One-pot hydrothermal synthesis of β-MnO2 crystals and their magnetic properties

β-MnO₂ nanorods and flower-like structures were synthesized via a one-pot hydrothermal route at 160 °C without using any template and surfactant. It is demonstrated that H⁺ in the solution has a significant effect on the morphology and resultant magnetic property of β-MnO₂ crystals. Magnetic measurements indicate that the Néel temperature of the β-MnO₂ flower-like structures is 98 K, which is about 2 K higher than that of the nanorods counterpart.     

Novel one-dimensional polyaniline/Ni0.5Zn0.5Fe2O4 hybrid nanostructure: synthesis,magnetic, and electromagnetic wave absorption properties

For the first time, the novel one-dimensional uniform polyaniline (PANI)/Ni_0.5Zn_0.5Fe₂O₄ (NZFO) hybrid nanorods were synthesized by an in situ polymerization approach with the assistance of ultrasound and magnetic field. Owing to the unique shape, structure, and chemical composition, the as-synthesized hybrid nanorods with different PANI/NZFO mass ratios possess adjustable magnetic properties, high-saturated magnetization, and coercivity. In addition, these hybrid nanorods present stronger reflection loss and a wider absorption band than pure NZFO. Especially, the hybrid nanorods containing 59 wt% NZFO exhibit excellent microwave absorption properties, with a maximum reflection loss (R _L) of ?27.5 dB observed at 6.2 GHz. And the widest absorption band (R _L ≤ ?10 dB) is 8.1 GHz, corresponding to a matching thin thickness of 2 mm. It is superior to the previously reported value of PANI/ferrite. Therefore, these PANI/NZFO hybrid nanorods may be candidates for lightweight, low-cost, broadband, and highly efficient microwave-absorbing materials.     

EMI shielding effectiveness of graphene decorated with graphene quantum dots and silver nanoparticles reinforced PVDF nanocomposites

Graphene decorated with graphene quantum dots (G-D-GQDs) have been successfully synthesized using solvothermal cutting of graphene oxide. The incorporation of G-D-GQDs in polyvinyledene fluoride (PVDF) matrix shows the total EMI shielding effectiveness (SE_T) of 31 dB at 8 GHz. The main mechanism of high EMI shielding effectiveness is reflection and absorption of EM radiation. The high absorption of EM radiation is due to tunneling of electrons from GQDs. Further, decoration of G-D-GQDs with conducting Ag nanoparticles (G-D-GQDsAg) enhances the SE_T value to 43 dB at 8 GHz of PVDF/G-D-GQDsAg nanocomposite, due to increase in electrical conductivity of PVDF/G-D-GQDsAg nanocomposite and enhanced dispersion of G-D-GQDsAg in PVDF matrix. The incorporation of G-D-GQDs and G-D-GQDsAg in PVDF matrix also increases the thermal stability and crystallinity of PVDF. The increase in thermal stability and crystallinity are more for PVDF/G-D-GQDsAg nanocomposite as compare to PVDF/G-D-GQDs nanocomposite, due to better dispersion of G-D-GQDsAg in PVDF matrix. Thus, PVDF/G-D-GQDsAg nanocomposite having high SE_T value can shield 99.9% of electromagnetic radiation in X-band range, which make it suitable for EMI shielding application for consumer electronic equipment’s.     

Synthesis of δ-MnO<Subscript>2</Subscript> film on FTO glass with high electrochemical performance

δ-Manganese dioxide (MnO₂) has been proved to own the excellent electrochemical performances for a long time. But few of studies report the electrochemical performances of δ-MnO₂ film. Here, we synthesize δ-MnO₂ film on fluorine-doped tin oxide (FTO) glass via a simple redox reaction at the room temperature. The X-ray diffraction (XRD) and Raman spectroscopy are used to confirm the physical structure, whilst cyclic voltammetry and galvanostatic charge-discharge measurements are performed to investigate the electrochemical performances. Encouragingly, δ-MnO₂ film delivers a high specific capacitance (C _s) of 350.5 F g^?1 at 100 mV s^?1 and 275.0 F g^?1 at 5 A g^?1. The capacitance retention of δ-MnO₂ film can be up to 100 % after being charge/discharge at 2 A g^?1 with 1000 cycles. This research might further indicate that δ-MnO₂ film is a promising electrode material for supercapacitors.     

Vertically aligned α-MnO<Subscript>2</Subscript> nanosheets on carbon nanotubes as cathodic materials for aqueous rechargeable magnesium ion battery

In this work, vertically aligned α-MnO₂ nanosheets on carbon nanotubes are synthesized simply by a solution process and the electrochemical performance as host materials of magnesium ion is tested in aqueous solution. Cyclic voltammetry analysis confirms the enhanced electrochemical activity of carbon nanotube-supported samples. Moreover, carbon nanotubes skeleton could reduce the charge transfer resistant of the cathode materials, which is confirmed by electrochemical impedance spectroscopy. Furthermore, when tested as magnesium ion batteries cathodic electrode, the α-MnO₂/carbon nanotube sample registers a prominent discharge capacity of 144.6 mAh g^?1 at current density of 0.5 A g^?1, which is higher than the discharge capacity of α-MnO₂ (87.5 mAh g^?1) due to the synergistic effect of insertion/deinsertion reaction and physical adsorption/desorption process. After the 1000th cycle, a remarkable discharge capacity of 48.3 mAh g^?1 is collected for α-MnO₂/carbon nanotube at current density of 10 A g^?1, which is 85% of the original. It is found that the carbon skeleton not only improved the capacity but also enhanced the cycling performance of the α-MnO₂ electrode significantly. Therefore, α-MnO₂/carbon nanotube is a very promising candidate for further application in environmentally benign magnesium ion batteries.     

Synthesis and lithium ion insertion/extraction properties of hollandite-type MnO2 prepared by acid digestion of Mn2O3

Single-phase specimens of α-MnO₂ (hollandite-type) and β-MnO₂ (rutile-type) were synthesized by the acid digestion of Mn₂O₃ under reflux conditions. The type of polymorph of MnO₂ products was strongly dependent on the reaction temperature, type of acid used, and its concentration. The pH titration curve of α-MnO₂ displayed a monobasic acid behavior toward Li⁺, but β-MnO₂ showed a poor ion-exchange property. In contrast, both α-MnO₂ and β-MnO₂ acted as a rechargeable active material in a liquid organic electrolyte lithium cell. The initial discharge capacities of both electrodes exceeded 200 mAh/g (cut-off voltage: 2 V). After discharge–charge repetition, the α-MnO₂ structure was still retained without structure collapse, although the β-MnO₂ structure was destroyed. These findings show that Li⁺ ions can be inserted only into the hollandite-type tunnels in α-MnO₂ and cannot diffuse the rutile-type linkages in α-MnO₂ as well as those in β-MnO₂ without structure collapse.     

Synthesis of sea urchin-like LiMn2O4 hollow macrospheres via in situ conversion for rechargeable lithium-ion batteries

Among several materials (transition metal oxide) under development for use as a cathode in lithium-ion batteries, cubic spinel LiMn₂O₄ is one of the most promising cathode materials. In this study, the sea urchin-like LiMn₂O₄ hollow macrospheres were synthesized by using sea urchin-like α-MnO₂ precursors through solid-state in situ self-sacrificing conversion route. The as-prepared LiMn₂O₄ was assembled by many single-crystalline “thorns” of ca.10–20 nm in diameter and ca. 400–500 nm in length. Galvanostatic battery testing showed that sea urchin-like LiMn₂O₄ had an initial discharge capacity of 126.8 mAh/g at the rate of 0.2 C in the potential range between 3.0 and 4.5 V. More than 96.67 % of the initial discharge capacity was maintained for over 50 cycles. The improved electrochemical properties were attributed to the reduced particle size and enhanced electrical contacts by the materials. This particular sea urchin-like structured composite conceptually provides a new strategy for designing electrodes in energy storage applications.     

White-light-controlled resistance switching in TiO2/α-Fe2O3 composite nanorods array

White-light-controlled resistance switching in TiO₂/α-Fe₂O₃ composite nanorods array grown on fluorine-doped tin oxide substrate by hydrothermal process is investigated. The average length of TiO₂/α-Fe₂O₃ nanorods is about 3.5 μm, and the average diameter is about 250 nm. The sizes of the α-Fe₂O₃ particles are in the range of 30 ~ 70 nm. The current–voltage characteristics of the composite nanorods array show a good rectifying property and bipolar resistive-switching behavior, and the resistive-switching behavior can be regulated by white-light illumination at room temperature. This study is helpful for exploring the multifunctional materials and their applications in nonvolatile multistate memory devices.     

Optical properties of TiO2-MnO2 thin films prepared by electron-beam evaporation

The optical constants and thickness of TiO₂-MnO₂ films (with MnO₂ concentration of 0, 1, and 5%) prepared by electron-beam evaporation are determined. A considerable dependence of the optical properties of thin TiO₂ films on the manganese concentration is observed. It is found that thin films are indirect gap semiconductors with gap width E _g = 3.43 eV (TiO₂), 2.89 eV (TiO₂-MnO₂ (1%)), and 2.73 eV (TiO₂-MnO₂ (5%)).     

Hydrothermal synthesis of pure LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> from nanostructured MnO<Subscript>2</Subscript> precursors for aqueous hybrid supercapacitors

Pure LiMn₂O₄ samples with high crystallinity (LMO-1# and LMO-2#) were successfully synthesized by a facile hydrothermal method using δ-MnO₂ nanoflowers and α-MnO₂ nanowires as the precursors. The as-prepared samples were analyzed by XRD, SEM, and Brunauer-Emmett-Teller (BET), and their capacitive properties were investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge test. Two LiMn₂O₄ samples showed good capacitive behavior in aqueous hybrid supercapacitors. AC//LMO-1# and AC//LMO-2# delivered the initial specific capacitance of 45.4 and 40.7 F g^?1 in 1 M Li₂SO₄ electrolyte at a current density of 200 mA g^?1 in the potential range of 0～1.5 V, respectively. After 1000 cycles, the capacitance retention was 97.6% for AC//LMO-1# and 93.7% for AC//LMO-2#. Obviously, LMO-1# from δ-MnO₂ nanoflowers exhibited higher specific capacitance and better cycling performance than LMO-2#, so LMO-1# was more suitable as the positive electrode material in hybrid supercapacitors.     

A facile low temperature synthesis of TiO2 nanorods for high efficiency dye sensitized solar cells

Titania (TiO₂) nanorods have been synthesized with controlled size for dye-sensitized solar cells (DSSCs) via hydrothermal route at low hydrothermal temperature of 100 °C for 24 h. The titania nanorods were characterized using XRD, SEM, TEM/HRTEM, UV-vis Spectroscopy, FTIR and BET specific surface area (S _BET), as well as pore-size distribution by BJH. The results indicated that the bulk traps and the surface states within the TiO₂ nanorods films have enhanced the efficiency of DSSCs. The size of the titania nanorods was 6.7 nm in width and 22 nm in length. The high surface area can provide more sites for dye adsorption, while the fast photoelectron-transfer channel can enhance the photogenerated electron transfer to complete the circuit. The specific surface area S _BET was 77.14 m²?g^?1 at the synthesis conditions. However, the band gap energy of the obtained titania nanorods was 3.2 eV. The oriented nanorods with appropriate lengths are beneficial in improving the electron transport property and thus leading to the increase of photocurrent, together enhancing the power conversion efficiency. A nearly quantitative absorbed photon-to-electrical current conversion achieved upon excitation at wave length of 550 nm and the power efficiency was enhanced from 5.6 % for commercial TiO₂ nanoparticles Degussa (P25) cells to 7.2 % for TiO₂ nanorods cells under AM 1.5 illumination (100 mW?cm^?2). The TiO₂ cells performance was improved due to their high surface area, hierarchically mesoporous structures and fast electron-transfer rate compared with the Degussa (P25).     

Dependence of the selectivity of SnO2 nanorod gas sensors on functionalization materials

Effects of functionalization materials on the selectivity of SnO₂ nanorod gas sensors were examined by comparing the responses of SnO₂ one-dimensional nanostructures functionalized with CuO and Pd to ethanol and H₂S gases. The response of pristine SnO₂ nanorods to 500 ppm ethanol was similar to 100 ppm H₂S. CuO-functionalized SnO₂ nanorods showed a slightly stronger response to 100 ppm H₂S than to 500 ppm ethanol. In contrast, Pd-functionalized SnO₂ nanorods showed a considerably stronger response to 500 ppm ethanol than to 100 ppm H₂S. In other words, the H₂S selectivity of SnO₂ nanorods over ethanol is enhanced by functionalization with CuO, whereas the ethanol selectivity of SnO₂ nanorods over H₂S is enhanced by functionalization with Pd. This result shows that the selectivity of SnO₂ nanorods depends strongly on the functionalization material. The ethanol and H₂S gas sensing mechanisms of CuO- and Pd-functionalized SnO₂ nanorods are also discussed.     

Engineering performance of barristors by varying the thickness of WS2

We have investigated the performances of barristors with a graphene-tungsten disulfide (WS₂) junction by varying the thickness of WS₂ and gate oxide. On-current density (J_ON) and on- and off-current ratio (J_ON/J_OFF) increases, and sub-threshold swing (V_SS) decreases with the WS₂ thickness. Also, barristors with thicker WS₂ required less workfunction shift, to switch the barristors. Therefore, unlike the traditional devices, V_SS of barristor with gate dielectric 300 nm was smaller than that of 90 nm, when the former is fabricated with thicker WS₂ than the latter. Since materials properties of 2-dimensional semiconductors generally vary with their thickness, the thickness of 2D semiconductors could become a key parameter to engineer the performance of barristors with graphene and the 2D semiconductors.     

Ultrasonic synthesis of α-MnO2 nanorods: An efficient catalytic conversion of refractory pollutant,methylene blue

In this work, uniform α-MnO₂ nanorods were synthesized via a simple hydrothermal followed by ultrasonication method using ultrasonic bath (20 kHz, 100 W) without using any surfactant and template. The crystallographic phases and surface morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transition electron microscopy (TEM) analysis, respectively. Functional group identification and chemical states of α-MnO₂ nanorods were confirmed by Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The as-synthesized uniform nanorods of α-MnO₂ exhibit excellent catalytic conversion of toxic organic contaminant (methylene blue (MB)) in the presence of NaBH₄ as reductant. The α-MnO₂ exhibits excellent stability up to four repeated catalytic cycles with nearly 92% conversion. The kinetic rate constant (k), and turnover frequency (TOF) were 0.736 min⁻¹ and 0.02 mmol mg⁻¹ min⁻¹, respectively. In addition, the fast electron transfer mechanism were investigated and discussed. These results open a new avenue for developing various metal oxide catalysts, which are expected to be very useful catalytic conversions.     

Transport phenomena in superionic Na<Subscript><Emphasis Type="Italic">х</Emphasis></Subscript>Cu<Subscript>2 − <Emphasis Type="Italic">х</Emphasis></Subscript>S (<Emphasis Type="Italic">х</Emphasis> = 0.05; 0.1; 0.15; 0.2) compounds

The electronic and ionic conductivity, the electronic and ionic Seebeck coefficients, and the thermal conductivity of Na _x Cu_2 ? x S (x = 0.05, 0.1, 0.15, 0.2) compounds were measured in the temperature range of 20–450 °С. The total cationic conductivity of Na_0.2Cu_1.8S is about 2 S/cm at 400 °С (the activation energy ≈ 0.21 eV). Over the studied compounds, the composition Na_0.2Cu_1.8S has the highest electronic conductivity (500–800 S/cm) in the temperature range from 20 to 300 °С, and the highest electronic Seebeck coefficient (about 0.2 mV/K) in the same temperature range is observed for Na_0.15Cu_1.85S composition; the electronic Seebeck coefficient increases abruptly above 300 °С for all compounds. The thermal conductivity of superionic Na_0.2Cu_1.8S is low, which causes high values of the dimensionless thermoelectric figure of merit ZT from 0.4 to 1 at temperatures from 150 to 340 °С.     

First-principles study on the electronic and optical properties of Si and Al co-doped zinc oxide for solar cell devices

Electronic and optical properties of co-doped zinc oxide ZnO with silicon (Si) and aluminum (Al), in Zn_1?2x Si _x Al _x O (0 ≤ x ≤ 0.0625) original structure forms, are investigated by the first-principles calculations based on the density functional theory (DFT). The optical constants and dielectric functions are investigated with the full-potential linearized augmented plane wave (FP-LAPW) method and the generalized gradient approximation (GGA) by WIEN2k package. The complex dielectric functions, refractive index and band gap of the pure as well as doped and co-doped ZnO were investigated, which are in good agreement with the available experimental results for the undoped ZnO. Thus, the maximum optical transmittance of the co-doped ZnO of about 95 % was achieved; it is higher than that of pure ZnO. Thus, we showed for the Si–Al co-doped ZnO with x = 0.0315 that the optical transmittance can cover a larger range in the visible light region. In addition, an occurrence of important energy levels around Fermi levels was showed, which is mainly due to doping atoms that lead to an overlap between valence and conduction bands, and consequently to the significant conductor behavior of the Si–Al co-doped ZnO. The original Zn_1?2x Si _x Al _x O structure reveals promising optical and electronic properties, and it can be investigated as good candidates for practical uses as transparent and conducting electrodes in solar cell devices.     

Hierarchical nanostructured 3D flowerlike BiOX particles with excellent visible-light photocatalytic activity

BiOX (X = Cl, Br, and I) semiconductors were firstly prepared by a facile mixed solvent solvothermal route. Several characterization tools were employed to study the phase structures, morphologies, and optical properties of the samples. The in situ chemically mixed prepared BiOX particles with diameters 3.0–5.0 μm, fabricated by nanoplates in the thickness range of 5–18 nm, exhibited the highest visible-light photocatalytic activity among the as-prepared samples and Degussa P₂₅ for the degradation of Rhodamine B (RhB). This result can be due to the narrow bandgap, broad sunlight range, high electronic negativity, and efficient separation of photoinduced electron–hole pairs. Finally, a possible photocatalytic mechanism has been proposed.     

First-Principles Study of Pressure-Induced Phase Transition in CuGaO<Subscript>2</Subscript>

We have studied the structural, elastic, electronic properties, and pressure-induced phase transition of CuGaO₂ by using the plane-wave ultrasoft pseudopotential technique based on the first-principles density-functional theory (DFT). The obtained ground state properties of three phases were in agreement with previous works. The calculated enthalpy variations with pressure showed that the structural phase transition (β → 3R/2H) appeared at 65.5 ± 1 GPa. The changes in volume and band gap of β phase showed that there was a break between 30 and 40 GPa. The independent elastic constants of three phases were calculated. The 3R, 2H, and β phases were all mechanical stability and behaved in ductile manner under zero pressure.     

Designing of multiwalled carbon nanotubes reinforced low density polyethylene nanocomposites for suppression of electromagnetic radiation

High aspect ratio multi-walled carbon nanotubes (MWCNTs) reinforced low density polyethylene (LDPE) composites were prepared by solvent casting followed by compression molding technique. Electromagnetic interference (EMI) shielding effectiveness (SE) of these composites was investigated in the frequency range of 12.4?C18 GHz (Ku-band) for the first time. The experimental results indicate that the EMI-SE of these composites is sensitive to the MWCNT loading. The average value of EMI-SE reaches 22.4 dB for 10 wt% MWCNT-LDPE composites, indicating the usefulness of this material for EMI shielding in the Ku-band. The main reason for improved SE has been attributed to significant improvement in the electrical conductivity of the composites by 20 orders of magnitude, i.e., from 10^?20 for pure LDPE to 0.63 S/cm for MWCNT-LDPE, which is three order of magnitude higher than the previous reports for MWCNT-LDPE composites. Differential scanning calorimetry of the MWCNT-LDPE composites showed around 37% improvement in the crystalline contents over pure LDPE samples which resulted into enhanced thermal stability of the composites. The thermal decomposition temperature of LDPE is shifted by 40 °C on addition of 5 wt% MWCNT. The studies therefore show that these composite can be used as light weight, thermally stable EMI shielding, and antistatic material.     

Enhanced ethanol sensing properties of TiO2/ZnO core–shell nanorod sensors

TiO₂-core/ZnO-shell nanorods were synthesized using a two-step process: the synthesis of TiO₂ nanorods using a hydrothermal method followed by atomic layer deposition of ZnO. The mean diameter and length of the nanorods were ～300 nm and ～2.3 μm, respectively. The cores and shells of the nanorods were monoclinic-structured single-crystal TiO₂ and wurtzite-structured single-crystal ZnO, respectively. The multiple networked TiO₂-core/ZnO-shell nanorod sensors showed responses of 132–1054 % at ethanol (C₂H₅OH) concentrations ranging from 5 to 25 ppm at 150 ^°C. These responses were 1–5 times higher than those of the pristine TiO₂ nanorod sensors at the same C₂H₅OH concentration range. The substantial improvement in the response of the pristine TiO₂ nanorods to C₂H₅OH gas by their encapsulation with ZnO may be attributed to the enhanced absorption and dehydrogenation of ethanol. In addition, the enhanced sensor response of the core–shell nanorods can be attributed partly to changes in resistance due to both the surface depletion layer of each core–shell nanorod and the potential barriers built in the junctions caused by a combination of homointerfaces and heterointerfaces.