Facile self-assembly approach to construct a novel MXene-decorated nano-sized phase change material emulsion for thermal energy storage

In recent years, phase change material emulsions (PCMEs) with enhanced energy storage capacities and good flow characteristics have drawn significant attention. However, due to the thermodynamically unstable nature and tiny particle confinement, the nanomaterial modification strategies at PCM/water interface to improve stabilities and reduce supercooling of nano-sized PCMEs (NPCMEs) are very limited and challenging. Herein, we report a facile strategy for constructing MXene-decorated NPCME with good stability, little supercooling, and high thermal conductivity by self-assembly of MXene nanosheets at PCM/water interface. The concentrations of MXene have great influences on the average droplet diameters, stabilities, and thermophysical properties of the NPCMEs. The results show that the PCMs have been well dispersed into the water in the form of quasi-spherical droplets, with average droplet diameters of 242–805 nm. The thermal conductivity of 10 wt% n-tetradecane/water NPCME containing 9 mg ml^-1 MXene is 0.693 W m^-1·K^-1, achieving an enhancement by 15.5%, as compared to that of water. Besides, the MXene-decorated paraffin/water NPCMEs exhibit little supercooling and enhanced heat storage capacities. More importantly, this facile self-assembly strategy opens a new platform for preparing high-performance NPCMEs, which can be used as novel heat transfer fluids for thermal energy storage systems.     

Self-assembly of nanoparticle-rich interphases in fiber reinforced polymeric composites using migrating agents

Thermoplastic additives, known as migrating agents, can be added to nanoparticle loaded thermosetting resins to form self-assembled nanoparticle structures. Most notably, in fiber reinforced thermosetting composites, self-assembled nanoparticle rich fiber-matrix interphases can be formed. While the self-assembly mechanism remains unclear, depletion interaction correctly describes the types of self-assembled structures formed. Formulations containing modest concentrations of migrating agent form self-assembled fiber-matrix interphases without causing aggregation in the bulk. Slight overdoses of migrating agent can lead to the formation of nanoparticle aggregates in the bulk phase, which can ultimately reduce the mechanical properties of the composite. Even larger overdoses of migrating agent cause the formation of large and open nanoparticle aggregates, indicative of rapid aggregation. Depletion theory predicts that larger molecular weight migrating agents should induce greater attractive forces, thus reducing the concentrations required to form these self-assembled structures. In this study, the migrating agent molecular weight dependence on the self-assembly and aggregation phenomenon are investigated. As predicted by depletion theory, larger molecular weights led to the formation of self-assembled interphases and aggregates at lower concentrations.     

Self-assembly of ultralight and compressible inorganic sponges with hierarchical porosity by electrospinning

The construction of three dimensional macroporous architectures holds exciting implications for applications such as catalysis, sensing, tissue engineering and thermal insulation. Here, we report a general self-assembly process for inorganic sponges with hierarchical porosity of intrafibre micro-/meso-/macropores and interfibre macropores. The as-fabricated SiO₂-TiO₂ sponge possesses a high porosity of >99.86%, ultralow bulk density of 2.9 mg cm⁻³ and enhanced compressibility (recovery from 50% compression). The self-assembly mechanism of the SiO₂-TiO₂ sponge has been investigated in detail. The results confirmed that the hydrolysis and polycondensation of mixed inorganic alkoxides could affect the solidification process and the charge transpote during electrospinning, and plays an essential role on the hierarchical porosity and the self-assembly of the sponge macro-structure. The concerted effects of the solidification and electrostatic repulsion between fibres are responsible for the self-assembly process of the electrospun PVP-SiO₂-TiO₂ sponge. When used as a thermal insulation material, the SiO₂-TiO₂ sponge shows good fireproof performances. The current contribution may guide more construction of functional inorganic macroporous architectures for advance applications in future.     

Self-assembled cubic-hexagonal perovskite nanocomposite as intermediate-temperature solid oxide fuel cell cathode

Self-assembly is an emerging strategy for preparing composite cathodes with good oxygen electrochemical reduction activity and congenital chemical compatibility for intermediate-temperature solid oxide fuel cell (IT-SOFC). Here we report that a self-assembled BaCo_0.6Zr_0.4O_3-δ (BZC-BC) nanocomposite is prepared through one-pot glycine-nitrate process and exhibits high cathode performance. The BZC-BC nanocomposite is composed of 62 mol% cubic perovskite BaZr_0.82Co_0.18O_3-δ (BZC) as an ionic conductor and 38 mol% hexagonal perovskite BaCo_0.96Zr_0.04O_2.6+δ (12H-BC) as a mixed ionic and electronic conductor. The BZC-BC nanocomposite has the pomegranate-like particles aggregated with a larger number of nanoparticles (50-100 nm) which greatly enlarge the three-phase boundary sites. The BZC-BC nanocomposite exhibits a thermal expansion coefficient of 12.89 × 10⁻⁶ K⁻¹ well-matched with that of Ce_0.8Gd_0.2O_3-δ (12.84 × 10⁻⁶ K⁻¹) electrolyte. The high electro-catalytic activity of BZC-BC nanocomposite cathode for oxygen reduction is reflected by the low polarization resistances of oxygen ions incorporation at cathode/electrolyte interface (0.02823 Ω cm²), oxygen species diffusion (0.03702 Ω cm²) and oxygen adsorptive dissociation (0.07609 Ω cm²) at 700 °C. The single cell with BZC-BC nanocomposite cathode achieves the maximum power density of 1094 mW cm⁻² at 650 °C and shows good stability under 25 h run.     

Hierarchical,template-free self-assembly morphologies in CeO2 synthesized via urea-hydrothermal method

Nano-crystalline CeO₂ was synthesized via the urea-hydrothermal method without templates or structure-directing agents. The synthesis parameters Ce³⁺ to Ce⁴⁺ and urea to cation molar ratios, reaction temperature and reaction time were varied to analyze their effect on morphology, texture and reducibility. The analysis of the obtained morphologies provides strong evidence of a hierarchical and sequential template-free self-assembly process that evolves from shuttles to dumbbells to spheres. In all cases, the morphology of samples remains unchanged even after calcination at 500 °C. The presence of Ce⁴⁺ in the initial solution clearly provides the full self-assembly sequence and is decisive for obtaining non-hollow spheres of CeO₂ with high specific surface area and high pore volume. Besides, if only Ce³⁺ is present, typical CeOHCO₃ shuttle-like particles with orthorhombic structure are obtained. The use of Ce³⁺ in combination with Ce⁴⁺ produces partial sequences of the self-assembly process that provide a strong indication of the hierarchical sequence.The urea to cation molar ratio controls the nucleation process and proves to be crucial to obtain the self-assembly sequence. On the other hand, temperature and reaction time show a moderate effect on morphology.     

To pursue FexCoy-PANI/CNT catalysts for oxygen reduction reaction in acid medium with controlled molecular self-assembly method

The mainstream of pyrolyzed transitional metal-nitrogen-carbon (M-N-C) catalysts for ORR still confront difficulty in PEMFC application. To pursue M-N-C structure from wet chemistry at ambient temperature, this paper prepares Fe_xCo_y-PANI/CNT porous structures composed of amorphous Fe and Co NPs into PANI layer on CNT surface, supported by the controlled molecular self-assembly mechanism (MS). For their ORR behaviors in acid medium, all Fe_xCo_y-PANI/CNT catalysts demonstrate similar features as Pt-based catalyst in low current density region, and 4e pathway and active sites in pore utilization in high current density region. Specifically, we disclosed nitrogen in PANI matrix dominates specific activity for ORR, and a little transitional metal attain mass activity at maximum. The active sites mounted into PANI matrix and 4e pathway help catalysts to achieve high durability. Thus, we extend a new type of platinum-free catalyst and develop a bottom-up approach for preparation-structure-activity, expecting to drive PEMFC remarkably.     

Two-dimensional engineering of Pd nanosheets as advanced electrocatalysts toward formic acid oxidation

Two-dimensional self-assembled nanostructures of palladium nanosheets are created during one-step strategies at room temperature. Palladium nanosheets are synthesized in the absence and presence of surfactant (CTAB) agent with the aim of considering the surfactant effect on the morphology and electrocatalytic activity of palladium nanosheets. In both reactions, carbon monoxide and acetic acid act as reducing agent and solvent, respectively. Both palladium nanosheets serve as two-dimensional advanced supportless electrocatalysts for oxidation of formic acid, and clarify higher mass activity and durability in comparison to the palladium anchored on carbon. The exceptional performance of both palladium nanosheets is ascribed to their self-support and huge surface area characteristics. Moreover, the paper well proves that the morphology and electrocatalytic efficiency of palladium nanosheets were seriously affected by the presence of surfactant. Palladium nanosheets synthesized in the absence and presence of surfactant display the flat and stack nanosheets with thicknesses of 3.48 and 4.22 nm, respectively. In addition, comparison of both palladium nanosheets demonstrates that palladium nanosheets synthesized in the absence of surfactant reflect better catalytic efficiency and durability. The presence and bonding of surfactant to the surface of palladium nanosheets lead to the occupancy of active sites and degradation of palladium nanosheets performance. We believe that these palladium nanosheets can be applied as advanced electrocatalysts for diverse applications, especially direct formic acid fuel cells.     

Synthesis and photocatalytic activity of g-C3N4/ZnO composite microspheres under visible light exposure

In this paper, a novel g-C₃N₄/ZnO composite microspheres (CZCM) with enhanced photocatalytic activity under visible light exposure were successfully prepared by a self-assembly method followed by calcination in the air. A hierarchical structure in which ZnO microspheres were closely covered with g-C₃N₄ nanosheets was constructed. The microstructure and photocatalytic activities of the CZCM were characterized. The photocatalytic property of CZCM was evaluated by degrading solution Methyl Orange (MO) and Tetracycline (TC). The effects of varied contents of g-C₃N₄ on the photocatalytic capability of CZCM were systematically investigated and the results show that the optimized CZ-15% sample exhibit much higher photocatalytic degradation efficiency than that of bare g-C₃N₄ or ZnO under identical conditions. The analysis of Photoluminescence (PL) and photocurrent (PC) independently conformed that the photo-induced electron-hole (e^?-h⁺) pairs in the CZCM were effectively generated and responsible for the observed photocatalysis. The enhanced adsorption of visible-light and the effective charge separation on the surface of CZCM enabled significant improvement of photocatalytic performance. According to the experimental results and relative energy band levels of the two semiconductors, a possible photocatalysis mechanism for the reaction process is proposed.     

Flash technology-based self-assembly in nanoformulation: Fabrication to biomedical applications

Advances in nanoformulation have driven progress in biomedicine by producing nanoscale tools for biosensing, imaging, and drug delivery. Flash-based technology, the combination of rapid mixing technique with the self-assembly of macromolecules, is a new engine for the translational nanomedicine. Here, we review the state-of-the-art in flash-based self-assembly including theoretical and experimental principles, mixing device design, and applications. We highlight the fields of flash nanocomplexation (FNC) and flash nanoprecipitation (FNP), with an emphasis on biomedical applications of FNC, and discuss challenges and future directions for flash-based nanoformulation in biomedicine.     

Histidine as a key modulator of molecular self-assembly: Peptide-based supramolecular materials inspired by biological systems

Histidine, a versatile proteinogenic amino acid, plays a broad range of roles in all living organisms and behaves as a key mediator of the interactions of biomolecules with inorganic constituents. The self-assembly of histidine-rich peptides and proteins is critical in biology, as the histidine unit is both a multifunctional regulator and an ideal motif for the construction of complex biological structures. In particular, non-covalent interactions between the imidazole ring and other molecular building blocks and metal ions are routinely employed to generate these complexes. Therefore, this strategy can be duplicated in an artificial context to create sophisticated bioactive materials. In this review, we first highlight a clear perspective of the bio-inspired design strategies which can replicate the hierarchical structure of biological systems allowing the engineering of the supramolecular self-assembly of histidine-functionalized peptides. We further summarize advancements in the field of peptide supramolecular structures incorporating histidine residues in the peptide backbone to generate organized functional supramolecular biomaterials with customizable features. We also discuss significant advances and future prospects in supramolecular self-assembly of histidine-functionalized peptides, as well as provide an overview of advanced techniques for the fabrication of histidine-based biomaterials for bio-nanotechnology, optoelectronic engineering, and biomedicine. Overall, artificial supramolecular materials based on histidine functionalized peptides, motivated by the intriguing properties discovered in natural proteins, bear the potential to boost the creation of sustainable bio-inspired materials.