Mussel-Inspired, Underwater Self-Healing Ionoelastomers Based on α-Lipoic Acid for Iontronics.

Weak adhesion and lack of underwater self-healability hinder advancing soft iontronics particularly in wet environments like sweaty skin and biological fluids. Mussel-inspired, liquid-free ionoelastomers are reported based on seminal thermal ring-opening polymerization of a biomass molecule of α-lipoic acid (LA), followed by sequentially incorporating dopamine methacrylamide as a chain extender, N,N'-bis(acryloyl) cystamine, and lithium bis(trifluoromethanesulphonyl) imide (LiTFSI). The ionoelastomers exhibit universal adhesion to 12 substrates in both dry and wet states, superfast self-healing underwater, sensing capability for monitoring human motion, and flame retardancy. The underwater self-repairabilitiy prolongs over three months without deterioration, and sustains even when mechanical properties greatly increase. The unprecedented underwater self-mendability benefits synergistically from the maximized availability of dynamic disulfide bonds and diverse reversible noncovalent interactions endowed by carboxylic groups, catechols, and LiTFSI, along with the prevented depolymerization by LiTFSI and tunability in mechanical strength. The ionic conductivity reaches 1.4 × 10-6 -2.7 × 10-5 S m-1 because of partial dissociation of LiTFSI. The design rationale offers a new route for creating a wide range of LA- and sulfur-derived supramolecular (bio)polymers with superior adhesion, healability, and other functionalities, and thus has technological implications for coatings, adhesives, binders and sealants, biomedical engineering and drug delivery, wearable and flexible electronics, and human-machine interfaces.

Suppressing the Coffee-Ring Effect in Semitransparent MnO2 Film for a High-Performance Solar-Powered Energy Storage Window.

We introduce a simple and effective method to deposit a highly uniform and semitransparent MnO2 film without coffee-ring effect (CRE) by adding ethanol into MnO2 ink for transparent capacitive energy storage devices. By carefully controlling the amount of ethanol added in the MnO2 droplet, we could significantly reduce the CRE and thus improve the film uniformity. The electrochemical properties of supercapacitor (SC) devices using semitransparent MnO2 film electrodes with or without CRE were measured and compared. The SC device without CRE shows a superior capacitance, high rate capability, and lower contact resistance. The CRE-free device could achieve a considerable volumetric capacitance of 112.2 F cm(-3), resulting in a high volumetric energy density and power density of 10 mWh cm(-3) and 8.6 W cm(-3), respectively. For practical consideration, both flexible SC and large-area rigid SC devices were fabricated to demonstrate their potential for flexible transparent electronic application and capacitive energy-storage window application. Moreover, a solar-powered energy storage window which consists of a commercial solar cell and our studied semitransparent MnO2-film-based SCs was assembled. These SCs could be charged by the solar cell and light up a light emitting diode (LED), demonstrating their potential for self-powered systems and energy-efficient buildings.

Controllable in situ synthesis of epsilon manganese dioxide hollow structure/RGO nanocomposites for high-performance supercapacitors.

Well-organized epsilon-MnO2 hollow spheres/reduced graphene oxide (MnO2HS/RGO) composites have been successfully constructed via a facile and one-pot synthetic route. The ε-MnO2 hollow spheres with the diameter of ∼500 nm were grown in situ with homogeneous distribution on both sides of graphene oxide (GO) sheets in aqueous suspensions. The formation mechanism of the MnO2HS/RGO composites has been systematically investigated, and a high specific capacitance and good cycling capability were achieved on using the composites as supercapacitors. The galvanostatic charge/discharge curves show a specific capacitance of 471.5 F g(-1) at 0.8 A g(-1). The hollow structures of ε-MnO2 and the crumpled RGO sheets can enhance the electroactive surface area and improve the electrical conductivity, thus further facilitating the charge transport. The MnO2HS/RGO composite exhibits a high capacitance of 272 F g(-1) at 3 A g(-1) (92% retention) even after 1000 cycles. The prominent electrochemical performance might be attributed to the combination of the pseudo-capacitance of the MnO2 nanospheres with a hollow structure and to the good electrical conductivity of the RGO sheets. This work explores a new concept in designing metal oxides/RGO composites as electrode materials.

Aqueous manganese dioxide ink for paper-based capacitive energy storage devices.

We report a simple approach based on a chemical reduction method to synthesize aqueous inorganic ink comprised of hexagonal MnO2 nanosheets. The MnO2 ink exhibits long-term stability and continuous thin films can be formed on various substrates without using any binder. To obtain a flexible electrode for capacitive energy storage, the MnO2 ink was printed onto commercially available A4 paper pretreated with multiwalled carbon nanotubes. The electrode exhibited a maximum specific capacitance of 1035 F g(-1) (91.7 mF cm(-2)). Paper-based symmetric and asymmetric capacitors were assembled, which gave a maximum specific energy density of 25.3 Wh kg(-1) and a power density of 81 kW kg(-1). The device could maintain a 98.9% capacitance retention over 10 000 cycles at 4 A g(-1). The MnO2 ink could be a versatile candidate for large-scale production of flexible and printable electronic devices for energy storage and conversion.

Morphology-controlled synthesis of self-assembled LiFePO4/C/RGO for high-performance Li-ion batteries.

Novel architectured LiFePO4 (LFP) that consisted of ordered LFP nanocubes was prepared through a facile hydrothermal method using polyethylene glycol (PEG) as a surfactant. The micro/nanostructured LFP with various morphologies ranging from cube cluster to rugby-like structure was synthesized via controlling the pH values of the precursor. A reasonable assembly process elucidating the formation of the hierarchical structure is also provided based on the experimental results. After a combination of carbon (C) coating and reduced graphene oxide (RGO) wrapping, the obtained LFP/C/RGO composites exhibit enhanced electrochemical performance compared to that of blank LFP synthesized under the same condition. Among as-synthesized cube-cluster-like, dumbbell-like, rod-like, and rugby-like composites, the rugby-like LFP/C/RGO reveal the best electrochemical properties with the discharge specific capacity of ∼150 mA h g(-1) after 100 cycles and a high reversible specific capacity of 152 mA h g(-1) at 0.1 C. The prepared LFP/C/RGO composite can be a promising cathode material for high energy, low cost, and environmentally friendly lithium-ion batteries.

Capture and release of cancer cells based on sacrificeable transparent MnO2 nanospheres thin film.

A CTCs detection assay using transparent MnO2 nanospheres thin films to capture and release of CTCs is reported. The enhanced local topography interaction between extracellular matrix scaffolds and the antibody-coated substrate leads to improved capture efficiency. CTCs captured from artificial blood sample can be cultured and released, represent a new functional material capable of CTCs isolation and culture for subsequent studies.

Enhancing multiphoton upconversion through energy clustering at sublattice level.

The applications of lanthanide-doped upconversion nanocrystals in biological imaging, photonics, photovoltaics and therapeutics have fuelled a growing demand for rational control over the emission profiles of the nanocrystals. A common strategy for tuning upconversion luminescence is to control the doping concentration of lanthanide ions. However, the phenomenon of concentration quenching of the excited state at high doping levels poses a significant constraint. Thus, the lanthanide ions have to be stringently kept at relatively low concentrations to minimize luminescence quenching. Here we describe a new class of upconversion nanocrystals adopting an orthorhombic crystallographic structure in which the lanthanide ions are distributed in arrays of tetrad clusters. Importantly, this unique arrangement enables the preservation of excitation energy within the sublattice domain and effectively minimizes the migration of excitation energy to defects, even in stoichiometric compounds with a high Yb(3+) content (calculated as 98 mol%). This allows us to generate an unusual four-photon-promoted violet upconversion emission from Er(3+) with an intensity that is more than eight times higher than previously reported. Our results highlight that the approach to enhancing upconversion through energy clustering at the sublattice level may provide new opportunities for light-triggered biological reactions and photodynamic therapy.

Synergistic effect of surface plasmon resonance and constructed hierarchical TiO2 spheres for dye-sensitized solar cells.

We demonstrate a strategy for incorporating plasmon resonant metallic nanoparticles in the construction of hierarchical TiO(2) spheres. Localized electric fields can be produced by the addition of Au nanoparticles, which can excite dye molecules more effectively than incident far-field light. The synergistic effect of surface plasmon resonance with constructed TiO(2) nanostructures has been investigated, and was confirmed by optical spectroscopy, J-V characteristics, EIS analysis and OCVD measurements. When Au nanoparticles are incorporated into the constructed TiO(2) spheres, the device achieves a power conversion efficiency of 6.62%, a 4.6% increase compared to the device based on constructed TiO(2) spheres without plasmon resonant Au nanoparticles, and a 17.4% increase compared to that without any treatment.

Tuning the shape and thermoelectric property of PbTe nanocrystals by bismuth doping.

We report the synthesis of a series of monodispersed Bi-doped PbTe nanocrystals with tunable morphologies by using a doping precursor of bismuth(III) 2-ethylhexanoate. The as-synthesized Pb(1-x)Bi(x)Te (x = 0.005, 0.010, 0.015, 0.020) nanocrystals are characterized by X-ray diffraction, X-ray photoelectron spectroscopy and Hall measurements. The nanocrystals with controlled spherical, cuboctahedral, and cubic shapes were readily prepared by varying the Bi doping concentration. Thermoelectric investigation of these nanocrystals shows that the Bi(3+) doping increases electrical conductivity from 350 to 650 K and changes the Seebeck coefficient sign from positive to negative.

Superwetting nanowire membranes for selective absorption.

The construction of nanoporous membranes is of great technological importance for various applications, including catalyst supports, filters for biomolecule purification, environmental remediation and seawater desalination. A major challenge is the scalable fabrication of membranes with the desirable combination of good thermal stability, high selectivity and excellent recyclability. Here we present a self-assembly method for constructing thermally stable, free-standing nanowire membranes that exhibit controlled wetting behaviour ranging from superhydrophilic to superhydrophobic. These membranes can selectively absorb oils up to 20 times the material's weight in preference to water, through a combination of superhydrophobicity and capillary action. Moreover, the nanowires that form the membrane structure can be re-suspended in solutions and subsequently re-form the original paper-like morphology over many cycles. Our results suggest an innovative material that should find practical applications in the removal of organics, particularly in the field of oil spill cleanup.

Synthesis of single crystal manganese oxide octahedral molecular sieve (OMS) nanostructures with tunable tunnels and shapes.

A new and facile route is reported to manipulate the self-assembly synthesis of hierarchically ordered Rb-OMS-2 and pyrolusite with an interesting flowerlike morphology by a direct and mild reaction between rubidium chromateand manganese sulfate without any organic templates. The crystal forms, morphologies, and tunnel sizes of the obtained OMS materials can be controlled. A mechanism for the growth of manganese dioxides with flowerlike architectures was proposed. The obtained products exhibit potential for use in catalysis and other applications.

Shape-controlled synthesis of manganese oxide octahedral molecular sieve three-dimensional nanostructures.

Cryptomelane-type manganese oxide octahedral molecular (OMS) sieve three-dimensional (3D) nanostructures were synthesized via facile temple-free low-temperature hydrothermal reactions. Morphologies of the cryptomelane-type OMS-2 nanoparticles with tunnel dimension of 4.6 x 4.6 A can be tuned by varying reaction temperatures. At low temperature (120 degrees C), OMS-2 dendritic nanoclusters composed of uniform single-crystal nanotetragonal prisms with square cross-sections were formed. At high temperature (180 degrees C), the morphologies of OMS-2 became spherical dandelion-like microspheres composed of uniform single-crystal OMS-2 nanoneedles. Slow oxidation of Mn(2+) by Cr(2)O(7)(-) under hydrothermal conditions is critical for the formation of the hierarchically ordered OMS-2 3D nanostructures.

Synthesis and characterization of silicon nanowires on mesophase carbon microbead substrates by chemical vapor deposition.

Silicon nanowires (SiNWs) have been fabricated by chemical vapor deposition at ambient pressure using SiCl(4) as a silicon source and mesophase carbon microbead powder as a substrate without any templates and/or metal catalysts. The SiNWs have a crystalline core with a very thin amorphous SiO(x) sheath. The obtained SiNWs are homogeneous with average diameters below 50 nm and lengths up to micrometers. Temperature and time effects on the growth of SiNWs were systematically studied. Higher reaction temperatures and longer reaction times resulted in larger diameters and higher yields of SiNWs. SiNWs with a better crystallinity can be obtained at higher temperatures and longer reaction times. The obtained SiNWs were characterized by field-emission scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy.

Self-assembly of microporous manganese oxide octahedral molecular sieve hexagonal flakes into mesoporous hollow nanospheres.

Manganese oxide hollow nanospheres were prepared using a straightforward, template-free synthesis. The resulting material was mesoporous, crystalline, and of uniform diameter. The nanospheres were characterized by XRD, HR-SEM, and HR-TEM, and pore size distributions were calculated from nitrogen desorption. Unlike previous synthesis methods that use an inorganic template, this procedure requires no separation after synthesis to remove the template. The nanospheres are composed of hexagonal gamma-manganese oxide flakes and are approximately 400 nm in diameter. gamma-MnO2 is composed of a ramsdellite matrix (1 x 2 tunnels) with randomly distributed microdomains of pyrolusite (1 x 1 tunnels). These materials could have applications as cathodic battery materials, oxidation catalysts, catalyst supports, and adsorbents for pollutants.