A nonmetallic plasmonic catalyst for photothermal CO2 flow conversion with high activity, selectivity and durability.

The meticulous design of active sites and light absorbers holds the key to the development of high-performance photothermal catalysts for CO2 hydrogenation. Here, we report a nonmetallic plasmonic catalyst of Mo2N/MoO2-x nanosheets by integrating a localized surface plasmon resonance effect with two distinct types of active sites for CO2 hydrogenation. Leveraging the synergism of dual active sites, H2 and CO2 molecules can be simultaneously adsorbed and activated on N atom and O vacancy, respectively. Meanwhile, the plasmonic effect of this noble-metal-free catalyst signifies its promising ability to convert photon energy into localized heat. Consequently, Mo2N/MoO2-x nanosheets exhibit remarkable photothermal catalytic performance in reverse water-gas shift reaction. Under continuous full-spectrum light irradiation (3 W·cm-2) for a duration of 168 h, the nanosheets achieve a CO yield rate of 355 mmol·gcat-1·h-1 in a flow reactor with a selectivity exceeding 99%. This work offers valuable insights into the precise design of noble-metal-free active sites and the development of plasmonic catalysts for reducing carbon footprints.

Nanoarray-Embedded Hierarchical Surfaces for Highly Durable Dropwise Condensation.

Durable dropwise condensation of saturated vapor is of significance for heat transfer and energy saving in extensive industrial applications. While numerous superhydrophobic surfaces can promote steam condensation, maintaining discrete microdroplets on surfaces without the formation of a flooded filmwise condensation at high subcooling remains challenging. Here, we report the development of carbon nanotube array-embedded hierarchical composite surfaces that enable ultra-durable dropwise condensation under a wide range of subcooling (ΔT sub = 8 K-38 K), which outperforms existing nanowire surfaces. This performance stems from the combined strategies of the hydrophobic nanostructures that allow efficient surface renewal and the patterned hydrophilic micro frames that protect the nanostructures and also accelerate droplet nucleation. The synergistic effects of the composite design ensure sustained Cassie wetting mode and capillarity-governed droplet mobility (Bond number < 0.055) as well as the large specific volume of condensed droplets, which contributes to the enhanced condensation heat transfer. Our design provides a feasible alternative for efficiently transferring heat in a vapor environment with relatively high temperatures through the tunable multiscale morphology.

Atomistic Insights into the Tunable Transition from Cavitation to Crazing in Diamond Nanothread-Reinforced Polymer Composites.

Cavitation and crazing in thermosetting polymers can be sophisticatedly designed for valuable applications in optics, electronics, and biotechnology. It is a great challenge for numerical study to describe the formations of cavity and fibrils in polymer composite due to the complicated interfacial interaction. To explore this challenging task, we exploit a two-phase coarse-grained framework which serves as an efficient atomistic level-consistent approach to expose and predict the transition between cavitation and crazing in a polymeric system. The coarse-grained framework is utilized to transmit the information between single phase and interface in polymer composite, and the learning tasks of force field are fulfilled through parameterization of mechanical performances and structural characterizations. We elaborate on the intrinsic characteristics of the cavitation-crazing transition in diamond nanothread- (DNT-) reinforced polymethyl methacrylate composites, in which DNT plays a specific role of nanomodulator to tune the cavity volume ratio. The transition from cavitation to crazing can be induced through a novel dissipative mechanism of opening an interlocked network, in which case the DNT is stretched to the aligned fibrils and links crazing tightly by interfacial adhesion. The designed computational framework can broaden the scope of theoretical tools for providing better insights into the microstructure design of polymer composites.

Cu-Mn-Ce ternary oxide catalyst coupled with KOH sorbent for air pollution control in confined space.

For air pollution control in confined space such as submarine and spacecraft, copper-manganese-cerium ternary oxide catalysts coupled with KOH sorbent were synthesized through the wet impregnation method, solid-state impregnation method A and B, and wet/solid-state impregnation method. The samples were tested for CO and CO2 removal dynamically and isothermally from 30 °C to 150 °C using two fixed bed reactors, and then characterized by XRD, nitrogen adsorption and desorption, and FE-SEM/EDS. The results showed that all the coupled CuMnCe/KOHs were able to catalyze CO and capture the produced CO2 in situ. While the coupling treatments affected the CO oxidation and CO2 absorption performance of the samples significantly and differently. Among all samples, CuMnCe/KOH-WSI with the large KOH bulk phase exhibited the outstanding CO catalytic activity and CO2 sorption efficiency, higher than the uncoupled CuMnCe/KOH. While for CuMnCe/KOH-WI and CuMnCe/KOH-SI-I samples demonstrating high-dispersed KOH species in the catalyst, the addition of the sorbent could inhibit the catalyst activity due to the occupation of the surface site and pore structure. Furtherly, the effect of the temperature was varied for CO conversion and CO2 capture performances of the sample, while they achieved an optimization balance at 150 °C for CuMnCe/KOH-WSI.

Nacre-Inspired Tunable Electromagnetic Interference Shielding Sandwich Films with Superior Mechanical and Fire-Resistant Protective Performance.

With the rapidly increasing development of portable device hardware and flexible electronics, ultrathin electromagnetic interference (EMI) shielding films with a combination of high flexibility and excellent mechanical properties are noticeably required. In addition to minimizing the electromagnetic wave pollution problem, the fire hazards caused by accidental electrical leakage or aging are also a cause of extensive concern. Inspired by nacre and sandwich structure, herein, we fabricated for the first time an electrical insulating sandwich-structured film based on Ca ion cross-linked sodium alginate (SA)-montmorillonite (MMT) and Ti3C2Tx MXene through a step-by-step vacuum-assisted filtration process. This novel design strategy not only maintains the inner EMI shielding network but also can act as an excellent fire-resistant barrier to protect the electronic device in case of accidental fire. Compared with the pure Ti3C2Tx layer, such kind of sandwich film can effectively maintain the EMI shielding performance (50.01 dB), dramatically enhance the mechanical properties (84.4 MPa), and exhibit excellent fire-resistant performance. Especially, compared with the film composed of mixture, the EMI shielding effectiveness value is only 55% that of sandwich films. Besides, it functions well under long-term heat aging test at 80 °C. Therefore, this unique design provides a novel EMI material strategy to facilitate its future applications in flexible electronics.

Controlled self-template synthesis of manganese-based cuprous oxide nanoplates towards improved fire safety properties of epoxy composites.

To date epoxy resins have been extensively used in the field of chemical engineering, aerospace and building materials. Nevertheless, the utilization of flammable epoxy resins has posed a huge threat to lives and properties, which restricted their applications. In this work, manganese-based cuprous oxides two-dimensional nanosheets (Mn@Cu2O-M) are rationally designed and successfully prepared to improve the toxic effluent elimination of epoxy resin. The fire safety properties of the prepared Mn@Cu2O-M based nanocomposites improved the heat release rate (<35 %) and total heat release (<40 %) compared to the control epoxy. Moreover, the production of smoke and toxic volatiles of the composites with Mn@Cu2O-M nanosheets is significantly reduced. The mechanism investigations indicate that the improved flame retardancy and toxic effluent elimination of epoxy composites are attributed to the physical barrier effect and catalytic carbonization awarded by Mn@Cu2O-M nanosheets during burning. This work provides a promising strategy to develop eco-friendly, efficient and fire-safe polymers by both physical barrier effect and catalytic carbonization.

Self-assembly of zinc hydroxystannate on amorphous hydrous TiO2 solid sphere for enhancing fire safety of epoxy resin.

Zinc hydroxystannate (ZHS) was fabricated on the surface of amorphous hydrous TiO2 solid spheres (AHTSS) via a layer-by-layer method for improving the fire safety of epoxy resin. AHTSS@PEI@ZHS was prepared by self-assembly of AHTSS, PEI and ZHS. The well-organized fabrication process was proved by TEM, XPS, XRD and SEM tests. TG results illustrated that the incorporation of AHTSS@PEI@ZHS show a higher residue compared with the addition of AHTSS or ZHS alone. In addition, AHTSS@PEI@ZHS filled EP composites exhibits improved flame retardancy and smoke suppression properties evaluated by cone calorimeter test. TG-IR results also indicated that the catalytic labyrinth structure of AHTSS@PEI@ZHS can effectively decrease the permeation of volatile organic compounds, thereby improving the fire safety of EP resin.

Studies on Synthesis of Electrochemically Exfoliated Functionalized Graphene and Polylactic Acid/Ferric Phytate Functionalized Graphene Nanocomposites as New Fire Hazard Suppression Materials.

Practical application of functionalized graphene in polymeric nanocomposites is hampered by the lack of cost-effective and eco-friendly methods for its production. Here, we reported a facile and green electrochemical approach for preparing ferric phytate functionalized graphene (f-GNS) by simultaneously utilizing biobased phytic acid as electrolyte and modifier for the first time. Due to the presence of phytic acid, electrochemical exfoliation leads to low oxidized graphene sheets (a C/O ratio of 14.8) that are tens of micrometers large. Successful functionalization of graphene was confirmed by the appearance of phosphorus and iron peaks in the X-ray photoelectron spectrum. Further, high-performance polylactic acid/f-GNS nanocomposites are readily fabricated by a convenient masterbatch strategy. Notably, inclusion of well-dispersed f-GNS resulted in dramatic suppression on fire hazards of polylactic acid in terms of reduced peak heat-release rate (decreased by 40%), low CO yield, and formation of a high graphitized protective char layer. Moreover, obviously improvements in crystallization rate and thermal conductivities of polylactic acid nanocomposites were observed, highlighting its promising potential in practical application. This novel strategy toward the simultaneous exfoliation and functionalization for graphene demonstrates a simple yet very effective approach for fabricating graphene-based flame retardants.

Integrated effect of supramolecular self-assembled sandwich-like melamine cyanurate/MoS2 hybrid sheets on reducing fire hazards of polyamide 6 composites.

A novel strategy of using supramolecular self-assembly for preparing sandwich-like melamine cyanurate/MoS2 sheets as the hybrid flame retardants for polyamide 6 (PA6) is reported for the first time. The introduction of MoS2 sheets function not only as a template to induce the formation of two-dimensional melamine cyanurate capping layers but also as a synergist to generate integrated flame-retarding effect of hybrid sheets, as well as a high-performance smoke suppressor to reduce fire hazards of PA6 materials. Once incorporating this well-designed structures (4wt%) into PA6 matrix, there resulted in a remarkable drop (40%) in the peak heat release rate and a 25% reduction in total heat release. Moreover, the smoke production and pyrolysis gaseous products were efficiently suppressed by the addition of sandwich-like hybrid sheets. The integrated functions consisting of inherent flame retarding effect, physical barrier performance and catalytic activity are believed to the crucial guarantee for the reduced fire hazards of PA6 nanocomposites. Furthermore, this novel strategy with facile and scalable features may provide reference for developing various kinds of MoS2 based hybrid sheets for diverse applications.

Ionic Adsorption and Desorption of CNT Nanoropes.

A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment.

High-Performance Poly(ethylene oxide)/Molybdenum Disulfide Nanocomposite Films: Reinforcement of Properties Based on the Gradient Interface Effect.

Herein, the molybdenum disulfide (MoS2) was simultaneously exfoliated and noncovalently functionalized by ultrasonication in a Pluronic aqueous solution and then was used to prepare the poly(ethylene oxide) (PEO) based nanocomposite films. The homogeneous dispersion of MoS2 and strong nanosheets/matrix interfacial adhesion were confirmed by representative electron microscopes. The considerable barrier action of the effective MoS2 nanosheets obviously restricted the ordering of crystal lamellae and the motion of polymer chains and then resulted in the formation of the devastated spherocrystal structure and morphological alterations in the nanocomposites, which were confirmed by polarized optical microscopy and the high value of the glass transition temperature. Importantly, MoS2 nanosheets hold great promise in reinforcing the thermal stability and mechanical property of polymer by increasing the effective volume of MoS2 nanosheets. A substantial reinforcement effect of PEO/MoS2 composite films was achieved: even at a relatively low loading level (0.9 wt %), 88.1% increase in Young's modulus, 72.7% increase in stress-at-failure, and 62.1 °C increment of the temperature corresponding to half weight loss were obtained. These significant reinforcements can be attributed to the gradient interface region, which could effectively transfer the stress from the weak polymer chains to the robust nanosheets, thus endowing the PEO/MoS2 composite films with excellent properties.

Formation of self-extinguishing flame retardant biobased coating on cotton fabrics via Layer-by-Layer assembly of chitin derivatives.

The self-extinguishing coating, consisting of biobased chitin derivatives, phosphorylated chitin and deacetylated chitin (chitosan), was deposited on cotton fabrics via the Layer-by-Layer (LbL) assembled method. The content of phosphorylated chitin prepared on cotton fabrics surface is dependent on the bilayers' number and concentration of phosphorylated chitin. In the vertical flame test, the cotton fabric with 20 bilayers prepared at the high phosphorylated chitin concentration (2 wt%) could extinguish the flame. Microcombustion calorimetry result showed that all coated cotton fabrics showed lower peak heat-release rate and total heat-release values compared with that of the pure one. Thermogravimetric analysis result indicated that thermal and thermal oxidation stability of all coated cotton fabrics were enhanced in the high temperature range (400-700°C). This work provided the flame retardant multilayer films based on fully biobased chitin derivatives on cotton fabrics to enhance its flame retardancy.

Formation of layer-by-layer assembled titanate nanotubes filled coating on flexible polyurethane foam with improved flame retardant and smoke suppression properties.

A fire blocking coating made from chitosan, titanate nanotubes and alginate was deposited on a flexible polyurethane (FPU) foam surface by a layer-by-layer assembly technique in an effort to reduce its flammability. First, titanate nanotubes were prepared by a hydrothermal method. And then the coating growth was carried out by alternately submerging FPU foams into chitosan solution, titanate nanotubes suspension and alginate solution. The mass gain of coating on the surface of FPU foams showed dependency on the concentration of titanate nanotubes suspension and the trilayers's number. Scanning electron microscopy indicated that titanate nanotubes were distributed well on the entire surface of FPU foam and showed a randomly oriented and entangled network structure. The cone calorimeter result indicated that the coated FPU foams showed reduction in the peak heat release rate (peak HRR), peak smoke production rate (peak SPR), total smoke release (TSR) and peak carbon monoxide (CO) production compared with those of the control FPU foam. Especially for the FPU foam with only 5.65 wt % mass gain, great reduction in peak HRR (70.2%), peak SPR (62.8%), TSR (40.9%) and peak CO production (63.5%) could be observed. Such a significant improvement in flame retardancy and the smoke suppression property for FPU foam could be attributed to the protective effect of titanate nanotubes network structure formed, including insulating barrier effect and adsorption effect.

Interface enhancement of glass fiber reinforced vinyl ester composites with flame-synthesized carbon nanotubes and its enhancing mechanism.

Interface enhancement with carbon nanotubes (CNTs) provides a promising approach for improving shock strength and toughness of glass fiber reinforced plastic (GFRP) composites. The effects of incorporating flame-synthesized CNTs (F-CNTs) into GFRP were studied, including on hand lay-up preparation, microstructural characterization, mechanical properties, fracture morphologies, and theoretical calculation. The experimental results showed that: (1) the impact strength of the GFRP modified by F-CNTs increased by more than 15% over that of the GFRP modified by CNTs from chemical vapor deposition; and (2) with the F-CNT enhancement, no interfacial debonding was observed at the interface between the fiber and resin matrix on the GFRP fracture surface, which indicated strong adhesive strength between them. The theoretical calculation revealed that the intrinsic characteristics of the F-CNTs, including lower crystallinity with a large number of defects and chemical functional groups on the surface, promoted their surface activity and dispersibility at the interface, which improved the interfacial bond strength of GFRP.