Modulating the interaction between gold and TiO2 nanowires for enhanced solar driven photoelectrocatalytic hydrogen generation.

The interaction strength of Au nanoparticles with pristine and nitrogen doped TiO2 nanowire surfaces was analysed using density functional theory and their significance in enhancing the solar driven photoelectrocatalytic properties was elucidated. In this article, we prepared 4-dimethylaminopyridine capped Au nanoparticle decorated TiO2 nanowire systems. The density functional theory calculations show {101} facets of TiO2 as the preferred phase for dimethylaminopyridine-Au nanoparticles anchoring with a binding energy of -8.282 kcal mol(-1). Besides, the interaction strength of Au nanoparticles was enhanced nearly four-fold (-35.559 kcal mol(-1)) at {101} facets via nitrogen doping, which indeed amplified the Au nanoparticle density on nitrided TiO2. The Au coated nitrogen doped TiO2 (N-TiO2-Au) hybrid electrodes show higher absorbance owing to the light scattering effect of Au nanoparticles. In addition, N-TiO2-Au hybrid electrodes block the charge leakage from the electrode to the electrolyte and thus reduce the charge recombination at the electrode/electrolyte interface. Despite the beneficial band narrowing effect of nitrogen in TiO2 on the electrochemical and visible light activity in N-TiO2-Au hybrid electrodes, it results in low photocurrent generation at higher Au NP loading (3.4 × 10(-7) M) due to light blocking the N-TiO2 surface. Strikingly, even with a ten-fold lower Au NP loading (0.34 × 10(-7) M), the synergistic effects of nitrogen doping and Au NPs on the N-TiO2-Au hybrid system yield high photocurrent compared to TiO2 and TiO2-Au electrodes. As a result, the N-TiO2-Au electrode produces nearly 270 µmol h(-1) cm(-2) hydrogen, which is nearly two-fold higher than the pristine TiO2 counterpart. The implications of these findings for the design of efficient hybrid photoelectrocatalytic electrodes are discussed.

Enhanced photocatalytic performance at a Au/N-TiO2 hollow nanowire array by a combination of light scattering and reduced recombination.

We demonstrate one-step gold nanoparticle (AuNP) coating and the surface nitridation of TiO2 nanowires (TiO2-NWs) to amplify visible-light photon reflection. The surface nitridation of TiO2-NW arrays maximizes the anchoring of AuNPs, and the subsequent reduction of the band gap energy from 3.26 eV to 2.69 eV affords visible-light activity. The finite-difference time-domain (FDTD) simulation method clearly exhibits the enhancement in the strengths of localized electric fields between AuNPs and the nanowires, which significantly improves the photocatalytic (PC) performance. Both nitridation and AuNP decoration of TiO2-NWs result in beneficial effects of high (e(-)/h(+)) pair separation through healing of the oxygen vacancies. The combined effect of harvesting visible-light photons and reducing recombination in Au/N-doped TiO2-NWs promotes the photocatalytic activity towards degradation of methyl orange to an unprecedented level, ∼4 fold (1.1 × 10(-2) min) more than does TiO2-NWs (2.9 × 10(-3) min(-1)). The proposed AuNP decoration of nitridated TiO2-NW surfaces can be applied to a wide range of n-type metal oxides for photoanodes in photocatalytic applications.

Simultaneous glucose sensing and biohydrogen evolution from direct photoelectrocatalytic glucose oxidation on robust Cu2O-TiO2 electrodes.

We report simultaneous photoelectrocatalytic (PEC) glucose sensing and biohydrogen generation for the first time from the direct PEC oxidation of glucose at multifunctional and robust Cu2O-TiO2 photocatalysts. Striking improvement of 30% in overall H2 gas evolution (∼122 µmol h(-1) cm(-2)) by photoholes assisted glucose oxidation opens a new platform in solar-driven PEC biohydrogen generation.

Successful demonstration of an efficient I(-)/(SeCN)2 redox mediator for dye-sensitized solar cells.

A new I(-)/(SeCN)(2) redox mediator has favorable properties for dye-sensitized solar cells (DSCs) such as less visible light absorption, higher ionic conductivity, and downward shift of redox potential than I(-)/I(3)(-). It was then applied for DSCs towards increasing energy conversion efficiency, giving a new potential for improving performance.

Size effect on the physical properties of CdS thin films prepared by integrated physical-chemical approach.

Using an integrated physical-chemical approach, nanocrystalline cadmium sulfide (CdS) thin films were prepared by evaporating chemically synthesized CdS nanorods. Both the CdS nanorods and nanocrystalline thin films exhibited hexagonal wurtzite structure. Chemically synthesized CdS nanorods of about 7 nm average diameter were flexible, frequently folded to have elliptical cage linked chain structures and aggregate to form nanorod bundles. The bandgap energy of the nanocrystalline CdS films suffered a blue shift of about 0.07 eV due to intermediate quantum confinement of charge carriers. The reaction atmosphere was found to have strong effects on the particle size control of the nanostructures. Room temperature photoluminescence (PL) spectra of the films revealed a broad emission at about 429 nm related to recombination of excitons and shallowly trapped electron-hole pairs, along with the near-band-edge emission. Influence of particle size and defects on the structural and optical properties of CdS nanorods and nanocrystalline thin films are discussed.

Nanocrystalline CdSe thin films of different morphologies in thermal evaporation process.

Cadmium selenide nanocrystalline thin films of quasi-spherical morphology are prepared by evaporating CdSe nanopowders on glass substrates. Slightly oval shaped CdSe particles of about 165 nm average size (in 2-D) could be assembled over glass substrates by controlling the film thickness. Morphologies like assembly of particles, interconnected particles with mosaic-like structures and thin films of smooth surfaces could be prepared simply by controlling film thickness. A mechanism for such morphological variations is proposed. Observed variation of band gap energy in the films is explained in terms of quantum confinement effect and substrate-film interface strain.

Single-step electrospun TiO2-Au hybrid electrodes for high selectivity photoelectrocatalytic glutathione bioanalysis.

Understanding the fundamentals of photoelectrocatalytic (PEC) biomolecular oxidation benefits the development of next-generation PEC biosensors. In this work, single-step electrospun titanium-di-oxide-gold (TiO2-Au) hybrid nanofibers (HNF) are reported as being a potential candidate for PEC glutathione (GSH) bioanalysis. The chemical environment of TiO2 and TiO2-Au HNFs were studied with X-ray photoelectron spectroscopy and found to have a strong electronic interaction between TiO2 and the Au nanoparticles (NPs). The PEC measurements revealed that the intramolecular backbone hydrogen bonding of GSH molecules predominantly contributes highly active Au-GSH bio-nano interfaces, which facilitate the PEC oxidation rate of GSH and thus enhance the photocurrent. Furthermore, the Au NPs present act as auxiliary electron transport channels resulting in enhanced charge collection at the external circuit. As a result, the TiO2-Au electrode generated a two-fold higher photocurrent density of ∼84.4 µA cm-2 in the presence of 0.5 mM GSH, where the pristine TiO2 NFs displayed only a negligible influence. Likewise, the TiO2-Au HNF electrode showed a higher sensitivity of 0.002 mM and a wide linear detection range between 0.022 mM and 0.7 mM, with a superior selectivity towards GSH bioanalysis over ascorbic acid and glucose at -0.33 V (versus silver/silver chloride) than that obtained with pristine TiO2. The implications of these findings towards the development of a next-generation PEC biosensor are discussed.

Pt-free solar driven photoelectrochemical hydrogen fuel generation using 1T MoS2 co-catalyst assembled CdS QDs/TiO2 photoelectrode.

The solar-to-hydrogen generation from the TiO2-CdS-ZnS-MoS2 (TCZM) heterointerface was demonstrated. We found that a Pt-free CdS quantum dot-sensitized TiO2 mesoporous electrode with a metallic-type 1T MoS2 co-catalyst resulted in 0.11 ml cm(-2) h(-1) H2 fuel generation in unassisted potential mode, which was strikingly improved to 1.47 ml cm(-2) h(-1) under 1 V applied potential.

Synergistic metal-metal oxide nanoparticles supported electrocatalytic graphene for improved photoelectrochemical glucose oxidation.

We report the fabrication of graphene-WO3-Au hybrid membranes and evaluate their photocatalytic activity towards glucose oxidase mediated enzymatic glucose oxidation. The dual-functionality of gold nanoparticles in the reinforcement of visible light activity of graphene-WO3 membranes and improving the catalytic activity of immobilized enzymes for unique photoelectrochemical sensing application is demonstrated. This work provides new insights into the fabrication of light-sensitive hybrid materials and facilitates their application in future.

Electrochemical and in vitro bioactivity of polypyrrole/ceramic nanocomposite coatings on 316L SS bio-implants.

The present investigation describes the versatile fabrication and characterization of a novel composite coating that consists of polypyrrole (PPy) and Nb2O5 nanoparticles. Integration of the two materials is achieved by electrochemical deposition on 316L stainless steel (SS) from an aqueous solution of oxalic acid containing pyrrole and Nb2O5 nanoparticles. Fourier transform infrared spectral (FTIR) and X-ray diffraction (XRD) studies revealed that the existence of Nb2O5 nanoparticles in PPy matrix with hexagonal structure. Surface morphological analysis showed that the presence of Nb2O5 nanoparticles strongly influenced the surface nature of the nanocomposite coated 316L SS. Micro hardness results revealed the enhanced mechanical properties of PPy nanocomposite coated 316L SS due to the addition of Nb2O5 nanoparticles. The electrochemical studies were carried out using cyclic polarization and electrochemical impedance spectroscopy (EIS) measurements. In order to evaluate the biocompatibility, contact angle measurements and in vitro characterization were performed in simulated body fluid (SBF) and on MG63 osteoblast cells. The results showed that the nanocomposite coatings exhibit superior biocompatibility and enhanced corrosion protection performance over 316L SS than pure PPy coatings.

Three dimensional-TiO(2) nanotube array photoanode architectures assembled on a thin hollow nanofibrous backbone and their performance in quantum dot-sensitized solar cells.

Facile synthesis of TiO2 nanotube branched (length ∼0.5 µm) thin hollow-nanofibers is reported. The hierarchical three dimensional photoanodes (H-TiO2-NFs) (only ∼1 µm thick) demonstrate their excellent candidature as photoanodes in QD-sensitized solar cells, exhibiting ∼3-fold higher energy conversion efficiency (η = 2.8%, Jsc = 8.8 mA cm(-2)) than that of the directly grown nanotube arrays on a transparent conducting oxide (TCO) substrate (η = 0.9%, Jsc = 2.5 mA cm(-2)).

N-Ion-implanted TiO2 photoanodes in quantum dot-sensitized solar cells.

Hierarchical nanostructured titanium dioxide (TiO(2)) clumps were fabricated using electrostatic spray with subsequent nitrogen-ion doping by an ion-implantation technique for improvement of energy conversion efficiency for quantum dot-sensitized solar cells (QDSCs). CdSe quantum dots were directly assembled on the produced N-ion-implanted TiO(2) photoanodes by chemical bath deposition, and their photovoltaic performance was evaluated in a polysulfide electrolyte with a Pt counter electrode. We found that the photovoltaic performance of TiO(2) electrodes was improved by nearly 145% upon N-ion implantation. The efficiency improvement seems to be due to (1) the enhancement of electron transport through the TiO(2) layer by inter-particle necking of primary TiO(2) particles and (2) an increase in the recombination resistance at TiO(2)/QD/electrolyte interfaces by healing the surface states or managing the oxygen vacancies upon N-ion doping. Therefore, N-ion-doped photoanodes offer a viable pathway to develop more efficient QD or dye-sensitized solar cells.

Efficient Performance of Electrostatic Spray-Deposited TiO2 Blocking Layers in Dye-Sensitized Solar Cells after Swift Heavy Ion Beam Irradiation.

A compact TiO2 layer (~1.1 µm) prepared by electrostatic spray deposition (ESD) and swift heavy ion beam (SHI) irradiation using oxygen ions onto a fluorinated tin oxide (FTO) conducting substrate showed enhancement of photovoltaic performance in dye-sensitized solar cells (DSSCs). The short circuit current density (Jsc = 12.2 mA cm(-2)) of DSSCs was found to increase significantly when an ESD technique was applied for fabrication of the TiO2 blocking layer, compared to a conventional spin-coated layer (Jsc = 8.9 mA cm(-2)). When SHI irradiation of oxygen ions of fluence 1 × 10(13) ions/cm(2) was carried out on the ESD TiO2, it was found that the energy conversion efficiency improved mainly due to the increase in open circuit voltage of DSSCs. This increased energy conversion efficiency seems to be associated with improved electronic energy transfer by increasing the densification of the blocking layer and improving the adhesion between the blocking layer and the FTO substrate. The adhesion results from instantaneous local melting of the TiO2 particles. An increase in the electron transport from the blocking layer may also retard the electron recombination process due to the oxidized species present in the electrolyte. These findings from novel treatments using ESD and SHI irradiation techniques may provide a new tool to improve the photovoltaic performance of DSSCs.

Synergistic catalytic effect of a composite (CoS/PEDOT:PSS) counter electrode on triiodide reduction in dye-sensitized solar cells.

Inorganic/organic nanocomposite counter electrodes comprised of sheetlike CoS nanoparticles dispersed in polystyrenesulfonate-doped poly(3,4-ethylenedioxythiophene (CoS/PEDOT:PSS) offer a synergistic effect on catalytic performance toward the reduction of triiodide for dye-sensitized solar cells (DSSCs), yielding 5.4% power conversion efficiency, which is comparable to that of the conventional platinum counter electrode (6.1%). The electrochemical impedance spectroscopy (EIS) and cyclic voltammetry measurements revealed that the composite counter electrodes exhibited better catalytic activity, fostering rate of triiodide reduction, than that of pristine PEDOT: PSS electrode. The simple preparation of composite (CoS/PEDOT:PSS) electrode at low temperature with improved electrocatalytic properties are feasible to apply in flexible substrates, which is at most urgency for developing novel counter electrodes for lightweight flexible solar cells.