Synthetic Control of Intrinsic Defect Formation in Metal Oxide Nanocrystals Using Dissociated Spectator Metal Salts.

Crystallographic defects are essential to the functional properties of semiconductors, controlling everything from conductivity to optical properties and catalytic activity. In nanocrystals, too, defect engineering with extrinsic dopants has been fruitful. Although intrinsic defects like vacancies can be equally useful, synthetic strategies for controlling their generation are comparatively underdeveloped. Here, we show that intrinsic defect concentration can be tuned during the synthesis of colloidal metal oxide nanocrystals by the addition of metal salts. Although not incorporated in the nanocrystals, the metal salts dissociate at high temperatures, promoting the dissociation of carboxylate ligands from metal precursors, leading to the introduction of oxygen vacancies. For example, the concentration of oxygen vacancies can be controlled up to 9% in indium oxide nanocrystals. This method is broadly applicable as we demonstrate by generating intrinsic defects in metal oxide nanocrystals of various morphologies and compositions.

Spectrally tunable infrared plasmonic F,Sn:In2O3 nanocrystal cubes.

A synthetic challenge in faceted metal oxide nanocrystals (NCs) is realizing tunable localized surface plasmon resonance (LSPR) near-field response in the infrared (IR). Cube-shaped nanoparticles of noble metals exhibit LSPR spectral tunability limited to visible spectral range. Here, we describe the colloidal synthesis of fluorine, tin codoped indium oxide (F,Sn:In2O3) NC cubes with tunable IR range LSPR for around 10 nm particle sizes. Free carrier concentration is tuned through controlled Sn dopant incorporation, where Sn is an aliovalent n-type dopant in the In2O3 lattice. F shapes the NC morphology into cubes by functioning as a surfactant on the {100} crystallographic facets. Cube shaped F,Sn:In2O3 NCs exhibit narrow, shape-dependent multimodal LSPR due to corner, edge, and face centered modes. Monolayer NC arrays are fabricated through a liquid-air interface assembly, further demonstrating tunable LSPR response as NC film nanocavities that can heighten near-field enhancement (NFE). The tunable F,Sn:In2O3 NC near-field is coupled with PbS quantum dots, via the Purcell effect. The detuning frequency between the nanocavity and exciton is varied, resulting in IR near-field dependent enhanced exciton lifetime decay. LSPR near-field tunability is directly visualized through IR range scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS). STEM-EELS mapping of the spatially confined near-field in the F,Sn:In2O3 NC array interparticle gap demonstrates elevated NFE tunability in the arrays.

Designing a highly near infrared-reflective black nanoparticles for autonomous driving based on the refractive index and principle.

HYPOTHESIS: The development of highly NIR reflective black single-shell hollow nanoparticles (BSS-HNPs) can overcome the Light Detection and Ranging (LiDAR) sensor limitations of dark-tone materials. The crystalline phase of TiO2 and the refractive index can be controlled by calcination temperature. The formation of hollow structure and the refractive index is expected to simultaneously increase the light reflection and LiDAR detectability. EXPERIMENTS: The BSS-HNPs are synthesized using the sol-gel method, calcination, NaBH4 reduction, and etching to form a hollow structure with true blackness. The computational bandgap calculation is conducted to determine the bandgap energy (Eg) of the white and black TiO2 with different crystalline structures. The blackness of the as-synthesized materials is determined by the Commission on Illumination (CIE) L*a*b* color system. FINDINGS: The hydrophilic nature of BSS-HNPs enables the formulation of hydrophilic paints, allowing the mono-layer coating. With the synergistic effects of hollow structure and the refractive index, BSS-HNPs manifested superb NIR reflectance at LiDAR detection wavelengths. The high detectability, blackness, and hollow structure of BSS-HNPs can expand the variety of LiDAR-detectable dark-tone materials.

Vivid-Colored Electrorheological fluids with simultaneous enhancements in color clarity and Electro-Responsivity.

HYPOTHESIS: Surface modification of dielectric materials changes the dipole-dipole interactions under electric fields, thereby controlling the electrorheological (ER) response. The introduction of metal oxides onto mica templates and further coating of dyes is expected to simultaneously improve the color clarity and ER performance. EXPERIMENTS: Dye-coated TiO2 platelets on mica are synthesized for high-performance colorful ER fluids. A sol-gel method is utilized to grow TiO2 on mica to prepare precursor light-colored mica/TiO2 materials, which are coated with appropriate dyes to enhance the vividness as determined by the Commission Internationale de clairage L*a*b* color system. The color expression and color clarity improvement are explained via the light interference effect and the presence of chromophores. FINDINGS: The uniform TiO2 layers can be obtained under low pH conditions with controlled nucleation kinetics. The addition of dyes to TiO2 increases the surface area and porosity of ER materials and introduces heteroatoms that act as positive factors. In practical ER applications, dye-coated TiO2-based ER fluids exhibit higher ER performances compared with the corresponding light-colored TiO2-based ER fluids. The vivid-colored ER fluids could provide an easy selection for a wide range of rheological systems requiring a specific magnitude of stress by confirming the color.

Designing Novel LiDAR-Detectable Plate-Type Materials: Synthesis, Chemistry, and Practical Application for Autonomous Working Environment.

Plate-type hollow black TiO2 (HL/BT) with a high NIR reflectance was fabricated for the first time as a LiDAR-detectable black material. A TiO2 layer was formed on commercial-grade glass by using the sol-gel method to obtain a plate-type structure. The glass template was then etched with hydrofluoric acid to form a hollow structure, and blackness was further achieved through NaBH4 reduction, which altered the oxidation state of TiO2 to black TixO2x-1 or Ti4+ to Ti3+ and Ti2+. The blackness of the HL/BT material was maintained by a novel approach that involved etching prior to reduction. The thickness of the TiO2 layer was controlled to maximize the NIR reflectance when applied as paint. The HL/BT material with a thickness of 140 nm (HL/BT140) showed a blackness (L*) of 13.3 and high NIR reflectance of 23.6% at a wavelength of 905 nm. This is attributed to the effective light reflection at the interface created by the TiO2 layer and the hollow structure. Plate-type HL/BT140 provides excellent spreadability, durability, and thermal stability in practical paint applications compared with sphere-type materials due to the higher contacting area to the applied surface, making it suitable for use as a LiDAR-detectable inorganic black pigment in autonomous environments.

Polyaniline-Coated Mesoporous Carbon Nanosheets with Fast Capacitive Energy Storage in Symmetric Supercapacitors.

Polyaniline-capped mesoporous carbon nanosheets with high conductivity and porosity are synthesized by vapor deposition polymerization. The mesoporous carbon template is prepared by removing ordered cubic iron oxide nanocrystals embedded in the carbon matrix obtained by thermal decomposition of an iron-oleate complex in a sodium chloride matrix. The evaporated aniline monomers are slowly polymerized on the carbon surface pretreated with FeCl3 as an initiator, partially filling the carbon pores to improve conductivity. The resulting products exhibit efficient hybrid energy storage mechanisms of electric double-layer capacitance and pseudocapacitance. When the nanosheets are assembled for a symmetric supercapacitor, the device capacitance reaches 107.8 F g-1 , at a current density of 0.5 A g-1 , and a capacitance retention of 69.6% is achieved at a ten times higher current density of 5 A g-1 . Electrochemical impedance spectroscopy reveals that the transition from resistive to capacitive behavior occurs within 0.63 s, indicating that fast ion and charge transport results in high capacitance and rate capability. The corresponding energy and power densities are 9.59 Wh kg-1 and 200.1 W kg-1 at a current density of 0.5 A g-1 , demonstrating efficient energy storage in a symmetric supercapacitor.

Fabrication of Flexible All-Solid-State Asymmetric Supercapacitor Device via Full Recycling of Heated Tobacco Waste Assisted by PLA Gelation Template Method.

In this study, a flexible all-solid-state asymmetric supercapacitor (FASC) device has been successfully fabricated via full recycling of heated tobacco waste (HTW). Tobacco leaves and cellulose acetate tubes have been successfully carbonized (HTW-C) and mixed with metal oxides (MnO2 and Fe3O4) to obtain highly active materials for supercapacitors. Moreover, poly(lactic acid) (PLA) filters have been successfully dissolved in an organic solvent and mixed with the as-prepared active materials using a simple paste mixing method. In addition, flexible MnO2- and Fe3O4-mixed HTW-C/PLA electrodes (C-MnO2/PLA and C-Fe3O4/PLA) have been successfully fabricated using the drop-casting method. The as-synthesized flexible C-MnO2/PLA and C-Fe3O4/PLA electrodes have exhibited excellent electrical conductivity of 378 and 660 µS cm-1, and high specific capacitance of 34.8 and 47.9 mF cm-2 at 1 mA cm-2, respectively. A practical FASC device (C-MnO2/PLA//C-Fe3O4/PLA) has been assembled by employing the C-MnO2/PLA as the positive electrode and C-Fe3O4/PLA as the negative electrode. The as-prepared FASC device showed a remarkable capacitance of 5.80 mF cm-2 at 1 mA cm-2. Additionally, the FASC device manifests stable electrochemical performance under harsh bending conditions, verifying the superb flexibility and sustainability of the device. To the best of our knowledge, this is the first study to report complete recycling of heated tobacco waste to prepare the practical FASC devices. With excellent electrochemical performance, the experiments described in this study successfully demonstrate the possibility of recycling new types of biomass in the future.

3D Hierarchically Structured Tin Oxide and Iron Oxide-Embedded Carbon Nanofiber with Outermost Polypyrrole Layer for High-Performance Asymmetric Supercapacitor.

Herein, unique three-dimensional (3D) hierarchically structured carbon nanofiber (CNF)/metal oxide/conducting polymer composite materials were successfully synthesized by combinations of various experimental methods. Firstly, base CNFs were synthesized by carbonization of electrospun PAN/PVP fibers to attain electric double-layer capacitor (EDLC) characteristics. To further enhance the capacitance, tin oxide (SnO2) and iron oxide (Fe2O3) were coated onto the CNFs via facile hydrothermal treatment. Finally, polypyrrole (PPy) was introduced as the outermost layer by a dispersion polymerization method under static condition to obtain 3D-structured CNF/SnO2/PPy and CNF/Fe2O3/PPy materials. With each synthesis step, the morphology and dimension of materials were transformed, which also added the benign characteristic for supercapacitor application. For the practical application, as-synthesized CNF/SnO2/PPy and CNF/Fe2O3/PPy were applied as active materials for supercapacitor electrodes, and superb specific capacitances of 508.1 and 426.8 F g-1 (at 1 A g-1) were obtained (three-electrode system). Furthermore, an asymmetric supercapacitor (ASC) device was assembled using CNF/SnO2/PPy as the positive electrode and CNF/Fe2O3/PPy as the negative electrode. The resulting CNF/SnO2/PPy//CNF/Fe2O3/PPy device exhibited excellent specific capacitance of 101.2 F g-1 (at 1 A g-1). Notably, the ASC device displayed a long-term cyclability (at 2000 cycles) with a retention rate of 81.1%, compared to a CNF/SnO2//CNF/Fe2O3 device of 70.3% without an outermost PPy layer. By introducing the outermost PPy layer, metal oxide detachment from CNFs were prevented to facilitate long-term cyclability of electrodes. Accordingly, this study provides an effective method for manufacturing a high-performance and stable supercapacitor by utilizing unique 3D hierarchical materials, comprised of CNF, metal oxide, and conducting polymer.

Facile Enhancement of Electrochemical Performance of Solid-State Supercapacitor via Atmospheric Plasma Treatment on PVA-Based Gel-Polymer Electrolyte.

A facile oxygen (O2) atmospheric plasma treatment is applied to a polyvinyl alcohol (PVA) matrix to enhance its wettability and hydrophilicity. The optimal plasma treatment conditions are determined by varying the applied plasma power and plasma treatment time. A PVA matrix treated with a plasma power of 120 W for 5 s shows the most hydrophilicity owing to successful formation of carbonyl (-CO, >C=O) functional groups without any structural degradation. The plasma-treated PVA matrix is used as the gel-polymer electrolyte of a solid-state supercapacitor (SSC) by immersing solid matrix into various liquid electrolytes, such as sodium sulfate (Na2SO4), sulfuric acid (H2SO4), and potassium hydroxide (KOH). Compared with the pristine PVA-based device, PVA-120W5/Na2SO4-, PVA-120W5/H2SO4-, and PVA-120W5/KOH-based SSCs show 2.03, 2.05, and 2.14 times higher specific capacitances, respectively. The plasma-treated PVA matrix shows increased specific capacitance owing to the increased wettability, which in turn increases the ion transportation and reduces the electrical resistance. This study successfully demonstrates that the electrochemical performance of a SSC can be readily enhanced through plasma treatment for a short time (≤5 s).

A Study on Enhanced Electrorheological Performance of Plate-like Materials via Percolation Gel-like Effect.

The use of plate-like materials to induce a percolation gel-like effect in electrorheological (ER) fluids is sparsely documented. Hence, we dispersed plate-like materials, namely natural mica, synthetic mica, and glass, as well as their pulverized particles, in various concentrations in silicone oil to form ER fluids. Subsequently, the rheological properties of the fluids were evaluated and compared to identify the threshold concentration for percolating a gel-like state. The shear stress and viscoelastic moduli under zero-field conditions confirmed that plate-like materials can be used to induce percolation gel-like effects in ER fluids. This is because of the high aspect ratio of the materials, which enhances their physical stability. In practical ER investigations, ER fluids based on synthetic mica (30.0 wt%) showed the highest yield stress of 516.2 Pa under an electric field strength of 3.0 kV mm-1. This was attributed to the formation of large-cluster networks and additional polarization induced by the ions. This study provides a practical approach for developing a new type of gel-like ER fluid.

Preparation of a High-Performance Asymmetric Supercapacitor by Recycling Aluminum Paper and Filter Components of Heated Tobacco.

In this study, Al paper and cellulose acetate (CA) filters derived from heated tobacco waste were successfully converted into current collectors and active materials for a supercapacitor device. Typically, heated tobacco contains electrically discontinuous Al paper. First, Al was extracted from the tobacco waste using HCl to produce Lewis acid (AlCl3). This acid was then used in an Al electrodeposition process utilizing the chloroaluminate ionic liquid reaction between the acid and the base (RCl) at room temperature. To enhance the conductivity, a supplementary coating of Al metal was applied to the Al paper through electrodeposition, thus re-establishing the electrical continuity of the discontinuous parts and forming an Al-coated current collector. Moreover, the CA filters were carbonized under a nitrogen atmosphere, yielding carbon precursors (C-CA) for the supercapacitor electrodes. To further enhance the electrochemical performance, nickel oxide (NiO) was incorporated into C-CA, resulting in C-CA@NiO with pseudocapacitance. The specific surface area of CA increased with carbonization and the subsequent incorporation of NiO. The as-synthesized C-CA and C-CA@NiO materials were applied to an Al-coated current collector to obtain C-CA- and C-CA@NiO-based electrodes, exhibiting stable electrochemical behavior in the voltage range of -1.0 to 0 V and 0 to 1.0 V, respectively. An asymmetric supercapacitor (ASC) device was assembled with C-CA@NiO and C-CA as the positive and negative electrodes, respectively. This ASC device demonstrated a high specific capacitance of 40.8 F g-1, while widening the operating voltage window to 2.0 V. The high electrochemical performance of the device is attributed to the successful Al electrodeposition, which facilitates the electrical conductivity and increased porosity of the C-CA@NiO and C-CA materials. To the best of our knowledge, this is a pioneering study in regards to the conversion of biomass waste into current collectors and active materials to fabricate a practical ASC device. Our findings highlight the potential of reusing Al paper and CA filters from heated tobacco waste as essential components of energy storage devices.

Hollow TiO2 Nanoparticles Capped with Polarizability-Tunable Conducting Polymers for Improved Electrorheological Activity.

Hollow TiO2 nanoparticles (HNPs) capped with conducting polymers, such as polythiophene (PT), polypyrrole (PPy), and polyaniline (PANI), have been studied to be used as polarizability-tunable electrorheological (ER) fluids. The hollow shape of TiO2 nanoparticles, achieved by the removal of the SiO2 template, offers colloidal dispersion stability in silicone oil owing to the high number density. Conducting polymer shells, introduced on the nanoparticle surface using vapor deposition polymerization method, improve the yield stress of the corresponding ER fluids in the order of PANI < PPy < PT. PT-HNPs exhibited the highest yield stress of ca. 94.2 Pa, which is 5.0-, 1.5-, and 9.6-times higher than that of PANI-, PPy-, and bare HNPs, respectively. The improved ER response upon tuning with polymer shells is attributed to the space charge contribution arising from the movement of the charge carriers trapped by the heterogeneous interface. The ER response of studied ER fluids is consistent with the corresponding polarizability results as indicated by the permittivity and electrophoretic mobility measurements. In conclusion, the synergistic effect of hollow nanostructures and conducting polymer capping effectively enhanced the ER performance.

Synthesis of LiDAR-Detectable True Black Core/Shell Nanomaterial and Its Practical Use in LiDAR Applications.

Light detection and ranging (LiDAR) sensors utilize a near-infrared (NIR) laser with a wavelength of 905 nm. However, LiDAR sensors have weakness in detecting black or dark-tone materials with light-absorbing properties. In this study, SiO2/black TiO2 core/shell nanoparticles (SBT CSNs) were designed as LiDAR-detectable black materials. The SBT CSNs, with sizes of 140, 170, and 200 nm, were fabricated by a series of Stöber, TTIP sol-gel, and modified NaBH4 reduction methods. These SBT CSNs are detectable by a LiDAR sensor and, owing to their core/shell structure with intrapores on the shell (ca. 2−6 nm), they can effectively function as both color and NIR-reflective materials. Moreover, the LiDAR-detectable SBT CSNs exhibited high NIR reflectance (28.2 R%) in a monolayer system and true blackness (L* < 20), along with ecofriendliness and hydrophilicity, making them highly suitable for use in autonomous vehicles.

Development of Novel Colorful Electrorheological Fluids.

Herein, the electrorheological (ER) performances of ER fluids were correlated with their colors to allow for the visual selection of the appropriate fluid for a specific application using naked eyes. A series of TiO2-coated synthetic mica materials colored white, yellow, red, violet, blue, and green (referred to as color mica/TiO2 materials) were fabricated via a facile sol-gel method. The colors were controlled by varying the thickness of the TiO2 coating layer, as the coatings with different thicknesses exhibited different light interference effects. The synthesized color mica/TiO2 materials were mixed with silicone oil to prepare colored ER fluids. The ER performances of the fluids decreased with increasing thickness of the TiO2 layer in the order of white, yellow, red, violet, blue, and green materials. The ER performance of differently colored ER fluids was also affected by the electrical conductivity, dispersion stability, and concentrations of Na+ and Ca2+ ions. This pioneering study may provide a practical strategy for developing new ER fluid systems in future.

Smart Fluid System Dually Responsive to Light and Electric Fields: An Electrophotorheological Fluid.

Electrophotorheological (EPR) fluids, whose rheological activity is dually responsive to light and electric fields (E fields), is formulated by mixing photosensitive spiropyran-decorated silica (SP-sSiO2) nanoparticles with zwitterionic lecithin and mineral oil. A reversible photorheological (PR) activity of the EPR fluid is developed via the binding and releasing mechanism of lecithin and merocyanine (MC, a photoisomerized form of SP) under ultraviolet (UV) and visible (VIS) light applications. Moreover, the EPR fluid exhibits an 8-fold higher electrorheological (ER) performance compared to the SP-sSiO2 nanoparticle-based ER fluid (without lecithin) under an E field, which is attributed to the enhanced dielectric properties facilitated by the binding of the lecithin and SP molecules. Upon dual application of UV light and an E field, the EPR fluid exhibits high EPR performance (ca. 115.3 Pa) that far exceeds its separate PR (ca. 0.8 Pa) and ER (ca. 57.5 Pa) activities, because of the synergistic contributions of the PR and ER effects through rigid and fully connected fibril-like structures. Consequently, this study offers a strategy on formulation of dual-stimuli responsive smart fluid systems.

Dual external field-responsive polyaniline-coated magnetite/silica nanoparticles for smart fluid applications.

In this communication, an electromagnetorheological fluid containing Fe3O4/SiO2/PANI nanoparticles is reported to demonstrate its controllable rheological properties under electric and magnetic fields. The EMR performance was significantly enhanced under the dual fields in the parallel direction.

Enhanced Electrorheological Performance of Mixed Silica Nanomaterial Geometry.

The mixed geometrical effect on the electrorheological (ER) activity of bimodal ER fluids was investigated by mixing SiO2 spheres and rods of different dimensions. To gain an in-depth understanding of the mixed geometrical effect, 12 bimodal ER fluids were prepared from 4 sizes of SiO2 spheres (50, 100, 150, and 350 nm) and 3 types of SiO2 rods with different aspect ratios (L/D = 2, 3, and 5). Five concentrations of SiO2 spheres and rods were created for each bimodal ER fluid, resulting in a total of 60 sets of comprehensive ER measurements. Some bimodal ER fluids exhibited enhanced ER performance, as high as 23.0%, compared to single SiO2 rod-based ER fluids to reveal the mixed geometrical effect of bimodal ER fluids. This interesting experimental result is based on the structural reinforcement provided by spheres to fibrillated rod materials, demonstrating the mixed geometrical effect on ER activity.

Morphology-controlled mesoporous SiO2 nanorods for efficient scaffolds in organo-metal halide perovskite solar cells.

In meso-superstructured perovskite solar cells, the scaffolding layer, composed of insulating metal oxide nanoparticles, plays an important role in the loading efficiency of the perovskite layer. This communication describes 1D mesoporous silica nanoparticles that were successfully used as scaffolds to enhance the electron extraction from the perovskite absorber layer to the working electrode.

Enhanced electrorheological activity of polyaniline coated mesoporous silica with high aspect ratio.

Polyaniline-coated mesoporous silica (PANI/mSiO2) materials with different aspect ratios (L/D=1, 5, and 10) were fabricated by a vapor deposition polymerization (VDP) method to investigate the geometric effect on electrorheological (ER) activity. The PANI/mSiO2 materials were dedoped by a facile NH4OH treatment to reduce the conductivity to a level appropriate for ER applications. Notably, the PANI/mSiO2-based ER fluids exhibited enhanced ER performance with increasing aspect ratio. In particular, the PANI/mSiO2 material with the highest aspect ratio manifested the highest ER activity, which was attributed to geometric effects on flow resistance and mechanical stability. Moreover, the ER materials with higher aspect ratios showed improved dielectric properties of large achievable polarizability and short relaxation time. Hence, the synergistic contribution of geometric effects and dielectric properties resulted in enhanced ER activity. Consequently, this study provides insight into an effective method to improve ER performance by simple manipulation of the particle geometry.

A comparative study of the electrorheological properties of various N-doped nanomaterials using ammonia plasma treatment.

A new, simple method is reported to enhance the electrorheological (ER) activity of nanomaterials. Plasma treatment was the ideal technique owing to its ease of use, versatility, and common usage in mass production. Multi-gram quantities of ER nanomaterials with different morphologies, sizes, and compositions were successfully treated by ammonia plasma.