TiO2 nanorods decorated Si nanowire hierarchical structures for UV light activated photocatalytic application.

Water remediation techniques like photolysis have recently piqued the interest of many researchers due to water contamination resulting from heavy industrialization and urbanization. In the current work, as-synthesized TiO2 nanorod decorated vertically aligned silicon nanowire (SiNW) leads to a hierarchical morphological structure formation. The photocatalytic nature of the fabricated SiNW/TiO2 nanoheterojunction is examined by the dye degradation of textile pollutants like methylene blue (MB), rhodamine B (RhB), and eosin B (EB). The catalytic dye degradation investigations revealed that 4 h hydrothermal synthesis of TiO2 on the surface of SiNW (ST4) exhibited excellent catalytic behaviour. In the presence of H2O2 and UV irradiation, the ST4 nanoheterostructure can degrade 98.89% of the model pollutant methylene blue (MB) in 15 min, demonstrating remarkable photocatalytic performance. The direct Z-scheme heterojunction exhibited by the SiNW/TiO2 structure facilitates a more efficient charge transfer mechanism with higher reducing and oxidizing ability leading to enhanced photocatalytic behaviour. The degradation pathway examined by LC-MS studies demonstrated the complete breakdown of the organic MB dye molecules ultimately mineralizing into CO2, H2O, and other inorganic substances. The photocatalyst ST4 exhibited excellent reusability and stability after multiple cycles of dye degradation enabling its use in practical water purification purposes.

Significant enhancement in the cold emission characteristics of chemically synthesized super-hydrophobic zinc oxide rods by nickel doping.

The current article presents a huge enhancement in the field emission characteristics of zinc oxide (ZnO) micro/nanorods by nickel doping. The synthesis of pure and nickel-doped zinc oxide (ZnO) micro/nanorods was done by a simple low-temperature chemical method. Both the as-prepared pure and doped samples were analyzed by X-ray diffraction and electron microscopy to confirm the proper phase formation and the developed microstructure. UV-vis transmittance spectra helped in determining the band gap of the samples. Fourier-Transform Infrared Spectroscopy (FTIR) spectra showed the different bonds present in the sample, whereas X-ray Photoelectron Spectroscopy (XPS) confirmed the presence of nickel in the doped sample. Photoluminescence (PL) spectra showed that after doping, the band-to-band transition was affected, whereas defect-induced transition had increased significantly. After the nickel doping, contact angle measurement revealed a significant decrease in the sample's surface energy, leading to a remarkably high water contact angle (within the superhydrophobic region). Simulation through ANSYS suggested that the doped sample has the potential to function as an efficient cold emitter, which was also verified experimentally. The cold emission characteristics of the doped sample showed a significant improvement, with the turn-on field (corresponding to J = 1 µA cm-2) reduced from 5.34 to 2.84 V µm-1. The enhancement factor for the doped sample reached 3426, approximately 1.5 times higher compared to pure ZnO. Efforts have been made to explain the results, given the favorable band bending as well as the increased number of effective emission sites.

Synthesis of different manganese tungstate nanostructures for enhanced charge-storage applications: theoretical support for experimental findings.

Manganese tungstate (MnWO4) has been widely studied over the past few years due to its outstanding magnetic, catalytic, and sensing features. However, the electrochemical properties of the morphology tuned MnWO4 nanoform is less explored in the literature. Herein, we report the synthesis of MnWO4 nanostructures of different aspect ratios by subtle tuning of the reaction temperature and reaction time. An immediate utility of the size-controlled nanostructures is their use as the electrode material for supercapacitors. The impact of various reaction parameters, namely the growth time and processing temperature, over the MnWO4 nanorods size was studied by different characterization techniques, such as X-ray diffraction, field emission scanning electron microscopy, and Raman spectroscopy. It was shown that all the samples showed considerably good charge-storage properties with the highest values of specific capacitance being 455.07 and 239.07 F g-1 at 2 mV s-1 and 1 A g-1, respectively. The corresponding sample further showed an appreciable capacitance retention of ∼94% even after 10 000 long charge-discharge cycles, indicating a high electrochemical stability of the electrode. Theoretical analysis using density functional theory predicted that the presence of electronic states near Fermi level and the enhanced quantum capacitance were the prime reasons behind the excellent charge-storage performance of the as-synthesized MnWO4.

Mechanism of Oxygen Reduction Reaction in Alkaline Medium on Nitrogen-Doped Graphyne and Graphdiyne Families: A First Principles Study.

Using extensive first principles protocols, a systematic investigation is performed to probe the oxygen reduction reaction (ORR) mechanism on nitrogen (N) doped graphynes (Gys, e. g. αGy, ßGy, γGy and 6,6,12Gy) and graphdiyne (Gdy) in alkaline medium. We considered both associative and dissociative pathways, as well as two distinct intermediate forks for each of them depending on the first protonation site(s). Following the dissociative approach, the activation energy to form an O2 dissociated configuration is found as a function of the distances migrated by the O atoms over the catalyst surface and the amount of charge transferred from the C atoms linked to N. N doped αGy and 6,6,12Gy emerged as the best electrocatalyst comparing both pathways having lowest overpotentials of 0.88 and 0.82 V, respectively. The rate-limiting steps for the two different intermediate routes are observed to be dependent on the first protonation site(s) and related to the desorption of the OH radical from the sp hybridized C atom site(s) linked to N. Hence, the OH adsorption energy is identified as a descriptor for the efficiency of the ORR for the considered systems. The stabilities of the ORR intermediates are further elaborated in terms of pH and electrode potential.

1D-2D hybrids as efficient optoelectronic materials: a study on graphitic carbon nitride nanosheets wrapped with zinc oxide rods.

Zinc oxide (ZnO) nanorods (NRs) wrapped with graphitic carbon nitride (GCN) nanosheet (NS) hybrids have been synthesized by a simple chemical process. The as-prepared samples are characterized by X-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy, Fourier transformed infrared spectroscopy, UV-Vis spectroscopy and photoluminescence spectroscopy. The images obtained from the transmission electron microscopic study and the existence of C-N stretching modes as observed from Fourier transform infrared spectroscopy confirm the successful attachment of GCN NSs onto the ZnO NRs. It is seen that hybrid samples show broad photoluminescence (PL) emission with enhanced defect related emission along with a quenching effect due to the charge transfer mechanism. The results have been explained by taking into consideration the three different types of electron transitions occurring within the type-II band structure of the hybrid samples. Moreover a study on the conductivity of the samples is carried out under dark conditions and also under ultraviolet (UV) light irradiation. It is observed that the hybrid samples show significantly improved conductivity under both dark and UV irradiated conditions. The absorbance of the samples in the UV range shows better conductivity under UV conditions as compared to dark conditions.

Graphene-Anchored p-Type CuBO2 Nanocrystals for a Transparent Cold Cathode.

CuBO2 nanostructures were synthesized by employing a low-cost hydrothermal technique to combine into the CuBO2-RGO nanocomposite for the first time using chemically prepared graphene sheets. The nanohybrid samples were characterized for structural information using X-ray diffraction (XRD) that revealed the proper crystalline phase formation of CuBO2 unaltered by composite formation with graphene. Raman spectroscopic studies were employed to confirm the presence of graphene. A morphological study with field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) suggested the proper wrapping of RGO sheets over CuBO2 nanocubes. Moreover, the close proximity of lattice planes of CuBO2 and RGO to each other was observed in high-resolution TEM studies that were correlated with the Raman spectroscopic studies. Finally, the samples were characterized to study the field emission (FE) properties of the same using a laboratory-made high-vacuum field-emission setup. Finite-element-based theoretical simulation studies were carried out to explain and compare the field emission properties with the experimental results. The FE properties of the composite samples were found to be tuned by the nature of wrapping the RGO sheets over the CuBO2 nanocubes, which was typically dependent upon the spiky morphology of the nanocubes.

Novel Quaternary Chalcogenide/Reduced Graphene Oxide-Based Asymmetric Supercapacitor with High Energy Density.

In this work we have synthesized quaternary chalcogenide Cu2NiSnS4 (QC) nanoparticles grown in situ on 2D reduced graphene oxide (rGO) for application as anode material of solid-state asymmetric supercapacitors (ASCs). Thorough characterization of the synthesized composite validates the proper phase, stoichiometry, and morphology. Detailed electrochemical study of the electrode materials and ASCs has been performed. The as-fabricated device delivers an exceptionally high areal capacitance (655.1 mF cm-2), which is much superior to that of commercial micro-supercapacitors. Furthermore, a remarkable volumetric capacitance of 16.38 F cm-3 is obtained at a current density of 5 mA cm-2 combined with a very high energy density of 5.68 mW h cm-3, which is comparable to that of commercially available lithium thin film batteries. The device retains 89.2% of the initial capacitance after running for 2000 cycles, suggesting its long-term capability. Consequently, the enhanced areal and volumetric capacitances combined with decent cycle stability and impressive energy density endow the uniquely decorated QC/rGO composite material as a promising candidate in the arena of energy storage devices. Moreover, Cu2NiSnS4 being a narrow band gap photovoltaic material, this work offers a novel protocol for the development of self-charging supercapacitors in the days to come.

TiO2 Nanowires/Poly(Methyl Methacrylate) Based Hybrid Photodetector: Improved Light Detection.

Hybrid photodetector with a maximum external quantum efficiency of ~3.08% in the UV region at 370 nm, was fabricated by spin-coated poly(methyl methacrylate) (PMMA) polymer onto glancing angle deposited (GLAD) vertically aligned TiO2 nanowire (NW) arrays. The TiO2 NWs/PMMA detector shows excellent rectification and constant 1.3 times photo-responsivity in the reverse bias condition from -1 V to -10 V. The photodiode possesses a low ideality factor of 5.1 as compared to bared TiO2 NWs device of 7.1. The hybrid device produces sharp turn-on of -0.8 s and turn-off transient of -0.9 s respectively.

Implications of boron doping on electrocatalytic activities of graphyne and graphdiyne families: a first principles study.

Dispersive force corrected density functional theory is used to map the oxygen reduction reaction (ORR) kinetics of six kinds of graphyne (Gy) and graphdiyne (Gdy) systems (namely αGy, ßGy, γGy, δGy, 6,6,12Gy, RGy and Gdy) with substitutional boron (B) atom doping. To this end, the most favorable sites for B doping of each structures are determined by comparing their formation energies and then the best configuration for di-oxygen (O2) adsorption is computed by analyzing the corresponding adsorption energies. Even though oxygen adsorption is found to be energetically favorable on all of these and all Gys and Gdy are found to distinctly favor the four electron pathways for ORR, a reaction scheme with monotonically exothermic ΔG is observed only for B doped RGy. Further computations performed by varying electrode potential indicated this monotonically exothermic nature of the ΔG of B doped RGy to persist in the range 0-0.22 V and also indicated the first (H(+) + e) transfer step to be the rate limiting step.

Band Gap Tailoring of TiO2 Nanowires by Nitrogen Doping Under N2/Ar Plasma Environment.

Glancing angle deposited TiO2 nanowires (NWs) were doped with nitrogen (N) using plasma-enhanced chemical vapour deposition technique, under the treatment of N2/Ar plasma. A red shift (- 0.51 eV) in the main band transition and oxygen defect related transition (-2.1 eV) was observed for the N doped TiO2 nanowires. The interstitial nitrogen introduces mid-gap levels N (2P) above the O (2P) in the TiO2 forbidden gap. The photoluminescence measurement revealed a small red shift of -7 nm of anatase band gap from N doped TiO2 nanowires due to radiative recombination of carriers from conduction band to the N (2P) trap state. The low frequency Raman peaks at 304 cm(-1) (acoustical phonons with LA mode), 618 cm(-1) (optical phonons with LO modes) and the high frequency peak at 832 cm(-1) was observed from Ti-O-N due to the partial replacement of oxygen molecules by nitrogen into TiO2, during the doping process.

A carbon fiber-ZnS nanocomposite for dual application as an efficient cold cathode as well as a luminescent anode for display technology.

In the current work we present a simple technique to develop a carbon nanofiber (CNF)/zinc sulfide (ZnS) composite material for excellent FED application. CNFs and ZnS microspheres were synthesized by following a simple thermal chemical vapor deposition and hydrothermal procedure, respectively. A rigorous chemical mixture of CNF and ZnS was prepared to produce the CNF-ZnS composite material. The cathodo-luminescence intensity of the composite improved immensely compared to pure ZnS, also the composite material showed better field emission than pure CNFs. For pure CNF the turn-on field was found to be 2.1 V µm(-1) whereas for the CNF-ZnS composite it reduced to a value of 1.72 V µm(-1). Altogether the composite happened to be an ideal element for both the anode and cathode of a FED system. Furthermore, simulation of our CNF-ZnS composite system using the finite element modeling method also ensured the betterment of field emission from CNF after surface attachment of ZnS nanoclusters.

Structural and optical properties of glancing angle deposited TiO2 nanowires array.

TiO2 nanowires (NWs) have been synthesized by glancing angle deposition technique using e-beam evaporator. The average length 490 nm and diameter 80 nm of NWs were examined by field emission-scanning electron microscopy. Transmission electron microscopy emphasized that the NWs were widely dispersed at the top. X-ray diffraction has been carried out on the TiO2 thin film (TF) and NW array. A small blue shift of 0.03 eV was observed in Photoluminescence (PL) main band emission for TiO2 NW as compared to TiO2 TF. The high temperature annealing at 980 degrees C partially removed the oxygen vacancy from the sample, which was investigated by PL and optical absorption measurements.

Electronic structure and optical properties of CuAlO2 under biaxial strain.

An ab initio calculation has been carried out to investigate the biaxial strain ( - 10.71% < ε < 9.13%) effect on elastic, electronic and optical properties of CuAlO(2). All the elastic constants (c(11), c(12), c(13), c(33)) except c(44) decrease (increase) during tensile (compressive) strain. The band gap is found to decrease in the presence of tensile as well as compressive strain. The relative decrease of the band gap is asymmetric with respect to the sign of the strain. Significant differences between the parallel and perpendicular components of the dielectric constant and the optical properties have been observed due to anisotropic crystal structure. It is further noticed that these properties are easily tunable by strain. Importantly, the collective oscillation of the valence electrons has been identified for light polarized perpendicular to the c-axis. From calculations, it is clear that the tensile strain can enhance the hole mobility as well as the transparency of CuAlO(2).

Flexible cold cathode with ultralow threshold field designed through wet chemical route.

A flexible cold cathode based on a uniform array of ZnO nanowires over carbon fabrics was designed via a simple wet chemical route. The structural parameters of the nanowires (i.e. length, diameter) as well as their arrangement over the carbon fibers were tailored by adjusting nutrient solution composition and growth duration. The optimized arrays of ZnO nanowires exhibit excellent electron emission performance with ultralow turn-on as well as threshold fields of 0.27 and 0.56 V µm(-1). This threshold field value is the lowest compared to any of the previous zinc-oxide-based cold cathodes realized through either chemical or vapor phase processes. In addition, the current density can reach an exceptionally high value of ∼ 11 mA cm(-2) at an applied electric field of only 0.8 V µm(-1). Flexible electronic devices based on a field emitter cold cathode may thus be realized through chemical processing at low budget but having high efficiency.

Fluorinated diamond like carbon as an electron field emission material.

Fluorinated DLC films were deposited via plasma enhanced chemical vapor deposition technique on glass and silicon substrates. The precursor gas used was acetylene and for fluorine incorporation hydrofluoric acid dissolved in methanol was used. The at.% of fluorine in the films was varied from 0% to 15.3% as measured from energy dispersive X-ray analysis. The chemical binding was investigated by XPS studies. AFM studies showed that the increase of surface roughness with fluorine percentage. We have studied electron field emission from F:DLC thin films for a fixed anode-sample separation of 100 microm for different F at.% in the films. The threshold field was found to vary from 8.5 to 2.9 V/microm with a variation of fluorine at.% in the films 0% to 15.3%. The threshold field and field enhancement factor are calculated and we have tried to explain the emission mechanism there from. It was found that the threshold field and effective emission barrier were reduced by F doping than undoped DLC.

Enhanced p-type conductivity and band gap narrowing in heavily Al doped NiO thin films deposited by RF magnetron sputtering.

Stoichiometric NiO, a Mott-Hubbard insulator at room temperature, shows p-type electrical conduction due to the introduction of Ni(2+) vacancies (V(Ni)('')) and self-doping of Ni(3+) ions in the presence of excess oxygen. The electrical conductivity of this important material is low and not sufficient for active device fabrication. Al doped NiO thin films were synthesized by radio frequency (RF) magnetron sputtering on glass substrates at a substrate temperature of 250 °C in an oxygen + argon atmosphere in order to enhance the p-type electrical conductivity. X-ray diffraction studies confirmed the correct phase formation and also oriented growth of NiO thin films. Al doping was confirmed by x-ray photoelectron spectroscopic studies. The structural, electrical and optical properties of the films were investigated as a function of Al doping (0-4 wt%) in the target. The room temperature electrical conductivity increased from 0.01-0.32 S cm (-1) for 0-4% Al doping. With increasing Al doping, above the Mott critical carrier density, energy band gap shrinkage was observed. This was explained by the shift of the band edges due to the existence of exchange and correlation energies amongst the electron-electron and hole-hole systems and also by the interaction between the impurity quasi-particle system.

CdS nanoparticles grown in a polymer matrix by chemical bath deposition.

Nanocrystallites of CdS have been grown by chemical bath deposition within the pores of poly(vinyl alcohol) (PVA) on glass and Si substrates. The CdS-PVA composite films are transparent in the visible region. XRD and TEM diffraction patterns confirmed the nanocrystalline CdS phase formation. TEM study of the film revealed the manifestation of nano CdS phase formation and the average particles size was varied in the range 5-12 nm. UV-vis spectrophotometric measurement showed high transparency (nearly 80% in the wavelength range 550-900 nm) of the films with a direct allowed band gap lying in the range 2.64-3.25 eV. Particle sizes have also been calculated from the shift of band gap with respect to that of bulk value and were found to be in the range 3.3-6.44 nm. The high dielectric constant (lies in the range 120-250 at high frequency) of PVA/CdS nanocomposite compared to that of pure PVA (-28) has been observed. The dielectric constant decreases with increase of dispersibility of the CdS nanoparticles within PVA. The nanocrystalline PVA/CdS thin films have also showed field emission properties with a turn-on field of approximately 6.6 V/microm, whereas only PVA thin film and bulk CdS on PVA have shown no field emission.