Morphology-controlled fabrication of magnetic phase-change microcapsules for synchronous efficient recovery of wastewater and waste heat.

Contamination and waste heat are major issues in water pollution. Aiming at efficient synchronous recovery wastewater and waste heat, we designed a novel CaCO3-based phase-change microcapsule system with an n-docosane core and a CaCO3/Fe3O4 composite shell. The system was fabricated through an emulsion-templated in situ precipitation approach in a structure-directing mode, resulting in a controllable morphology for the resultant microcapsules, varying from a peanut hull through ellipsoid to dumbbell shapes. The system has a significantly enlarged specific surface area of approximately 55 m2·g-1 with the CaCO3 phase transition from vaterite to calcite. As a result, the microcapsule system exhibits improved adsorption capacities of 497.6 and 79.1 mg/g for Pb2+ and Rhodamine B removal, respectively, from wastewater. Moreover, increase in the specific surface area of the microcapsule system with a sufficient latent heat capacity of approximately 130 J·g-1 also resulted in an enhanced heat energy-storage capability and thermal conductance for waste-heat recovery. The microcapsule system also exhibits a good leakage-prevention capability and good multicycle reusability owing to the tight magnetic CaCO3/Fe3O4 composite shell. This study provides a promising approach for developing CaCO3-based phase-change microcapsules with enhanced thermal energy storage and adsorption capabilities for efficient synchronous recovery of wastewater and waste heat.

High-performance polyurethane nanocomposites based on UPy-modified cellulose nanocrystals.

Densely H-bonding assemblies are the key strategy found by nature to enhance the rupture strength of natural polymers without sacrificing their toughness, such as spider silk, while it still remains a great challenge using such intriguing strategy to prepare high-performance synthesized polymer or biopolymer enhanced polymer nanocomposites. To address this challenge, we report here a bio-inspired strategy using densely H-bonding assembly for facile fabrication of high performance polyurethane (PU) nanocomposites reinforced by hydroxyl-rich cellulose nanocrystals (CNCs) functionalized with 2-ureido-4-[1 H]-pyrimidinone motifs (CNC-UPy) containing self-complementary hydrogen bonds. These PU/CNC-UPy nanocomposites showed remarkably improved mechanical strength without sacrificing the elongation at break and toughness compared to pure PU matrix. Differential scanning calorimetry(DSC) results indicated that CNC-UPy could induce the formation of long range ordering of hard segment domains, due to the strong hydrogen bonding interactions between UPy motifs attached on CNC-UPy and PU matrix. Furthermore, wide angle X-ray diffraction (WAXD) measurements demonstrated that the strain-induced crystallization (SIC) was enhanced significantly by introducing CNC-UPy into PU, leading to a large stress at break. The enhanced interfacial H-bonding interactions between CNC and PU though UPy anchoring could overcome the inherent trade-off between the stiffness and toughness of polymer composites. The proposed bio-inspired strategy using densely H-bonding assembly will be with more extensive application prospects.

Lyotropic liquid crystal self-assembly of H2O2-hydrolyzed chitin nanocrystals.

H2O2 hydrolysis of mechanically-defibrillated chitin nanofibrils was explored as a green way of fabricating rod-like chitin nanocrystals (H2O2-hydrolyzed CHNs) that have an average length of 350 nm and width of 40 nm. We investigated the structure and morphology of CHNs as well as the rheology and lyotropic self-assembly behavior of its colloidal dispersions. The results show that although H2O2-hydrolyzed CHNs maintained the crystalline structure of α-chitin, surface charge of the nanorods was switched from positive to negative. As a consequence, the colloidal nanocrystals were well-dispersed in neutral or alkaline aqueous media, and behaved as a lyotropic liquid crystal between two critical concentrations. It is interesting that lyotropic liquid crystal transition was a spontaneously self-assembly from well-aligned nanofibers, to nanobelts, and to multi-layered lamellae. At high critical concentration, H2O2-hydrolyzed CHN colloids exhibited a sol-gel transition, which was discovered to be highly dependent on the storage time, concentration, temperature, and surface charge density. It is also suggested that nematic mesophases rather than gel could be effectively maintained by improving the surface charge density or lowering the aging temperature and colloidal concentration of CHNs.

Vapor sensing with color-tunable multilayered coatings of cellulose nanocrystals.

Colloidal cellulose nanocrystals were LBL deposited to form firmly-stacked optical coatings in which the nanorods regulated their head-to-tail association and aligned in the axial-centrifuged direction. The periodically transition from blue to orange of reflected colors was tunable via deposition layer adjustment. While the sensing coating was exposed to vapors of NH3.H2O, H2O, HCl and HAc, respectively, the color variation in the response process was irreversible at room temperature and highly dependent on vapor diffusion and chemical interface interaction. Consequently, HAc vapor presented the longest sensing transition of wavelength, whereas the alkaline NH3.H2O displays a less recovery ratio than HAc and H2O at room temperature. Under heating at 50°C, the sensed coatings could mostly be restored to their original state except HCl-etched one. Therefore, the naked-eyed qualitative detectability of vapors by nanocellulose could be realized by the divergence in color shift which is of great importance in chemical sensors.

Conformations and Intermolecular Interactions in Cellulose/Silk Fibroin Blend Films: A Solid-State NMR Perspective.

Fabricating materials with excellent mechanical performance from the natural renewable and degradable biopolymers has drawn significant attention in recent decades due to the environmental concerns and energy crisis. As two of the most promising substitutes of synthetic polymers, silk fibroin (SF), and cellulose, have been widely used in the field of textile, biomedicine, biotechnology, etc. Particularly, the cellulose/SF blend film exhibits better strength and toughness than that of regenerated cellulose film. Herein, this study is aimed to understand the molecular origin of the enhanced mechanical properties for the cellulose/SF blend film, using solid-state NMR as a main tool to investigate the conformational changes, intermolecular interactions between cellulose and SF and the water organization. It is found that the content of the ß-sheet structure is increased in the cellulose/SF blend film with respect to the regenerated SF film, accompanied by the reduction of the content of random coil structures. In addition, the strong hydrogen bonding interaction between the SF and cellulose is clearly elucidated by the two-dimensional (2D) 1H-13C heteronuclear correlation (HETCOR) NMR experiments, demonstrating that the SF and cellulose are miscible at the molecular level. Moreover, it is also found that the -NH groups of SF prefer to form hydrogen bonds with the hydroxyl groups bonded to carbons C2 and C3 of cellulose, while the hydroxyl groups bonded to carbon C6 and the ether oxygen are less favorable for hydrogen bonding interactions with the -NH groups of SF. Interestingly, bound water is found to be present in the air-dried cellulose/SF blend film, which is predominantly associated with the cellulose backbones as determined by 2D 1H-13C wide-line-separation (WISE) experiments with spin diffusion. This clearly reveals the presence of nanoheterogeneity in the cellulose/SF blend film, although cellulose and SF are miscible at a molecular level. Without doubt, these in-depth atomic-level structural information could help reveal the molecular origin of the enhanced mechanical properties of the blend film, and thus to establish the structure-property relationship, which could further provide guidance for the fabrication of high performance biopolymer-based materials.

Chitin nanofibrils for rapid and efficient removal of metal ions from water system.

Joint mechanical defibrillation was successfully used to downsize chitin micro-particles (CMP) into nanofibrils without changing its chemical or crystalline structure. The fine chitin nanofibrils (CNF) bearing width of about 50 nm and length of more than 1 µm were then developed as heavy metal ion sorbents. The uptake performance of CNF dependent on pH, ionic concentration, time, and temperature was investigated. Results show that fixation amount of Cd(II), Ni(II), Cu(II), Zn(II), Pb(II), Cr(III) on CNF was up to 2.94, 2.30, 2.22, 2.06, 1.46, and 0.31 mmol/g, respectively, much higher than CMP due to high specific surface area and widely distributed pores of CNF. Adsorption kinetics of CMP and CNF followed pseudo-second-order model and Freundlich isotherm although CNF exhibited higher rate constant and sorption capacity than that of CMP. The defibrillated CNF is renewable, feasible, easily recyclable, and is thought as good candidate for heavy metal ion treatment due to their low sorption energy, rapid and efficient uptake capacity.