Ni/Co/Co3O4@C nanorods derived from a MOF@MOF hybrid for efficient overall water splitting.

The design of nanostructured materials for efficient bifunctional electrocatalysts has gained tremendous attention, yet developing a fast and effective synthesis strategy remains a challenge. Here, we present a fast and scalable synthetic method of Ni/Co/Co3O4@C nanorods for efficient overall water splitting. Using microwave synthesis, we first produced a unique Ni-MOF@Co-MOF in a few minutes. Subsequently, we transformed the MOF@MOF into hybrid Ni/Co/Co3O4 nanoparticles covered with graphitic carbon in a few seconds using laser-scribing. The prepared bimetallic catalysts showed remarkably low overpotentials of 246 mV for the oxygen evolution reaction (OER) and 143 mV for the hydrogen evolution reaction (HER) at a current density of 30 mA cm-2. An electrolyzer assembled with the bimetallic catalysts delivered a high current density of 20 mA cm-2 at a voltage of 1.6 V and exhibited good durability (nearly 91.6% retention even after a long-running operation of 24 h at a voltage of 1.52 V). Our proposed method could serve as a powerful method for creating various multimetallic hybrid nanocatalysts with unique hierarchical structures from diverse MOFs.

Enhanced thermoelectric performance of defect engineered monolayer graphene.

We propose a method of improving the thermoelectric properties of graphene using defect engineering through plasma irradiation and atomic layer deposition (ALD). We intentionally created atomic blemishes in graphene by oxygen plasma treatment and subsequently healed the atomistically defective places using Pt-ALD. After healing, the thermal conductivity of the initially defective graphene increased slightly, while the electrical conductivity and the square of the Seebeck coefficient increased pronouncedly. The thermoelectric figure of merit of the Pt-ALD treated graphene was measured to be over 4.8 times higher than the values reported in the literature. We expect that our study could provide a useful guideline for the development of graphene-based thermoelectric devices.

Tuning the Thermal Conductivity of the Amorphous PAA Polymer via Vapor-Phase Infiltration.

The thermal properties of the polymer, together with mechanical stability, have been one of the key engineering factors to be considered for various applications. Here, we engineered the thermal conductivity of the amorphous poly(acrylic acid) (PAA) polymer by vapor-phase infiltration (VPI), which has usually occurred during the atomic layer deposition process. We observed that the VPI causes metal infiltration (e.g., Al and Zn) into the amorphous PAA polymer, which noticeably increases the thermal conductivity of the PAA polymer. From spectroscopy analysis and density functional theory simulations, we found that the carboxyl groups (-COOH) in PAA are notably modified and the bonding states of carbon and oxygen are significantly altered by the infiltrated metal. The newly formed Al-mediated bonds likely provide continuous phonon propagation pathways, thereby enhancing the thermal conductance. We believe that VPI could be a simple and useful way to engineer the thermal properties of various polymeric materials.

Photocatalytic exoskeleton: Chitin nanofiber for retrievable and sustainable TiO2 carriers for the decomposition of various pollutants.

Loading a photocatalytic TiO2 to organic carriers has been desired for volumetric TiO2 incorporation, facile retrieval, and sustainable utilization. Traditionally, suspended TiO2 nanoparticles or its thin film on two-dimensional substrate are popularly fabricated for pollutants decomposition without carriers; due to poor thermomechanical properties of the organic carriers. Herein, a combination of the chitin nanofiber carrier and atomic layer deposition proves relevance for formation of anatase TiO2 thin layer so that photocatalytic decomposition in three-dimensional surface. Moreover, chitin nanofiber is capable of holding the TiO2 nanoparticles for multiple cycles of photocatalysis. Those types of TiO2 show characteristic degradation performance for gaseous (acetaldehyde) and aqueous pollutants (4-chlorophenol and rhodamine B). After catalytic reaction, chitin/TiO2 is retrievable owing to carrier's robustness even in water without TiO2 aggregation and loss. This work suggests that chitin-based photocatalyst is applicable to numerous pollutants through chitin's relatively high chemical resistance and stably wedged TiO2 during photocatalytic reaction.

Graphitic Carbon with MnO/Mn7 C3 Prepared by Laser-Scribing of MOF for Versatile Supercapacitor Electrodes.

Pseudocapacitive materials encapsulated in conductive carbon matrix are of paramount importance to develop energy storage devices with high performance and long lifespan. Here, via simple laser-scribing, the Mn-based metal-organic framework [EG-MOF-74(Mn)] is transformed into pseudocapacitive hybrid MnO/Mn7 C3 encapsulated in highly conductive graphitic carbon. It is revealed that the rapid carbothermic reduction of MnO (C + MnO → C' + Mn7 C3 + CO) leads to the formation of the intermediate pseudocapacitive MnO/Mn7 C3 and the concurrent catalytic graphitization of disordered carbon. This reaction produces a new type of pseudocapacitive material in the form of MnO/Mn7 C3 fully embedded in highly conductive graphitic carbon. Thanks to the synergistic effect of the MnO/Mn7 C3 nanoparticles and the graphitic carbon, the composite exhibits a high specific capacitance of 403 F g-1 with excellent stability. Asymmetric coin-cell supercapacitors based on the composite demonstrate high energy (29.2 Wh kg-1 ) and power densities (8000 W kg-1 ) with a long lifespan. Prototypes of flexible paper-based supercapacitors made of the composite also show great potential toward applications of flexible electronics.

Enhanced Mechanical Stability and Biodegradability of Ti-Infiltrated Polylactide.

Biodegradable polymers have been often used in place of conventional nondegradable polymers for industrial and medical applications. In particular, polylactide (PLA) has been regarded as a popular ecofriendly plastic and has many advantages like good biocompatibility and processability. Yet, it still has some drawbacks in mechanical properties. Here, we prepared Ti-infiltrated PLA by mimicking the gelatinous jaw of a seaworm whose mechanical properties are toggled up and down by the tiny amount of metal ions, expecting to prepare a new type of alternative. Ti induced significant chemical and microstructural changes in the PLA, which led to a notable improvement in the mechanical properties as compared to the neat PLA. The Ti-infiltrated PLA exhibited high resistance to rapid degradation. More importantly, the toxicity assessment demonstrated that the resulting PLA is still biocompatible and nontoxic. Consequently, we proved that the Ti-infiltrated PLA has high mechanical properties comparable to conventional nondegradable polymers and good biocompatibility as well as delayed biodegradability. We anticipate the current Ti-infiltrated PLA to be an ecofriendly replacement of some conventional plastics, which helps preserve a green environment.

Laser Synthesis of MOF-Derived Ni@Carbon for High-Performance Pseudocapacitors.

Although nanosizing of multiphase pseudocapacitive nanomaterials could dramatically improve their electrochemical properties, a proper way to simultaneously control both the size and the phase of the pseudocapacitive materials is still elusive. Herein, we employed a commercial CO2 laser engraver to do the transformation of a metal-organic framework (MOF-74(Ni)) into size-controlled Ni nanoparticles (4-12 nm) in porous carbon. The produced Ni@carbon hybrid showed the best specific capacitance of 925 F/g with excellent cycling stability when the particle size is 5.5 nm. We found that the highly redox-active α-Ni(OH)2 is more predominantly formed than the less redox-active ß-Ni(OH)2 as the particle size becomes smaller. Our results substantiate that various MOFs could be created into high-performance pseudocapacitive materials with the controlled size and phase. It is believed that the laser-based synthesis could also serve as a powerful tool for the discovery of new MOF-derived materials in the field of energy storage and catalysis.

Single-layer metamaterial bolometer for sensitive detection of low-power terahertz waves at room temperature.

This study demonstrates a metamaterial bolometer that can detect terahertz (THz) waves by measuring variations in electrical resistance. A metamaterial pattern for enhanced THz waves absorption and a composite material with a high temperature coefficient of resistance (TCR) are incorporated into a single layer of the bolometer chip to realize a compact and highly sensitive device. To detect the temperature change caused by the absorption of the THz waves, a polydimethylsiloxane mixed with carbon black microparticles is used. The thermosensitive composite has TCR ranging from 1.88%/K to 3.11%/K at room temperature (22.2-23.8°C). In addition, a microscale metamaterial without a backside reflector is designed to enable the measurement of the resistance and to enhance the sensitivity of the bolometer. The proposed configuration effectively improves thermal response of the chip as well as the absorption of the THz waves. It was confirmed that the irradiated THz waves can be detected via the increment in the electrical resistance. The resistance change caused by the absorption of the THz waves is detectable in spite of the changes in resistance originating from the background thermal noise. The proposed metamaterial bolometer could be applied to detect chemical or biological molecules that have fingerprints in the THz band by measuring the variation of the resistance without using the complex and bulky THz time-domain spectroscopy system.

Prolonged Biodegradation and Improved Mechanical Stability of Collagen via Vapor-Phase Ti Stitching for Long-Term Tissue Regeneration.

Collagen, one of the most popular biomedical materials, exhibits rapid biodegradation accompanied by a notable decrease of mechanical stability in the human body. This is a key challenge for its use in large-sized tissue regeneration, which takes a long time. In order to resolve this problem, we introduced vapor-phase titanium (Ti) derivatives into the interchain regions in collagen via TiO2 atomic layer deposition (ALD), which has been widely used for thin-film deposition. The introduced Ti simultaneously enhanced both the tensile strength (∼384.45 MPa) and Young's modulus (∼1.56 GPa) by approximately 29 and 26% compared to the pristine commercial collagen membrane. In vitro tests demonstrated that approximately 31% of Ti-infiltrated collagen is retained after 4 weeks, whereas the pristine commercial collagen rapidly degrades by up to 90% within 1 week. The in vivo biodegradation rate was greatly improved and inversely proportional to the number of TiO2 ALD cycles. Moreover, bone mineralization, which is observed during the late stage of bone healing, appeared only in the Ti-infiltrated collagen. We believe that our simple vapor-phase treatment method could be widely used with xenograft materials, which typically require adequate biodegradation rates and stable mechanical properties.

Tough and Immunosuppressive Titanium-Infiltrated Exoskeleton Matrices for Long-Term Endoskeleton Repair.

Although biodegradable membranes are essential for effective bone repair, severe loss of mechanical stability because of rapid biodegradation, soft tissue invasion, and excessive immune response remain intrinsically problematic. Inspired by the exoskeleton-reinforcing strategy found in nature, we have produced a Ti-infiltrated chitin nanofibrous membrane. The membrane employs vapor-phase infiltration of metals, which often occurs during metal oxide atomic layer deposition (ALD) on organic substrates. This metal infiltration manifests anomalous mechanical improvement and stable integration with chitin without cytotoxicity and immunogenicity. The membrane exhibits both impressive toughness (∼13.3 MJ·m-3) and high tensile strength (∼55.6 MPa), properties that are often mutually exclusive. More importantly, the membrane demonstrates notably enhanced resistance to biodegradation, remaining intact over the course of 12 weeks. It exhibits excellent osteointegrative performance and suppresses the immune response to pathogen-associated molecular pattern molecules indicated by IL-1ß, IL-6, and granulocyte-macrophage colony-stimulating factor expression. We believe the excellent chemico-biological properties achieved with ALD treatment can provide insight for synergistic utilization of the polymers and ALD in medical applications.

Laser-Induced Reduction of Graphene Oxide by Intensity-Modulated Line Beam for Supercapacitor Applications.

Supercapacitors are irreplaceable energy-storage devices for high power output and rapid charge/discharge of electrical energy. In this study, the laser-based fabrication of reduced graphene oxide (rGO) electrodes for supercapacitors is demonstrated with several new features of laser irradiation. A conventional CO2 laser irradiation system is equipped with (1) a nitrogen blower to avoid combustion of the GO paper, (2) a cylindrical lens for producing a wide line beam, and (3) an optical chopper system for generating an intensity-modulated laser beam. Scanning of the intensity-modulated line beam transforms an extended area of GO into chemically reduced and physically porous graphene. The effects of the laser beam modifications and scanning parameters on the electrochemical performance of the rGO electrode are investigated. The rGO electrode exhibits a high specific capacitance (up to ∼130 F/g) at a current density of 1 A/g. This work can serve as a reference for the process optimization of laser-induced GO reduction.

Abnormal elastic modulus behavior in a crystalline-amorphous core-shell nanowire system.

We investigated the elastic modulus behavior of crystalline InAs/amorphous Al2O3 core-shell heterostructured nanowires with shell thicknesses varying between 10 and 90 nm by conducting in situ tensile tests inside a transmission electron microscope (TEM). Counterintuitively, the elastic modulus behaviors of InAs/Al2O3 core-shell nanowires differ greatly from those of bulk-scale composite materials, free from size effects. According to our results, the elastic modulus of InAs/Al2O3 core-shell nanowires increases, peaking at a shell thickness of 40 nm, and then decreases in the range of 50-90 nm. This abnormal behavior is attributed to the continuous decrease in the elastic modulus of the Al2O3 shell as the thickness increases, which is caused by changes in the atomic/electronic structure during the atomic layer deposition process and the relaxation of residual stress/strain in the shell transferred from the interfacial mismatch between the core and shell materials. A novel method for estimating the elastic modulus of the shell in a heterostructured core-shell system was suggested by considering these two effects, and the predictions from the suggested method coincided well with the experimental results. We also found that the former and latter effects account for 89% and 11% of the change in the elastic modulus of the shell. This study provides new insight by showing that the size dependency, which is caused by the inhomogeneity of the atomic/electronic structure and the residual stress/strain, must be considered to evaluate the mechanical properties of heterostructured nanowires.

Transformation of Solid Waste into Nanoporous Carbon via Carbothermic Reduction.

Continuous population growth and rapid urbanization will outpace the global capacity of solid-waste disposal. Although pyrolysis, in the waste management sector, has been regarded as a savior to bring potential returns, it has struggled against high operation costs. Here, we found that simple pyrolysis of properly mixed wastes [e.g., organic wastes (C) + metal wastes in the form of metal oxides (M x O y )] can bring about the carbothermic reduction [C(s) + M x O y (s) → C'(s) + M(s) + CO(g)] caused by the thermodynamic reducibility of metal oxide. This process consequently produced not only nanoporous carbon powder usable for energy storage devices but also nanoporous carbon fully decorated with magnetic nanoparticles useful for magnetic applications. We believe that the carbothermic reduction process, historically used for metal refining, could be a promising alternative to resolve the long-pending issues of the conventional pyrolysis approach as well as to produce useful nanoporous carbon with ease. Our method could be a simple and effective way to transform ubiquitous solid waste into useful resources in the form of nanoporous carbon.

Carbon Textile Decorated with Pseudocapacitive VC/Vx Oy for High-Performance Flexible Supercapacitors.

It is demonstrated that, via V2 O5 coating by low temperature atomic layer deposition and subsequent pyrolysis, ubiquitous cotton textile can readily turn into high-surface-area carbon textile fully decorated with pseudocapacitive Vx Oy /VC widely usable as electrodes of high-performance supercapacitor. It is found that carbothermic reduction of V2 O5 (C + V2 O5 → C' + VC + CO/CO2 (g)) leads to chemical/mechanical activation of carbon textile, thereby producing high-surface-area conductive carbon textile. In addition, sequential phase transformation and carbide formation (V2 O5 → Vx Oy → VC) occurred by carbothermic reduction trigger decoration of the carbon textile with redox-active Vx Oy /VC. Thanks to the synergistic effect of electrical double layer and pseudocapacitance, the supercapacitors made of the hybrid carbon textile exhibit far better energy density (over 30-fold increase) with excellent cycling stability than the carbon textile simply undergone pyrolysis. The method can open up a promising and facile way to synthesize hybrid electrode materials for electrochemical energy storages possessing advantages of both electrical double layer and pseudocapacitive material.

Effects of ß-sheet crystals and a glycine-rich matrix on the thermal conductivity of spider dragline silk.

We measured the thermal conductivity of Araneus ventricosus' spider dragline silk using a suspended microdevice. The thermal conductivity of the silk fiber was approximately 0.4Wm-1K-1 at room temperature and gradually increased with an increasing temperature in a manner similar to that of other disordered crystals or proteins. In order to elucidate the effect of ß-sheet crystals in the silk, thermal denaturation was used to reduce the quantity of the ß-sheet crystals. A calculation with an effective medium approximation supported this measurement result showing that the thermal conductivity of ß-sheet crystals had an insignificant effect on the thermal conductivity of SDS. Additionally, the enhancement of bonding strength in a glycine-rich matrix by atomic layer deposition did not increase the thermal conductivity. Thus, this study suggests that the disordered part of the glycine-rich matrix prevented the peptide chains from being coaxially extended via the cross-linking covalent bonds.

Activated Carbon Textile via Chemistry of Metal Extraction for Supercapacitors.

Carbothermic reduction in the chemistry of metal extraction (MO(s) + C(s) → M(s) + CO(g)) using carbon as a sacrificial agent has been used to smelt metals from diverse oxide ores since ancient times. Here, we paid attention to another aspect of the carbothermic reduction to prepare an activated carbon textile for high-rate-performance supercapacitors. On the basis of thermodynamic reducibility of metal oxides reported by Ellingham, we employed not carbon, but metal oxide as a sacrificial agent in order to prepare an activated carbon textile. We conformally coated ZnO on a bare cotton textile using atomic layer deposition, followed by pyrolysis at high temperature (C(s) + ZnO(s) → C'(s) + Zn(g) + CO(g)). We figured out that it leads to concurrent carbonization and activation in a chemical as well as mechanical way. Particularly, the combined effects of mechanical buckling and fracture that occurred between ZnO and cotton turned out to play an important role in carbonizing and activating the cotton textile, thereby significantly increasing surface area (nearly 10 times) compared with the cotton textile prepared without ZnO. The carbon textiles prepared by carbothermic reduction showed impressive combination properties of high power and energy densities (over 20-fold increase) together with high cyclic stability.

Carrier transport behaviors depending on the two orthogonally directional energy bands in the ZnO nanofilm affected by oxygen plasma.

An oxygen plasma treatment of ZnO nanostructures has frequently been used for obtaining a desired optoelectrical property. Nevertheless, a detailed study regarding carrier transport behaviors affected by the plasma has scarcely been managed, especially in the thin film structure, owing to its more complex physics than those of a one-dimensional nanostructure. Herein, we demonstrate an analysis of carrier transport behaviors on an oxygen plasma-treated ZnO nanofilm (50 nm thick) on a SiO2/Si substrate. By comparison with the as-grown sample, we observed drastic changes in carrier transport behavior according to the short exposure times of 30 s and 60 s. The plasma effect leading to the distinction was confirmed to originate from the bombardment of energetic ions near the surface and the diffusion of various oxygen ions and radicals into the host. The mechanism of the resulting carrier transport was comprehended through the revelation of two orthogonally directional energy band structures (surface band bending in the surface layer and localized energy bending at the grain boundary). Furthermore, we experimentally observed that the increased electrical barrier of the grain boundary, due to negatively absorbed oxygen ions, could be helpful in impeding persistent photoconductivity and in reducing dark current.

Sub-5 nm nanostructures fabricated by atomic layer deposition using a carbon nanotube template.

The fabrication of nanostructures having diameters of sub-5 nm is very a important issue for bottom-up nanofabrication of nanoscale devices. In this work, we report a highly controllable method to create sub-5 nm nano-trenches and nanowires by combining area-selective atomic layer deposition (ALD) with single-walled carbon nanotubes (SWNTs) as templates. Alumina nano-trenches having a depth of 2.6 âˆ¼ 3.0 nm and SiO2 nano-trenches having a depth of 1.9 âˆ¼ 2.2 nm fully guided by the SWNTs have been formed on SiO2/Si substrate. Through infilling ZnO material by ALD in alumina nano-trenches, well-defined ZnO nanowires having a thickness of 3.1 âˆ¼ 3.3 nm have been fabricated. In order to improve the electrical properties of ZnO nanowires, as-fabricated ZnO nanowires by ALD were annealed at 350 °C in air for 60 min. As a result, we successfully demonstrated that as-synthesized ZnO nanowire using a specific template can be made for various high-density resistive components in the nanoelectronics industry.

A robust and conductive metal-impregnated graphene oxide membrane selectively separating organic vapors.

A small amount of Zn impregnated by ALD triggered enhancement of the mechanical as well as electrical properties of the graphene oxide (GO) membrane. In addition, the Zn-impregnated membranes selectively separated diverse organic vapors while maintaining high water permeability.

In situ Raman spectroscopic study of Al-infiltrated spider dragline silk under tensile deformation.

Natural materials consisting of protein structures impregnated with a tiny amount of metals often exhibit impressive mechanical behavior, which represents a new design paradigm for the development of biomimetic materials. Here, we produced Al-infiltrated silks by applying a modified Al2O3 atomic layer deposition process to the dragline silk of the Nephila pilipes spider, which showed unusual mechanical properties. The deformation behavior of the molecular structure of the Al-infiltrated silk was investigated by performing in situ Raman spectroscopy, where Raman shifts were measured concurrently with macroscopic mechanical deformations. For identifying the role of the infiltrated Al atoms, the study was performed in parallel with untreated silk, and the results were compared. Our experimental results revealed that superior mechanical properties of the Al-infiltrated silk are likely to be caused by the alterations of the sizes of the ß-sheet crystals and their distribution.