Hierarchically Porous Carbon Networks Derived from Chitosan for High-Performance Electrochemical Double-Layer Capacitors.

Activated carbon (AC) compounds derived from biomass precursors have garnered significant attention as electrode materials in electric double-layer capacitors (EDLCs) due to their ready availability, cost-effectiveness, and potential for mass production. However, the accessibility of their active sites in electrochemistry has not been investigated in detail. In this study, we synthesized two novel macro/micro-porous carbon structures prepared from a chitosan precursor using an acid/potassium hydroxide activation process and then examined the relationship between their textural characteristics and capacitance as EDLCs. The material characterizations showed that the ACs, prepared through different activation processes, differed in porosity, with distinctive variations in particle shape. The sample activated at 800 °C (Act-chitosan) was characterized by plate-shaped particles, a specific surface area of 4128 m2/g, and a pore volume of 1.87 cm3/g. Assessment of the electrochemical characteristics of Act-chitosan showed its remarkable capacitance of 183.5 F/g at a scan rate of 5 mV/s, and it maintained exceptional cyclic stability even after 10,000 cycles. The improved electrochemical performance of both chitosan-derived carbon structures could thus be attributed to their large, well-developed active sites within pores < 2 nm, despite the fact that interconnected macro-porous particles can enhance ion accessibility on electrodes. Our findings provide a basis for the fabrication of biomass-based materials with promising applications in electrochemical energy storage systems.

Effect of Fluorination Position on the Crystalline Structure and Stretchability of Intrinsically Stretchable Polymer Semiconductors.

A clear understanding of the structure-property relationship of intrinsically stretchable polymer semiconductors (ISPSs) is essential for developing high-performance polymer-based electronics. Herein, we investigate the effect of the fluorination position on the crystalline structure, charge-carrier mobility, and stretchability of polymer semiconductors based on a benzodithiophene-co-benzotriazole configuration. Although four different polymer semiconductors showed similar field-effect mobilities for holes (µ ≈ 0.1 cm2 V-1 s-1), polymer semiconductors with nonfluorinated backbones exhibited improved thin-film stretchability confirmed with crack onset strain (εc ≈ 20%-50%) over those of fluorinated counterparts (εc ≤ 10%). The enhanced stretchability of polymer semiconductors with a nonfluorinated backbone is presumably due to the higher face-on crystallite ratio and π-π stacking distance in the out-of-plane direction than those of the other polymer semiconductors. These results provide new insights into how the thin-film stretchability of polymer semiconductors can be improved by using precise molecular tailoring without deteriorating electrical properties.

Competitive Effects of Oxidation and Quantum Confinement on Modulation of the Photophysical Properties of Metallic-Phase Tungsten Dichalcogenide Quantum Dots.

Metallic-phase transition metal dichalcogenide quantum dots (TMDs-mQDs) have been reported in recent years. However, a dominant mechanism for modulating their intrinsic exciton behaviors has not been determined yet as their size is close to the Bohr radius. Herein, we demonstrate that the oxidation effect prevails over quantum confinement on metallic-phase tungsten dichalcogenide QDs (WX2-mQDs; X = S, Se) when the QD size becomes larger than the exciton Bohr radius. WX2-mQDs with a diameter of ~12 nm show an obvious change in their photophysical properties when the pH of the solution changes from 2 to 11 compared to changing the size from ~3 nm. Meanwhile, we found that quantum confinement is the dominant function for the optical spectroscopic results in the WX2-mQDs with a size of ~3 nm. This is because the oxidation of the larger WX2-mQDs induces sub-energy states, thus enabling excitons to migrate into the lower defect energy states, whereas in WX2-mQDs with a size comparable to the exciton Bohr radius, protonation enhances the quantum confinement.

High-Performance Electrochromic Devices Based on Size-Controlled 2D WO3 Nanosheets Prepared Using the Intercalation Method.

It is difficult to obtain ultrathin two-dimensional (2D) tungsten trioxide (WO3) nanosheets through direct exfoliation from bulk WO3 in solution due to the strong bonding between interlayers. Herein, WO3 nanosheets with controllable sizes were synthesized via K+ intercalation and the exfoliation of WO3 powder using sonication and temperature. Because of the intercalation and expansion in the interlayer distance, the intercalated WO3 could be successfully exfoliated to produce a large quantity of individual 2D WO3 nanosheets in N-methyl-2-pyrrolidone under sonication. The exfoliated ultrathin WO3 nanosheets exhibited better electrochromic performance in an electrochromic device than WO3 powder and exfoliated WO3 without intercalation. In particular, the prepared small WO3 nanosheets exhibited excellent electrochromic properties with a large optical modulation of 41.78% at 700 nm and fast switching behavior times of 9.2 s for bleaching and 10.5 s for coloring. Furthermore, after 1000 cycles, the small WO3 nanosheets still maintained 86% of their initial performance.

Graphene Quantum Dots with Blue and Yellow Luminescence Fabricated by Modulating Intercalation State.

The development of graphene quantum dots (GQDs) with low toxicity, excellent dispersibility, and high photostability has led to extensive progress in bio-imaging and optical sensing applications. However, one-pot synthesis and mass production of GQDs, and tuning their photoluminescence, remains a challenge. Here we demonstrate a simple and scalable method for fabricating GQDs with high size uniformity and chemical stability, via a sequential process of inserting alkali metal into graphite (Stage I: KC8 and Stage II: KC24) and exfoliation to GQDs in a selected solvent. Structural and optical measurements were conducted, and the emitted colors of the as-prepared GQDs were blue (KC8) and yellow (KC24), respectively. The stage of graphite intercalation in the compounds played an important role in the size and thickness of the GQD. The as-prepared GQDs had clear characteristic peaks consistent with the quantum confinement effect and intrinsic/extrinsic states. Our approach will provide great potential for a wide variety of bioimaging and bioanalysis applications.

pH-Dependent Photophysical Properties of Metallic Phase MoSe2 Quantum Dots.

Fluorescence properties of quantum dots (QDs) are critically affected by their redox states, which is important for practical applications. In this study, we investigated the optical properties of MoSe2-metallic phase quantum-dots (MoSe2-mQDs) depending on the pH variation, in which the MoSe2-mQDs were dispersed in water with two sizes (Φ~3 nm and 12 nm). The larger MoSe2-mQDs exhibited a large red-shift and broadening of photoluminescence (PL) peak with a constant UV absorption spectra as varying the pH, while the smaller ones showed a small red-shift and peak broadening, but discrete absorption bands in the acidic solution. The excitation wavelength-dependent photoluminescence shows that the PL properties of smaller MoSe2-mQDs are more sensitive to the pH change compared to those of larger ones. From the time-resolved PL spectroscopy, the excitons dominantly decaying with an energy of ~3 eV in pH 2 clearly show the shift of PL peak to the lower energy (~2.6 eV) as the pH increases to 7 and 11 in the smaller MoSe2-mQDs. On the other hand, in the larger MoSe2-mQDs, the exciton decay is less sensitive to the redox states compared to those of the smaller ones. This result shows that the pH variation is more critical to the change of photophysical properties than the size effect in MoSe2-mQDs.

Metallic Phase Transition Metal Dichalcogenide Quantum Dots as Promising Bio-Imaging Materials.

Transition metal dichalcogenide-based quantum dots are promising materials for applications in diverse fields, such as sensors, electronics, catalysis, and biomedicine, because of their outstanding physicochemical properties. In this study, we propose bio-imaging characteristics through utilizing water-soluble MoS2 quantum dots (MoS2-QDs) with two different sizes (i.e., ~5 and ~10 nm). The structural and optical properties of the fabricated metallic phase MoS2-QDs (m-MoS2-QDs) were characterized by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, UV-vis absorption spectroscopy, and photoluminescence. The synthesized m-MoS2-QDs showed clear photophysical characteristic peaks derived from the quantum confinement effect and defect sites, such as oxygen functional groups. When the diameter of the synthesized m-MoS2-QD was decreased, the emission peak was blue-shifted from 436 to 486 nm under excitation by a He-Cd laser (325 nm). Density functional theory calculations confirmed that the size decrease of m-MoS2-QDs led to an increase in the bandgap because of quantum confinement effects. In addition, when incorporated into the bio-imaging of HeLa cells, m-MoS2-QDs were quite biocompatible with bright luminescence and exhibited low toxicity. Our results are commercially applicable for achieving high-performance bio-imaging probes.

Quaternary Artificial Nacre-Based Electronic Textiles with Enhanced Mechanical and Flame-Retardant Performance.

Interest in wearable electronics has led to extensive studies on woven textiles that are mechanically robust and stretchable, have high electrical conductivities, and exhibit fire resistance properties even at high temperatures. We demonstrate a highly easy and scalable method for fabricating defect-free graphene (dfG) nacre-based woven electronic textiles (e-textiles) with enhanced flame-retardant properties and high electronic conductivities. The as-prepared graphene shows perfect preservation of its inherent properties without any crystal damage during subsequent exfoliation and noncovalent melamine functionalization. The defect-free graphene functionalized by melamine (m-dfG) is well dispersed in various polar solvents. To investigate the synergistic effect of m-dfG, quaternary artificial nacre composites are fabricated by adding manganese(II) chloride to a m-dfG/polymer (carboxymethyl cellulose (CMC)) composite. Their mechanical, electrical, and thermal characteristics are then evaluated. The quaternary m-dfG-Mn2+-CMC artificial nacre exhibits exceptionally enhanced mechanical properties (tensile strength: 613.9 MPa; toughness: 7.13 MJ m-3) and the best flame retardancy (even at torch heating) as compared to those of graphene oxide/reduced graphene oxide (GO/rGO)-based nacres. In this context, our approach will be helpful to future wearable electronics and fire-retardant textiles with high strength, which can accelerate the commercial viability of e-textiles.

Synergistic Optimization of the Thermoelectric and Mechanical Properties of Large-Size Homogeneous Bi0.5Sb1.5Te3 Bulk Samples via Carrier Engineering for Efficient Energy Harvesting.

Manufacturing an economically viable, efficient commercial thermoelectric (TE) module is essential for power generation and refrigeration. However, mediocre TE properties, lack of good mechanical stability of the material, and significant difficulties involved in the manufacturing of large-scale powder as well as bulk samples hinder the potential applications of the modules. Herein, an economically feasible single-step water atomization (WA) is employed to synthesize BST powder (2 kg) by Cu doping within a short time and consolidated into large-scale bulk samples (500 g) for the first time with a diameter of 50 mm and a thickness of about 40 mm using spark plasma sintering (SPS). The incorporation of Cu into BST greatly boosts the carrier concentration, leading to a significant increase in electrical conductivity, and inhibits the bipolar thermal conductivity by 73%. Synchronously, the lattice contribution (κL) is greatly reduced by the effective scattering of phonons by comprising fine-grain boundaries and point defects. Therefore, the peak ZT is shifted to the mid-temperature range and obtained a maximum of ∼1.31 at 425 K and a ZTave of 1.24 from 300 to 500 K for the BSTCu0.05 sample, which are considerably greater than those of the bare BST sample. Moreover, the maximum compressive mechanical strength of large-size samples manufactured by the WA-SPS process is measured as 102 MPa, which is significantly higher than commercial zone melting samples. The thermoelectric module assembled with WA-SPS-synthesized BSTCu0.05 and commercial n-type BTS material manifests an outstanding cooling performance (-19.4 °C), and a maximum output power of 6.91 W is generated at ΔT ∼ 200 K. These results prove that the BSTCux samples are eminently suitable for the fabrication of industrial thermoelectric modules.

Hydrogen-Bonding-Mediated Molecular Vibrational Suppression for Enhancing the Fluorescence Quantum Yield Applicable for Visual Phenol Detection.

It is generally accepted that while efficient suppression of molecular vibration is inevitable for purely organic phosphors due to their long emission lifetime in the regime of 1 ms or longer, fluorophores having a lifetime in the nanoseconds regime are not sensitive to collisional quenching. Here, however, we demonstrate that a fluorophore, 2,5-bis(hexyloxy)terephthaldehyde (BHTA), capable of having hydrogen bonding (H bonding) via its two aldehyde groups can have a largely enhanced (450%) fluorescence quantum yield (QY) in amorphous poly(acrylic acid) (PAA) matrix compared to its crystalline powder. We ascribe this enhanced QY to the efficient suppression of molecular vibrations via intermolecular H bonding. We confirm this feasibility by conducting temperature-dependent fluorescence emission intensity measurement. As gaseous phenol can intervene with the H bonding between BHTA and PAA, interestingly, BHTA embedded in PAA can selectively detect gaseous phenol by a sharp fluorescence emission intensity drop that is visibly recognizable by the naked eye. The results provide an insightful molecular design strategy for a fluorophore and fluorometric sensory system design for enhanced photoluminescence QY and convenient detection of various volatile organic compounds.

Boosting Photovoltaic Performance in Organic Solar Cells by Manipulating the Size of MoS2 Quantum Dots as a Hole-Transport Material.

The design of photoactive materials and interface engineering between organic/inorganic layers play a critical role in achieving enhanced performance in energy-harvesting devices. Two-dimensional transitional dichalcogenides (TMDs) with excellent optical and electronic properties are promising candidates in this regard. In this study, we demonstrate the fabrication of size-controlled MoS2 quantum dots (QDs) and present fundamental studies of their optical properties and their application as a hole-transport layer (HTL) in organic solar cells (OSCs). Optical and structural analyses reveal that the as-prepared MoS2 QDs show a fluorescence mechanism with respect to the quantum confinement effect and intrinsic/extrinsic states. Moreover, when incorporated into a photovoltaic device, the MoS2 QDs exhibit a significantly enhanced performance (5/10-nanometer QDs: 8.30%/7.80% for PTB7 and 10.40%/10.17% for PTB7-Th, respectively) compared to those of the reference device (7.24% for PTB7 and 9.49% for PTB7-Th). We confirm that the MoS2 QDs clearly offer enhanced transport characteristics ascribed to higher hole-mobility and smoother root mean square (Rq) as a hole-extraction material. This approach can enable significant advances and facilitate a new avenue for realizing high-performance optoelectronic devices.

Biological Potential of Polyethylene Glycol (PEG)-Functionalized Graphene Quantum Dots in In Vitro Neural Stem/Progenitor Cells.

Stem cell therapy is one of the novel and prospective fields. The ability of stem cells to differentiate into different lineages makes them attractive candidates for several therapies. It is essential to understand the cell fate, distribution, and function of transplanted cells in the local microenvironment before their applications. Therefore, it is necessary to develop an accurate and reliable labeling method of stem cells for imaging techniques to track their translocation after transplantation. The graphitic quantum dots (GQDs) are selected among various stem cell labeling and tracking strategies which have high photoluminescence ability, photostability, relatively low cytotoxicity, tunable surface functional groups, and delivering capacity. Since GQDs interact easily with the cell and interfere with cell behavior through surface functional groups, an appropriate surface modification needs to be considered to get close to the ideal labeling nanoprobes. In this study, polyethylene glycol (PEG) is used to improve biocompatibility while simultaneously maintaining the photoluminescent potentials of GQDs. The biochemically inert PEG successfully covered the surface of GQDs. The PEG-GQDs composites show adequate bioimaging capabilities when internalized into neural stem/progenitor cells (NSPCs). Furthermore, the bio-inertness of the PEG-GQDs is confirmed. Herein, we introduce the PEG-GQDs as a valuable tool for stem cell labeling and tracking for biomedical therapies in the field of neural regeneration.

Ti3C2Tx MXene-Based Three-Dimensional Architecture for Carbon Dioxide Capture.

Dramatic increases in fossil fuel consumption inevitably led to the emission of huge amounts of CO2 gas, causing abnormalities in the climate system. Despite continuous efforts to resolve global atmospheric problems through CO2 capture and separation, success has been limited by poor CO2 selectivity in the CO2/N2 mixture. Herein, we demonstrate the fabrication of a three-dimensional (3D) nanostructure from two-dimensional transition metal carbides (Ti3C2Tx, MXene), and assess its utility as an adsorbent in a CO2 capture system. Through structural and textural analysis, we confirm that the as-prepared MXene possesses high size uniformity with a thickness of ~2.5 nm, and that an MXene aerogel interconnected by MXene nanosheets has a 3D porous architecture with micro/nano porosity (Barrett-Joyner-Halenda (BJH) pore size = 11.4 nm). Moreover, the MXene aerogel exhibits favorable adsorption behavior for CO2, due to the high-quality MXene nanosheets even with a low specific surface area. Our approach could lead to significant advances in CO2 capture by adsorbents and open up new opportunities for mass production.

Novel Exfoliation of High-Quality 2H-MoS2 Nanoflakes for Solution-Processed Photodetector.

Highly dispersive molybdenum disulfide nanoflakes (MoS2 NFs), without any phase transition during the exfoliation process, are desirable for full utilization of their semiconductor properties in practical applications. Here, we demonstrate an innovate approach for fabricating MoS2 NFs by using hydrazine-assisted ball milling via the synergetic effect of chemical intercalation and mechanical exfoliation. The NFs obtained have a lateral size of 600-800 nm, a thickness less than 3 nm, and high crystallinity in the 2H semiconducting phase. They form a stable dispersion in various solvents, which will be helpful for many applications, due to the oxygen functional group. To investigate production of a two-dimensional (2D) photodetector, 2D semiconducting MoS2, MoS2-p-Si vertical devices were fabricated, and their optical properties were characterized. The photodiode exhibited consistent responses with excellent photo-switching characteristics with wavelengths of 850, 530, and 400 nm.

In Situ Enhanced Raman and Photoluminescence of Bio-Hybrid Ag/Polymer Nanoparticles by Localized Surface Plasmon for Highly Sensitive DNA Sensors.

We experimentally demonstrate the simultaneous enhancement of Raman and photoluminescence (PL) of core-shell hybrid nanoparticles consisting of Ag (core) and polydiacetylene (PDA, shell) through the assistance of localized surface plasmon (LSP) effect for the effective biosensor. Core-shell nanoparticles (NPs) are fabricated in deionized water through a sequential process of reprecipitation and self-assembly. The Raman signal of PDA on core-shell NPs is enhanced more than 100 times. Also, highly enhanced photoluminescence is observed on Ag/PDA hybrid NPs after coupling of the complementary t-DNA with p-DNA which are immobilized on PDA shell. This indicates that the core Ag affects the Raman and PL of PDA through the LSP resonance, which can be caused by the energy and/or charge transfer caused by the LSP coupling and the strong electromagnetic field near Ag NP surface. Only electrons present on the surface interact with the PDA shell, not involving the electrically neutral part of the electrons inside the Ag NP. Furthermore, this work shows that as prepared Ag/PDA NPs functionalized by probe DNA can sense the target DNA with an attomolar concentration (100 attomole).

Highly luminescent polyethylene glycol-passivated graphene quantum dots for light emitting diodes.

The emergence of fluorescent graphene quantum dots (GQDs) is expected to enhance the usefulness of quantum dots (QDs), in terms of their unique luminescence, photostability, low toxicity, chemical resistance, and electron transport properties. Here we prepared blue-photoluminescent polyethylene glycol GQDs (PEG-GQDs) through PEG surface passivation. The photoluminescence (PL) quantum yield (QY) of PEG-GQDs with 320 nm excitation was about 4.9%, which was higher than that of pure GQDs. The as-fabricated PEG-GQDs with high QY were then used as light-emitting diode (PGQD-LED) emitters, in which the GQDs were incorporated into polymeric host layers in a multilayer electroluminescent device; blue emission with a luminance exceeding 800 cd m-2 was achieved, thus demonstrating the potential of PEG-GQDs as emitters in electroluminescence applications. Furthermore, the fluorescence mechanism of PEG-GQDs was investigated and proved that the origin of strong fluorescence of PEG-GQDs is associated with the luminescence from intrinsic states. The highly fluorescent PEG-GQDs will allow new devices, such as multicolor LEDs, to be developed with extraordinary properties, by tailoring the intrinsic and extrinsic states.

Synergistic Effect of a Defect-Free Graphene Nanostructure as an Anode Material for Lithium Ion Batteries.

Graphene nanosheets have been among the most promising candidates for a high-performance anode material to replace graphite in lithium ion batteries (LIBs). Studies in this area have mainly focused on nanostructured electrodes synthesized by graphene oxide (GO) or reduced graphene oxide (rGO) and surface modifications by a chemical treatment. Herein, we propose a cost-effective and reliable route for generating a defect-free, nanoporous graphene nanostructure (df-GNS) through the sequential insertion of pyridine into a potassium graphite intercalation compound (K-GIC). The as-prepared df-GNS preserves the intrinsic property of graphene without any crystal damage, leading to micro-/nano-porosity (microporosity: ~10-50 µm, nanoporosity: ~2-20 nm) with a significantly large specific surface area. The electrochemical performance of the df-GNS as an anode electrode was assessed and showed a notably enhanced capacity, rate capability, and cycle stability, without fading in capacity or decaying. This is because of the optimal porosity, with perfect preservation of the graphene crystal, allowing faster ion access and a high amount of electron pathways onto the electrode. Therefore, our work will be very helpful for the development of anode and cathode electrodes with higher energy and power performance requirements.

Versatile and Tunable Electrical Properties of Doped Nonoxidized Graphene Using Alkali Metal Chlorides.

With the rapid development of wearable and flexible electronics, graphene has been intensively studied for the transparent, hole transport electrode layer (HTL) of field-effect transistors, light-emitting diodes, and organic photovoltaic (OPV) cells. To modulate the sheet resistance and the work function of graphene as a HTL, the surface doping is versatile while retaining high transparency. In this work, we used a chemical doping method to control the charge carrier density, band gap, and work function of graphene with minimizing the damage of the carbon network, for which metal chlorides (NaCl, KCl, and AuCl3) were used as chemical dopants. The high-quality graphene flakes were synthesized with large lateral sizes of more than 5 µm using ternary graphite intercalation compounds. Interestingly, the AuCl3-doped graphene flake film with a film thickness of about 20 nm showed the lowest reported sheet resistance of ∼249 Ω/sq with ∼75% transmittance. Furthermore, it could control the work function from 4.32 to 5.1 eV. The interfacial dipole complexes of metal cations with a low work function and the reactive radicals such as -OH were discussed to explain this result. For the practical application, an OPV device using the AuCl3-doped graphene flake film as the HTL was fabricated and it demonstrated enhanced power conversion efficiency while maintaining high optical transparency in visible light.

Two-Dimensional WO3 Nanosheets Chemically Converted from Layered WS2 for High-Performance Electrochromic Devices.

Two-dimensional (2D) transitional metal oxides (TMOs) are an attractive class of materials due to the combined advantages of high active surface area, enhanced electrochemical properties, and stability. Among the 2D TMOs, 2D tungsten oxide (WO3) nanosheets possess great potential in electrochemical applications, particularly in electrochromic (EC) devices. However, feasible production of 2D WO3 nanosheets is challenging due to the innate 3D crystallographic structure of WO3. Here we report a novel solution-phase synthesis of 2D WO3 nanosheets through simple oxidation from 2D tungsten disulfide (WS2) nanosheets exfoliated from bulk WS2 powder. The complete conversion from WS2 into WO3 was confirmed through crystallographic and elemental analyses, followed by validation of the 2D WO3 nanosheets applied in the EC device. The EC device showed color modulation of 62.57% at 700 nm wavelength, which is 3.43 times higher than the value of the conventional device using bulk WO3 powder, while also showing enhancement of ∼46.62% and ∼62.71% in switching response-time (coloration and bleaching). The mechanism of enhancement was rationalized through comparative analysis based on the thickness of the WO3 components. In the future, 2D WO3 nanosheets could also be used for other promising applications such as sensors, catalysis, thermoelectric, and energy conversion.