Thermally Insulating and Moisture-Resilient Foams Based on Upcycled Aramid Nanofibers and Nanocellulose.

Low-density foams and aerogels based on upcycled and bio-based nanofibers and additives are promising alternatives to fossil-based thermal insulation materials. Super-insulating foams are prepared from upcycled acid-treated aramid nanofibers (upANFA ) obtained from Kevlar yarn and tempo-oxidized cellulose nanofibers (CNF) from wood. The ice-templated hybrid upANFA /CNF-based foams with an upANFA content of up to 40 wt% display high thermal stability and a very low thermal conductivity of 18-23 mW m-1 K-1 perpendicular to the aligned nanofibrils over a wide relative humidity (RH) range of 20% to 80%. The thermal conductivity of the hybrid upANFA /CNF foams is found to decrease with increasing upANFA content (5-20 wt%). The super-insulating properties of the CNF-upANFA hybrid foams are related to the low density of the foams and the strong interfacial phonon scattering between the very thin and partially branched upANFA and CNF in the hybrid foam walls. Defibrillated nanofibers from textiles are not limited to Kevlar, and this study can hopefully inspire efforts to upcycle textile waste into high-performance products.

Tunable Ordered Nanostructured Phases by Co-assembly of Amphiphilic Polyoxometalates and Pluronic Block Copolymers.

The assembly of polyoxometalate (POM) metal-oxygen clusters into ordered nanostructures is attracting a growing interest for catalytic and sensing applications. However, assembly of ordered nanostructured POMs from solution can be impaired by aggregation, and the structural diversity is poorly understood. Here, we present a time-resolved small-angle X-ray scattering (SAXS) study of the co-assembly in aqueous solutions of amphiphilic organo-functionalized Wells-Dawson-type POMs with a Pluronic block copolymer over a wide concentration range in levitating droplets. SAXS analysis revealed the formation and subsequent transformation with increasing concentration of large vesicles, a lamellar phase, a mixture of two cubic phases that evolved into one dominating cubic phase, and eventually a hexagonal phase formed at concentrations above 110 mM. The structural versatility of co-assembled amphiphilic POMs and Pluronic block copolymers was supported by dissipative particle dynamics simulations and cryo-TEM.

Assembly of cellulose nanocrystals and clay nanoplatelets studied by time-resolved X-ray scattering.

Time-resolved small-angle X-ray scattering (SAXS) was used to probe the assembly of cellulose nanocrystals (CNC) and montmorillonite (MNT) over a wide concentration range in aqueous levitating droplets. Analysis of the SAXS curves of the one-component and mixed dispersions shows that co-assembly of rod-like CNC and MNT nanoplatelets is dominated by the interactions between the dispersed CNC particles and that MNT promotes gelation and assembly of CNC, which occurred at lower total volume fractions in the CNC:MNT than in the CNC-only dispersions. The CNC dispersions displayed a d ∝ φ-1/2 scaling and a low-q power-law exponent of 2.0-2.2 for volume fractions up to 35%, which indicates that liquid crystal assembly co-exists and competes with gelation.

Self-assembly of amphiphilic polyoxometalates for the preparation of mesoporous polyoxometalate-titania catalysts.

Amphiphilic polyoxometalate (POM) surfactants were prepared by covalently grafting double hydrophobic tails with chain lengths C12H25, C14H29, C16H33 or C18H37 onto the lacunary Wells-Dawson {P2W17O61} headgroup. The critical micelle concentrations (CMCs) of these novel surfactants in aqueous solutions were determined by conductivity, and micelle formation was studied by small angle neutron scattering (SANS). Surprisingly, the amphiphiles with longer hydrophobic tails tend to form less elongated and more globular micelles in water. The self-assembled amphiphilic polyoxometalates were used as templates in the hydrothermal synthesis of mesoporous TiO2 containing dispersed, immobilised {P2W17O61} units, which showed enhanced activity for the photodegradation of rhodamine B (RhB). The catalyst was recycled eight times with no loss of efficiency, demonstrating the stability of the hybrid structure. The amphiphilic polyoxometalates, therefore have excellent potential for the synthesis of various types of catalytically active porous materials.

Antagonistic mixing in micelles of amphiphilic polyoxometalates and hexaethylene glycol monododecyl ether.

HYPOTHESIS: Polyoxometalates (POMs) are metal oxygen clusters with a range of interesting magnetic and catalytic properties. POMs with attached hydrocarbon chains show amphiphilic behaviour so we hypothesised that mixtures of a nonionic surfactant and anionic surfactants with a polyoxometalate cluster as headgroup would form mixed micelles, giving control of the POM density in the micelle, and which would differ in size and shape from micelles formed by the individual surfactants. Due to the high charge and large size of the POM, we suggested that these would be nonideal mixtures due to the complex interactions between the two types of surfactants. The nonideality and the micellar composition may be quantified using regular solution theory. With supplementary information provided by small-angle neutron scattering (SANS), an understanding of this unusual binary surfactant system can be established. EXPERIMENTS: A systematic study was performed on mixed surfactant systems containing polyoxometalate-headed amphiphiles (K10[P2W17O61OSi2(CnH2n+1)2], abbreviated as P2W17-2Cn, where n = 12, 14 or 16) and hexaethylene glycol monododecyl ether (C12EO6). Critical micelle concentrations (CMCs) of these mixtures were measured and used to calculate the interaction parameters based on regular solution theory, enabling prediction of micellar composition. Predictions were compared to micelle structures obtained from SANS. A phase diagram was also established. FINDINGS: The CMCs of these mixtures suggest unusual unfavourable interactions between the two species, despite formation of mixed micelles. Micellar compositions obtained from SANS concurred with those calculated using the averaged interaction parameters for P2W17-2Cn/C12EO6 (n = 12 and 14). We attribute the unfavourable interactions to a combination of different phenomena: counterion-mediated interactions between P2W17 units and the unfolding of the ethylene oxide headgroups of the nonionic surfactant, yet micelles still form in these systems due to the hydrophobic interactions between surfactant tails.

A Facile, Template-Free Synthesis of AgCl Hierarchical Architectures: Precursors of Highly Efficient Visible-Light Plasmonic Photocatalysts of Ag@AgCl.

This paper describes a facile, template-free synthesis of AgCl hierarchical structures by a gas-liquid interfacial method and the morphology of AgCl (microrods or film) can be conveniently varied or controlled by changing the solvents of AgNO3 without using any surfactants. The AgCl composites were then photoreduced to form highly efficient visible-light plasmonic photocatalyst Ag@AgCl nanostructures. SEM, XRD, X-ray photoelectron spectroscopy, and UV/Vis diffuse reflectance spectroscopy were used to characterize the obtained product. The photocatalytic activity of the obtained product was evaluated by the photodegradation of methyl orange pollutant under visible-light irradiation, and it was found that Ag@AgCl microrods exhibited high visible-light photocatalytic activity and good stability.