Electric field-assisted laser ablation fabrication and assembly of zinc oxide/carbon nanocomposites into hierarchical structures for supercapacitor electrodes.

One of the major challenges in the field of electrochemical energy storage device performance improvement is the development of suitable synthetic materials for electrodes that can provide high power and high energy density features combined with their long-term stability. Here, we have developed a novel two-step approach based on DC glow discharge plasma pre-treatment of a carbon cloth substrate followed by electric field-assisted laser ablation for the synthesis of ZnO/C nanocomposites in a liquid and their simultaneous assembly into hierarchically organized nanostructures onto the pre-processed carbon cloth to produce a supercapacitor electrode. To form such nanostructures, a processed carbon cloth was included in the electrical circuit as a cathode during laser ablation of zinc in water, while a zinc target served as an anode. A series of studies have been performed to explore the structure, morphology, composition and electrochemical characteristics of the synthesized ZnO/C nanocomposites. Application of the external field provided additional possibilities for tuning the particle morphology. The parameters of the obtained nanostructures were shown to depend on the direction of the applied electric field and liquid composition. SEM studies revealed a nanoflower-like morphology of the prepared nanomaterial having potential in supercapacitor applications due to a large surface area. The ZnO/C nanoflowers, deposited onto a carbon cloth substrate, were tested for energy storage by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) analysis. The results showed a pseudocapacitor behavior with a maximum specific capacitance of about 3045 F g-1 (at a scan rate of 1 mV s-1). These results demonstrate a promising storage efficiency of the synthesized ZnO/C nanocomposite as a material for supercapacitors.

Strain Sensing Coatings for Large Composite Structures Based on 2D MXene Nanoparticles.

Real-time strain monitoring of large composite structures such as wind turbine blades requires scalable, easily processable and lightweight sensors. In this study, a new type of strain-sensing coating based on 2D MXene nanoparticles was developed. A Ti3C2Tz MXene was prepared from Ti3AlC2 MAX phase using hydrochloric acid and lithium fluoride etching. Epoxy and glass fibre-reinforced composites were spray-coated using an MXene water solution. The morphology of the MXenes and the roughness of the substrate were characterised using optical microscopy and scanning electron microscopy. MXene coatings were first investigated under various ambient conditions. The coating experienced no significant change in electrical resistance due to temperature variation but was responsive to the 301-365 nm UV spectrum. In addition, the coating adhesion properties, electrical resistance stability over time and sensitivity to roughness were also analysed in this study. The electromechanical response of the MXene coating was investigated under tensile loading and cyclic loading conditions. The gauge factor at a strain of 4% was 10.88. After 21,650 loading cycles, the MXene coating experienced a 16.25% increase in permanent resistance, but the response to loading was more stable. This work provides novel findings on electrical resistance sensitivity to roughness and electromechanical behaviour under cyclic loading, necessary for further development of MXene-based nanocoatings. The advantages of MXene coatings for large composite structures are processability, scalability, lightweight and adhesion properties.

One-step synthesis and growth mechanism of nitrate intercalated ZnAl LDH conversion coatings on zinc.

An approach for the synthesis of ZnAl-NO3 LDH conversion coatings on zinc in an aqueous acidic Al(NO3)3/NaNO3 solution is demonstrated for the first time. The growth mechanism has been investigated using time resolved structural, microstructural and analytical methods. A LDH growth model involving both electrochemical and chemical processes is suggested.

Light-Induced Proton Pumping with a Semiconductor: Vision for Photoproton Lateral Separation and Robust Manipulation.

Energy-transfer reactions are the key for living open systems, biological chemical networking, and the development of life-inspired nanoscale machineries. It is a challenge to find simple reliable synthetic chemical networks providing a localization of the time-dependent flux of matter. In this paper, we look to photocatalytic reaction on TiO2 from different angles, focusing on proton generation and introducing a reliable, minimal-reagent-consuming, stable inorganic light-promoted proton pump. Localized illumination was applied to a TiO2 surface in solution for reversible spatially controlled "inorganic photoproton" isometric cycling, the lateral separation of water-splitting reactions. The proton flux is pumped during the irradiation of the surface of TiO2 and dynamically maintained at the irradiated surface area in the absence of any membrane or predetermined material structure. Moreover, we spatially predetermine a transient acidic pH value on the TiO2 surface in the irradiated area with the feedback-driven generation of a base as deactivator. Importantly we describe how to effectively monitor the spatial localization of the process by the in situ scanning ion-selective electrode technique (SIET) measurements for pH and the scanning vibrating electrode technique (SVET) for local photoelectrochemical studies without additional pH-sensitive dye markers. This work shows the great potential for time- and space-resolved water-splitting reactions for following the investigation of pH-stimulated processes in open systems with their flexible localization on a surface.

Light-Induced Water Splitting Causes High-Amplitude Oscillation of pH-Sensitive Layer-by-Layer Assemblies on TiO2.

We introduce a simple concept of a light induced pH change, followed by high amplitude manipulation of the mechanical properties of an adjacent polymer film. Irradiation of a titania surface is known to cause water splitting, and this can be used to reduce the environmental pH to pH 4. The mechanical modulus of an adjacent pH sensitive polymer film can thus be changed by more than an order of magnitude. The changes can be localized, maintained for hours and repeated without material destruction.

Photocatalytic Deposition of Hydroxyapatite onto a Titanium Dioxide Nanotubular Layer with Fine Tuning of Layer Nanoarchitecture.

A new effective method of photocatalytic deposition of hydroxyapatite (HA) onto semiconductor substrates is proposed. A highly ordered nanotubular TiO2 (TNT) layer formed on titanium via its anodization is chosen as the photoactive substrate. The method is based on photodecomposition of the phosphate anion precursor, triethylphosphate (TEP), on the semiconductor surface with the following reaction of formed phosphate anions with calcium cations presented in the solution. HA can be deposited only on irradiated areas, providing the possibility of photoresist-free HA patterning. It is shown that HA deposition can be controlled via pH, light intensity, and duration of the process. Energy-dispersive X-ray spectroscopy profile analysis and glow discharge optical emission spectroscopy of HA-modified TNT prove that HA deposits over the entire TNT depth. High biocompatibility of the surfaces is proven by protein adsorption and pre-osteoblast cell growth.

Photoelectrochemical and Raman characterization of In2O3 mesoporous films sensitized by CdS nanoparticles.

The method of successive ion layer adsorption and reaction was applied for the deposition of CdS nanoparticles onto a mesoporous In2O3 substrate. The filling of the nanopores in In2O3 films with CdS particles mainly occurs during the first 30 cycles of the SILAR deposition. The surface modification of In2O3 with CdS nanoparticles leads to the spectral sensitization of photoelectrochemical processes that manifests itself in a red shift of the long-wavelength edge in the photocurrent spectrum by 100-150 nm. Quantum-confinement effects lead to an increase of the bandgap from 2.49 to 2.68 eV when decreasing the number of SILAR cycles from 30 to 10. The spectral shift and the widening of the Raman line belonging to CdS evidences the lattice stress on the CdS/In2O3 interfaces and confirms the formation of a close contact between the nanoparticles.

Gelatin-templated mesoporous titania for photocatalytic air treatment and application in metal chalcogenide nanoparticle-sensitized solar cells.

Mesoporous titania as powders and thin films on ITO were prepared using gelatin as an available and non-expensive pore-forming agent. The mesoporous TiO2 manifested a much higher photocatalytic activity in the gas-phase air oxidation of ethanol and acetaldehyde than the commercial nanocrystalline TiO2 P25 (Degussa Corp.). The mesoporous ITO/TiO2 films exhibited 12-14% efficiency of photocurrent generation in aqueous Na2S electrolyte when illuminated by UV light. Deposition of CdS and PbS nanoparticles onto the surface of ITO/TiO2 further increases the photocurrent yields and expands the light sensitivity range of the films to 500-520 nm (CdS) and to 650-700 nm (PbS).

Electrochemical observation of the photoinduced formation of alloyed ZnSe(S) nanocrystals.

Electrochemical studies of thiol-capped ZnSe nanocrystals in aqueous solution have demonstrated several distinct oxidation and reduction peaks in the voltammograms, with the peak positions being dependent on the size of the nanocrystals and their photoluminescence quantum efficiency. The evolution of the specific features in the cyclic voltammetric curves of ZnSe NCs as a function of their photochemical treatment is studied. The interpretation of the results based on the approaches previously developed for CdTe NCs is found to be in good correlation with the proposed mechanism of the ZnSe NCs phototreatment, i.e., the formation of a sulfur-enriched surface shell. By this, cyclic voltammetry has been demonstrated to be a powerful method for probing surface states of semiconductor NCs as well as for monitoring the evolution of these states during photochemical processing.

Semiconductor nanocrystals photosensitize C60 crystals.

Semiconductor nanocrystals (SCNCs) made of CdSe, CdTe, and InP are used to photosensitize needlelike C(60) crystals. The photocurrent is increased by up to 3 orders of magnitude as compared with C(60) crystals without SCNCs. The photocurrent spectrum can be tuned precisely by the SCNC size and material, rendering the SCNC-functionalized C(60) crystals an excellent material for spectrally tuneable photodetectors. We explain the increased photocurrent as a result of photoexcited electrons transferring from the SCNCs to the C(60) crystals and causing photoconductivity, while the complementary holes remain trapped in the SCNCs.

Size-dependent electrochemical behavior of thiol-capped CdTe nanocrystals in aqueous solution.

Electrochemical studies of thiol-capped CdTe nanocrystals in aqueous solution have demonstrated several distinct oxidation and reduction peaks in the voltammograms, with the peak positions being dependent on the size of the nanocrystals. While the size dependence of the reduction and one of the oxidation potentials can be attributed to altering the energetic band positions owing to the quantum size effect, an extraordinary behavior was found for the oxidation peak observed at less positive potentials. In contrast to a prediction based on the quantum size effect, this peak moves to more negative potentials as the nanocrystals' size decreases. Moreover, the contribution of the charge associated with this peak compared to the total charge passed during the nanocrystal oxidation correlates well with the photoluminescence (PL) efficiency of individual fractions of the CdTe nanocrystals. These experimental observations allow a peak to be assigned to the oxidation of Te-related surface traps. The intra-band-gap energy level assigned to these Te-related trap states shifts toward the top of the valence band as the nanocrystal size increases, thus allowing the higher photostability of the larger nanocrystals to be explained. At a certain nanocrystal size, the trap level can even move out of the band gap.