, automotive, spacecraft, and mechanical systems.

Comparative Studies on Thermal, Mechanical, and Flame Retardant Properties of PBT Nanocomposites via Different Oxidation State Phosphorus-Containing Agents Modified Amino-CNTs.

High-performance poly(1,4-butylene terephthalate) (PBT) nanocomposites have been developed via the consideration of phosphorus-containing agents and amino-carbon nanotube (A-CNT). One-pot functionalization method has been adopted to prepare functionalized CNTs via the reaction between A-CNT and different oxidation state phosphorus-containing agents, including chlorodiphenylphosphine (DPP-Cl), diphenylphosphinic chloride (DPP(O)-Cl), and diphenyl phosphoryl chloride (DPP(O3)-Cl). These functionalized CNTs, DPP(Ox)-A-CNTs (x = 0, 1, 3), were, respectively, mixed with PBT to obtain the CNT-based polymer nanocomposites through a melt blending method. Scanning electron microscope observations demonstrated that DPP(Ox)-A-CNT nanoadditives were homogeneously distributed within PBT matrix compared to A-CNT. The incorporation of DPP(Ox)-A-CNT improved the thermal stability of PBT. Moreover, PBT/DPP(O3)-A-CNT showed the highest crystallization temperature and tensile strength, due to the superior dispersion and interfacial interactions between DPP(O3)-A-CNT and PBT. PBT/DPP(O)-A-CNT exhibited the best flame retardancy resulting from the excellent carbonization effect. The radicals generated from decomposed polymer were effectively trapped by DPP(O)-A-CNT, leading to the reduction of heat release rate, smoke production rate, carbon dioxide and carbon monoxide release during cone calorimeter tests.

Surface Manipulation of Thermal-Exfoliated Hexagonal Boron Nitride with Polyaniline for Improving Thermal Stability and Fire Safety Performance of Polymeric Materials.

In this article, the polyaniline (PANI)/thermal-exfoliated hexagonal boron nitride (BNO) hierarchical structure (PANI-BNO) was constructed via in situ deposition to improve the dispersion and interfacial adhesion of boron nitride in multi-aromatic polystyrene (PS) and polar thermoplastic polyurethane (TPU). Because of the conjugated structure and polar groups in PANI, the uniform dispersion and strong interfacial adhesion between PANI-BNO and PS and TPU were achieved. Thermogravimetric analysis results showed that the incorporation of PANI-BNO enhanced the thermal stability of PS and TPU, i.e., the temperatures at both 5 and 50 wt % mass loss. In addition, PANI with high charring ability also acted as a critical component to generate a synergistic effect with BNO on reducing the fire hazards of PS and TPU. This well-designed structure led to a remarkable reduction of flammable decomposed products and CO and CO2 yields. Meanwhile, a dramatic decrease in the real-time smoke density and total smoke production was observed for PS and TPU nanocomposites with 3 wt % PANI-BNO hybrids, respectively. The multiple synergistic effects (synergistic dispersion, char formation, and barrier effect) are believed to be the primary source for these enhanced properties of polymer nanocomposites.

Functionalized Carbon Nanotubes with Phosphorus- and Nitrogen-Containing Agents: Effective Reinforcer for Thermal, Mechanical, and Flame-Retardant Properties of Polystyrene Nanocomposites.

Aminated multiwalled carbon nanotubes (A-MWCNT) were reacted with diphenylphosphinic chloride (DPP-Cl) to prepare the functionalized MWCNT (DPPA-MWCNT). A-MWCNT and DPPA-MWCNT were respectively mixed with polystyrene (PS) to obtain composites through the melt compounding method. SEM observations demonstrated that the DPPA-MWCNT nanofillers were more uniformly distributed within the PS matrix than A-MWCNT. PS/DPPA-MWCNT showed improved thermal stability, glass transition temperature, and tensile strength in comparison with PS/A-MWCNT, resulting from good dispersion and interfacial interactions between DPPA-MWCNT and PS matrix. The incorporation of DPPA-MWCNT to PS significantly reduced peak heat release rate, smoke production rate, and carbon monoxide and carbon dioxide release in cone calorimeter tests. The enhanced fire-retardant properties should be ascribed to the barrier effect of carbon nanotubes, which could provide enough time for DPPA-MWCNT and its functionalized groups to trap the degrading polymer radicals to catalyze char formation. The char layer served as an efficient insulating barrier to reduce the exposure of polymer matrix to an external heat source as well as retarding the flammable gases from feeding the flame.