Preventing the Collapse Behavior of Polyurethane Foams with the Addition of Cellulose Nanofiber.

Polyurethane foam manufacturing depends on its materials and processes. A polyol that contains primary alcohol is very reactive with isocyanate. Sometimes, this may cause unexpected problems. In this study, a semi-rigid polyurethane foam was fabricated; however, its collapse occurred. The cellulose nanofiber was fabricated to solve this problem, and a weight ratio of 0.25, 0.5, 1, and 3% (based on total parts per weight of polyols) of the nanofiber was added to the polyurethane foams. The effect of the cellulose nanofiber on the polyurethane foams' rheological, chemical, morphological, thermal, and anti-collapse performances was analyzed. The rheological analysis showed that 3 wt% of the cellulose nanofiber was unsuitable because of the aggregation of the filler. It was observed that the addition of the cellulose nanofiber showed the improved hydrogen bonding of the urethane linkage, even if it was not chemically reacted with the isocyanate groups. Moreover, due to the nucleating effect of the cellulose nanofiber, the average cell area of the produced foams decreased according to the amount of the cellulose nanofiber present, and the average cell area especially was reduced about five times when it contained 1 wt% more of the cellulose nanofiber than the neat foam. Although the thermal stability declined slightly, the glass transition temperature shifted from 25.8 °C to 37.6, 38.2, and 40.1 °C by when the cellulose nanofiber increased. Furthermore, the shrinkage ratio after 14 days from the foaming (%shrinkage) of the polyurethane foams decreased 15.4 times for the 1 wt% cellulose nanofiber polyurethane composite.

KOH-Activated Hollow ZIF-8 Derived Porous Carbon: Nanoarchitectured Control for Upgraded Capacitive Deionization and Supercapacitor.

Herein, the synergistic effects of hollow nanoarchitecture and high specific surface area of hollow activated carbons (HACs) are reported with the superior supercapacitor (SC) and capacitive deionization (CDI) performance. The center of zeolite imidazolate framework-8 (ZIF-8) is selectively etched to create a hollow cavity as a macropore, and the resulting hollow ZIF-8 (HZIF-8) is carbonized to obtain hollow carbon (HC). The distribution of nanopores is, subsequently, optimized by KOH activation to create more nanopores and significantly increase specific surface area. Indeed, as-prepared hollow activated carbons (HACs) show significant improvement not only in the maximum specific capacitance and desalination capacity but also capacitance retention and mean desalination rates in SC and CDI, respectively. As a result, it is confirmed that well-designed nanoarchitecture and porosity are required to allow efficient diffusion and maximum electrosorption of electrolyte ions.

Tailored Nanoarchitecturing of Microporous ZIF-8 to Hierarchically Porous Double-Shell Carbons and Their Intrinsic Electrochemical Property.

Mesostructured polydopamine (PDA) coating has been successfully achieved on the surface of zeolitic imidazolate framework-8 (ZIF-8) particles by incorporating Pluronic F127 (with a pore-expanding agent, 1,3,5-trimethylbenzene) as a pore-directing agent during dopamine polymerization. Upon pyrolysis at high temperatures, mesostructured PDA-coated ZIF-8 particles become hierarchically porous double-shell carbons (HPDCs) with a wide pore size distribution ranging from micro- and meso- to macropores. The formation of a hollow inner shell progresses initially with the shrinkage of ZIF-8 at the periphery where the interface interactions with mesostructured PDA exist, and then the subsequent disintegration of the ZIF-8 core at higher temperatures occurs. Our HPDCs prepared in this study feature physical and electrochemical advantages of hierarchically porous carbons such as high electrochemically accessible surface area, short diffusion distance, and high mass-transfer rate, thus demonstrating significantly improved ion diffusion and surface-enhanced high specific capacitance at high charge-discharge rates. HPDC5.0 therefore exhibits the capacitance retention of up to 76.7% from 1 to 10 A g-1 and maximum specific capacitance of 344.7 F g-1 at 1 mV s-1. It also possesses superior electrochemical stability with about 108% capacitance retention even after 10,000 consecutive cycles of galvanostatic charge-discharge at 10 A g-1.

Layered transition metal dichalcogenide/carbon nanocomposites for electrochemical energy storage and conversion applications.

Layered transition metal dichalcogenide (LTMD)/carbon nanocomposites obtained by incorporating conductive carbons such as graphene, carbon nanotubes (CNT), carbon nanofibers (CF), hybrid carbons, hollow carbons, and porous carbons exhibit superior electrochemical properties for energy storage and conversion. Due to the incorporation of carbon into composites, the LTMD/carbon nanocomposites have the following advantages: (1) highly efficient ion/electron transport properties that promote electrochemical performance; (2) suppressed agglomeration and restacking of active materials that improve the cycling performance and electrocatalytic stability; and (3) unique structures such as network, hollow, porous, and vertically aligned nanocomposites that facilitate the shortening of the ion and electrolyte diffusion pathway. In this context, this review introduces and summarizes the recent advances in LTMD/carbon nanocomposites for electrochemical energy-related applications. First, we briefly summarize the reported synthesis strategies for the preparation of LTMD/carbon nanocomposites with various carbon materials. Following this, previous studies using rationally synthesized nanocomposites are discussed based on a variety of applications related to electrochemical energy storage and conversion including Li/Na-ion batteries (LIBs/SIBs), Li-S batteries, supercapacitors, and the hydrogen evolution reaction (HER). In particular, the sections on LIBs and the HER as representative applications of LTMD/carbon nanocomposites are described in detail by classifying them with different carbon materials containing graphene, carbon nanotubes, carbon nanofibers, hybrid carbons, hollow carbons, and porous carbons. In addition, we suggest a new material design of LTMD/carbon nanocomposites based on theoretical calculations. At the end of this review, we provide an outlook on the challenges and future developments in LTMD/carbon nanocomposite research.

Electrophoretic Deposition of Binder-Free MOF-Derived Carbon Films for High-Performance Microsupercapacitors.

Recently, miniaturized power supplies have become essential components of micro-electromechanical systems (MEMS) and portable microdevices due to their high-power density, moderate specific energy, and superior long-term cyclability. In this study, microsupercapacitors with ZIF-8-derived carbons as active materials were successfully fabricate by electrophoretic deposition method. The carbon materials on microsupercapacitors, which are directly deposited or obtained by pyrolyzing predeposited ZIF-8 particles, play a crucial role in achieving outstanding electrochemical performances. The microsupercapacitor of 16 interdigital finger electrodes, prepared by electrophoretic deposition of ZIF-8 particles and subsequent pyrolysis, shows maximum specific power 687.6 mW cm-3 , specific energy 2.87 mWh cm-3 , and 97.8 % capacitance retention rate after 10 000 cycles. The simple and facile process of electrophoretic deposition and subsequent pyrolysis of ZIF-8 particles generates a film of densely populated microporous carbon particles on microsupercapacitor, leading to superior capacitive performances.

Three-dimensional, millimeter-scale semiconducting SWCNT aerogels for highly sensitive ozone detection.

Semiconducting frameworks possessing porous structure are promising platforms for the detection of hazardous gas molecules. In this study, we propose a facile route to fabricate millimeter-scale, three-dimensional semiconducting SWCNT (s-SWCNT) aerogels and demonstrate deactivation of the co-existing metallic SWCNT (m-SWCNT) network via electrical breakdown process. In particular, the on-off ratio of the modulated semiconducting aerogel after the electrical breakdown process was 205, which is an increase of 18.9 times over that before the process. The modulated semiconducting SWCNT aerogels with a large specific surface area (∼1270 m2 g-1) demonstrated their applicability for highly sensitive ppb-level ozone detection. The modulated semiconducting networks led to a 1310 % increase in the magnitude of response to 30-ppb ozone gas injection compared with that of pristine SWCNT aerogels. Furthermore, the prepared aerogels could detect 3 ppb of ozone within 40 s and retain stable reversible ozone detection for 200 cyclic operations over 100 h. Thus, the proposed semiconducting SWCNT aerogels are a promising candidate for highly sensitive environmental gas sensors.

Gram-Scale Synthesis of Bimetallic ZIFs and Their Thermal Conversion to Nanoporous Carbon Materials.

The hybrid metal-organic frameworks (MOFs) with different Zn2+/Co2+ ratios are synthesized at room temperature with deionized water as the solvent. This use of deionized water can increase the yield of hybrid MOFs (up to 65-70%). After the pyrolysis, the obtained nanoporous carbons (NPCs) show a decrease in the surface area, in which the highest surface area is 655 m2 g-1. The as-prepared NPCs are subjected to activation with KOH in order to increase their surface area and convert cobalt nanoparticles (Co NPs) to Co oxides. These activated carbons are applied to electrical double-layer capacitors (EDLCs) and pseudocapacitors due to the presence of CoO and Co3O4 nanoparticles in the carbon framework, leading to significantly enhanced specific capacitance as compared to that of pristine NPCs. This synthetic method can be utilized in future research to enhance pseudocapacitance further while maintaining the maximum surface area of the carbon materials.

An Organic/Inorganic Nanocomposite of Cellulose Nanofibers and ZnO Nanorods for Highly Sensitive, Reliable, Wireless, and Wearable Multifunctional Sensor Applications.

Organic and inorganic one-dimensional nanomaterials were synthesized and combined into a nanocomposite film for a wearable sensor. Reproducible ZnO nanorod (NR) synthesis was achieved by the addition of an appropriate amount of water. Cellulose nanofibers (CNFs) were used due to their porous matrix formation. The interconnected channels of brittle ZnO NRs were well-fabricated in the flexible network of CNFs. The surface morphology, thermal, and mechanical properties of the CNF/ZnO NR nanocomposite film were characterized. The interfacial interactions between these two nanomaterials were also studied. The nanocomposite film is sufficiently flexible so that it shows no electrical resistance changes even after repeated bending tests with a minimum bending radius of 1.5 mm. In addition, ZnO NRs with different lengths were synthesized. The composite of longer ZnO NRs and CNF showed 2.8 × 103 times higher photocurrent and responsivity performance. The humidity sensing performance of the composite was also suggested. The CNF/ZnO NR film shows reasonable electrical signal changes enabling the evaluation of a calibration curve. Finally, a smart band including a CNF/ZnO NR film sensor was fabricated and connected to a smartphone by Bluetooth. These results open an avenue for developing wearable sensors by overcoming the brittleness of inorganic materials.

Nanoarchitectonics for Transition-Metal-Sulfide-Based Electrocatalysts for Water Splitting.

Heterogenous electrocatalysts based on transition metal sulfides (TMS) are being actively explored in renewable energy research because nanostructured forms support high intrinsic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, it is described how researchers are working to improve the performance of TMS-based materials by manipulating their internal and external nanoarchitectures. A general introduction to the water-splitting reaction is initially provided to explain the most important parameters in accessing the catalytic performance of nanomaterials catalysts. Later, the general synthetic methods used to prepare TMS-based materials are explained in order to delve into the various strategies being used to achieve higher electrocatalytic performance in the HER. Complementary strategies can be used to increase the OER performance of TMS, resulting in bifunctional water-splitting electrocatalysts for both the HER and the OER. Finally, the current challenges and future opportunities of TMS materials in the context of water splitting are summarized. The aim herein is to provide insights gathered in the process of studying TMS, and describe valuable guidelines for engineering other kinds of nanomaterial catalysts for energy conversion and storage technologies.

Scalable synthesis of holey graphite nanosheets for supercapacitors with high volumetric capacitance.

We prepared a material composed of high-density holey graphite nanosheets (HGNs) that supports a high gravimetric capacitance of 295 F g-1 and a volumetric capacitance of 384 F cm-3 for use as electrodes in supercapacitor devices. This method is a simple and scalable route to obtain large amounts of holey two-dimensional materials with high electrochemical performances.

Advanced Functional Carbons and Their Hybrid Nanoarchitectures towards Supercapacitor Applications.

Porous carbons have attracted much attention as electrode materials for supercapacitors due to their enormous surface area, high electrical conductivity, excellent corrosion resistance, high temperature stability, and relatively low cost. The design of porous architectures is considered key for determining electrochemical performance. Pore size distribution, pore size, and pore connectivity strongly affect electrochemical performance. Various carbon materials with pore size ranging from micro- to macropores were extensively studied. Herein, various types of porous carbon-based and hybrid materials from different approaches and their electrochemical applications are summarized. Appropriate tuning of the pore size of carbon materials is essential for ensuring good transport of ions with different sizes throughout the electrolyte, so that the electrode materials can be fully utilized. Many carbon materials were produced from a series of carbonization and activation processes that possess controllable pore structures, including activated carbons, graphite, carbon nanotubes, carbon aerogels, and templated porous carbons. Templated carbon materials were prepared by various approaches, such as direct carbonization from carbon precursors and soft- and hard-template methods. To enhance the electrochemical performance of the electrode materials, heteroatoms, such as nitrogen, sulfur, and boron, were doped into porous carbons. In addition, to optimize the overall capacitance without destroying the stability and morphology of electrode materials, pseudocapacitive materials, such as transition-metal oxides, were introduced into the carbon frameworks. In this review, recent advances in the fabrication of nanoarchitectured porous carbons and metal oxides through various approaches for supercapacitor applications are summarized.

Preparation of Bismuth Telluride Films with High Thermoelectric Power Factor.

Highly conductive n-type Bi2Te3 films on a flexible substrate were prepared via electrodeposition followed by a transfer process using an adhesive substrate. The growth of the Bi2Te3 crystals was precisely controlled by an electrochemical deposition potential (Vdep), which was critical to the preferred orientation of the crystal growth along the (110) direction and thus to the properties of a flexible thermoelectric generator (FTEG). A Bi2Te3 film prepared under Vdep of 0.02 V showed high electrical conductivity (691 S cm-1) with a maximum power factor of 1473 µW m-1 K-2, which is the highest among the Bi2Te3 films prepared by the electrodeposition methods. As-prepared FTEG was bendable, showing only a small resistance change after 300 repeated bending cycles. Combined with the n-type Bi2Te3 FTEG, a prototype p-n-type flexible thermoelectric (pn-FTEG) was prepared using p-type poly(3,4-ethylene dioxythiophene)s. The pn-FTEG (5-couples) generated an output voltage of 5 mV at ΔT = 12 K with high output power of 56 nW (or 105 nWg-1). These results indicate that the FTEG can reproducibly work well in a bent state and has high application potential for harvesting thermal energy from curved sources such as human body temperature.

Photothermally Activated Pyroelectric Polymer Films for Harvesting of Solar Heat with a Hybrid Energy Cell Structure.

Photothermal effects in poly(3,4-ethylenedioxythiophene)s (PEDOTs) were explored for pyroelectric conversion. A poled ferroelectric film was coated on both sides with PEDOT via solution casting polymerization of EDOT, to give highly conductive and effective photothermal thin films of PEDOT. The PEDOT films not only provided heat source upon light exposure but worked as electrodes for the output energy from the pyroelectric layer in an energy harvester hybridized with a thermoelectric layer. Compared to a bare thermoelectric system under NIR irradiation, the photothermal-pyro-thermoelectric device showed more than 6 times higher thermoelectric output with the additional pyroelectric output. The photothermally driven pyroelectric harvesting film provided a very fast electric output with a high voltage output (Vout) of 15 V. The pyroelectric effect was significant due to the transparent and high photothermal PEDOT film, which could also work as an electrode. A hybrid energy harvester was assembled to enhance photoconversion efficiency (PCE) of a solar cell with a thermoelectric device operated by the photothermally generated heat. The PCE was increased more than 20% under sunlight irradiation (AM 1.5G) utilizing the transmitted light through the photovoltaic cell as a heat source that was converted into pyroelectric and thermoelectric output simultaneously from the high photothermal PEDOT electrodes. Overall, this work provides a dynamic and static hybrid energy cell to harvest solar energy in full spectral range and thermal energy, to allow solar powered switching of an electrochromic display.

Photothermally induced local dissociation of collagens for harvesting of cell sheets.

The local heating of poly(3,4-ethylenedioxythiophene) (PEDOT) by a photothermal effect directed by near-infrared (NIR) light induces unfolding of absorbed collagen triple helices, yielding soluble collagen single-helical structures. This dissociation of collagens allowed the harvesting of a living idiomorphic cell sheet, achieved upon irradiation with NIR light (λ=808 nm). The PEDOT layer was patterned and cells were successfully cultured on the patterned substrate. Cell sheets of various shapes mirroring the PEDOT pattern could be detached after a few minutes of irradiation with NIR light. The PEDOT patterns guided not only the entire shape of the cell sheets but also the spreading direction of the cells in the sheets. This photothermally induced dissociation of collagen provided a fast non-invasive harvesting method and tailor-made cell-sheet patterns.

Highly fluorescent conjugated polyelectrolyte for protein sensing and cell-compatible chemosensing applications.

Using a highly fluorescent, water-soluble polymer derived from a triazine-bridged copolymer (DTMSPV), we explored the tunable fluorescence properties of the water-soluble DTMSPV by solvent polarity to function as a fluorescence sensory probe for protein sensing. The green-blue fluorescence from DTMSPV was significantly enhanced in the presence of bovine serum albumin through hydrophobic interactions. Meanwhile, complete quenching of the fluorescence from DTMSPV occurred in the presence of hemoglobin through iron complexation with the polyelectrolyte. In addition, the DTMSPVs were highly fluorescent and permeated into living mesenchymal stem cells (MSCs), enabling effective imaging of the MSCs. This permeation into stem cells is crucial to the detection of Al(3+) in living MSCs. The interaction between the triazine units in DTMSPV with the Al(3+) ions allows for the detection of Al(3+) in living cells. Thus, a strong fluorescence from living MSCs pretreated with DTMSPV was quenched as a function of the Al(3+) concentration, confirming that DTMSPV is a cell-permeable fluorescent polymer that can function as a versatile probe to detect Al(3+) in living cells.

Synthesis of photolabile fluorescent polymeric micelles.

A new amphiphilic block copolymers were synthesized with the atom transfer radical polymerization (ATRP) method. Then, the micelle structures were fabricated with a self-assembly method for application in nanocarriers and sensing. The fluorescent intensity was increased by a factor of 4 in the micelle solution due to more stacked pyrene moieties. The core-shell structure of the micelle was confirmed by HR-TEM images. The pyrene moieties were positioned in the core of the micelle, and the surface consisted of hydrophilic PMMA blocks. The ester bond of the polymer backbone was breakable by irradiation with UV light. Therefore, the micelle structure was deformed after UV irradiation, and the excimer peak was drastically reduced as the monomer peak appeared. The deformation of micelle structures was clearly confirmed by FE-SEM and NMR analysis. These photolabile polymeric micelles may be widely useful for photo-stimulative nanocarriers as well as for the design of new functional micelles with many other chromophores.

Waterborne polyacrylic/PEDOT nanocomposites for conductive transparent adhesives.

A new nanocomposite for conductive transparent adhesives (CTAs) was synthesized by emulsion polymerization of acrylate monomers dispersed with poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). Polymer particles of waterborne CTAs were uniform, and the average size of the particles was 330 nm. The conductive transparent adhesive nanocomposites (CTANs) were casted onto various substrates including slide glass, indium tin oxide (ITO) glass, and PET film. Upon thermal processing at 80 degrees C, highly transparent adhesive films were obtained with surface uniformity. The stress of the CTANs was affected by the contents of PEDOT:PSS, and a 7.5 wt% CTAN film had the highest maximum stress of 0.33 MPa. Importantly, polyacrylic nanoparticles were well dispersed with conductive filler PEDOT:PSS in water because of their high dispersity in water. Therefore, the polyacrylic/PEDOT nanocomposite had a low percolation threshold of approximately 8% due to the enhanced connection between conductive channels. The CTANs with an optimum content (10 wt%) of PEDOT:PSS had high electromagnetic interference shielding effectiveness (36 dB) and transparency (75%) for application to electronics including displays and solar cells.

Synthesis and preparation of fluorinated polycarbonates enhancing the light absorption of fluorescent nanoparticles.

A new synthetic method for fluorinated polycarbonates without the use of any toxic phosgene gas is presented. The synthesis consists of a monomer synthesis followed by polymerization. The fluorinated polycarbonate (FPC) was confirmed by Fourier transform infrared spectroscopy (FT-IR) and NMR spectroscopy. The refractive index of the polymer was 1.466 determined by an Abbe refractometer. The contact angle measurement of the FPC films showed the hydrophobicity with water contact angle about 112.6 degrees. These films of varying thicknesses had over 98% transmittance. Taking advantage of the hydrophobicity and high transmittance of the FPCs, nanoparticles of FPCs were prepared directly in an aqueous solution with a reprecipitation method. Combining FPC solution with a solution containing fluorescent polymer (DTMSPV), nanoparticles with a core-shell structure were obtained easily with the reprecipitation method. The fluorescence intensity of the DTMSPV in the core-shell nanoparticles were much enhanced up to 34.1% compared to the molecularly dispersed DTMSPV solution.

NIR-sensitive poly(3,4-ethylenedioxyselenophene) derivatives for transparent photo-thermo-electric converters.

Electrochromism, photothermal effect, and thermoelectric properties of hexyl-derivatized poly(3,4-ethylenedioxyselenophene) are investigated by precisely controlling the morphology. These properties are clearly demonstrated by controlling the applied electrical potential of the polymer films. Especially, the doped polymer film at -0.1 V reveals the highest photothermal conversion efficiency and a power factor of 42.5% and 354.7 µW m(-1) K(-2) , respectively. Efficient visible to near-infrared absorption, photon to heat, and heat to electric conversion has been realized in one film that could benefit in exploiting multifunctional film displays, invisible NIR sensors, photodynamic theragnosis, and thermoelectric devices.

Noninvasive photodetachment of stem cells on tunable conductive polymer nano thin films: selective harvesting and preserved differentiation capacity.

Viable mesenchymal stem cells (MSCs) were efficiently and selectively harvested by near-infrared (NIR) light using the photothermal effect of a conductive polymer nano thin film. The poly(3,4-ethylenedioxy thiophene) (PEDOT)-coated cell culture surfaces were prepared via a simple and fast solution-casting polymerization (SCP) technique. The absorption of PEDOT thin films in the NIR region was effectively triggered cell harvesting upon exposure to an NIR source. By controlling the NIR absorption of the PEDOT film through electrochemical doping or growing PEDOT with different thin film thickness from 70 to 300 nm, the proliferation and harvesting of MSCs on the PEDOT surface were controlled quantitatively. This light-induced cell detachment method based on PEDOT films provides the temporal and spatial control of cell harvesting, as well as cell patterning. The harvested stem cells were found to be alive and well proliferated despite the use of temperature increase by NIR. More importantly, the harvested MSCs by this method preserved their intrinsic characteristics as well as multilineage differentiation capacities. This PEDOT surfaces could be used for repetitive culture and detachment of MSCs or for efficient selection or depletion of a specific subset from heterogeneous population during culture of various tissue-derived cells because there were no photodegradation and photobreakage in the PEDOT films by NIR exposure.