Effect of morphology on the photoelectrochemical performance of nanostructured Cu2O photocathodes.

Cu2O is a promising earth-abundant semiconductor photocathode for sunlight-driven water splitting. Characterization results are presented to show how the photocurrent density (Jph), onset potential (Eonset), band edges, carrier density (NA), and interfacial charge transfer resistance (Rct) are affected by the morphology and method used to deposit Cu2O on a copper foil. Mesoscopic and planar morphologies exhibit large differences in the values ofNAandRct. However, these differences are not observed to translate to other photocatalytic properties of Cu2O. Mesoscopic and planar morphologies exhibit similar bandgap (e.g.) and flat band potential (Efb) values of 1.93 ± 0.04 eV and 0.48 ± 0.06 eV respectively.Eonsetof 0.48 ± 0.04 eV obtained for these systems is close to theEfbindicating negligible water reduction overpotential. Electrochemically deposited planar Cu2O provides the highest photocurrent density of 5.0 mA cm-2at 0 V vs reversible hydrogen electrode (RHE) of all the morphologies studied. The photocurrent densities observed in this study are among the highest reported values for bare Cu2O photocathodes.

Mapping the surface potential, charge density and adhesion of cellulose nanocrystals using advanced scanning probe microscopy.

Cellulose nanocrystals (CNC) are the focus of significant attention in the broad area of sustainable technologies for possessing many desirable properties such as a large surface area, high strength and stiffness, outstanding colloidal stability, excellent biocompatibility and biodegradability, low weight and abundance in nature. Yet, a fundamental understanding of the micro- and nanoscale electrical charge distribution on nanocellulose still remains elusive. Here we present direct quantification and mapping of surface charges on CNCs at ambient condition using advanced surface probe microscopy techniques such as Kelvin probe force microscopy (KPFM), electrostatic force microscopy (EFM) and force-distance (F-D) curve measurements. We show by EFM measurements that the surface charge in the solid-state (as contrasted with liquid dispersions) present at ambient condition on CNCs provided by Innotech Alberta is intrinsically negative and the charge density is estimated to be 13 µC/cm2. These charges also result in CNCs having two times the adhesive force exhibited by SiO2 substrates in adhesion mapping studies. The origin of negative surface charge is likely due to the formation of CNCs through sulfuric acid hydrolysis where sulfate half esters groups remained on the surface (Johnston et al., 2018).

Consistently High Voc Values in p-i-n Type Perovskite Solar Cells Using Ni3+-Doped NiO Nanomesh as the Hole Transporting Layer.

Leading edge p-i-n type halide perovskite solar cells (PSCs) severely underperform n-i-p PSCs. p-i-n type PSCs that use PEDOT:PSS hole transport layers (HTLs) struggle to generate open-circuit photovoltage values higher than 1 V. NiO HTLs have shown greater promise in achieving high Voc values albeit inconsistently. In this report, a NiO nanomesh with Ni3+ defect grown by the hydrothermal method was used to obtain PSCs with Voc values that consistently exceeded 1.10 V (champion Voc = 1.14 V). A champion device photoconversion efficiency of 17.75% was observed. Density functional theory modeling was used to understand the interfacial properties of the NiO/perovskite interface. The PCE of PSCs constructed using the Ni3+-doped NiO nanomesh HTL was ∼34% higher than that of conventional compact NiO-based perovskite solar cells. A suite of characterization techniques such as transmission electron microscopy, field emission scanning electron microscopy, intensity-modulated photocurrent spectroscopy, intensity-modulated photovoltage spectroscopy, time-resolved photoluminescence, steady-state photoluminescence, and Kelvin probe force microscopy provided evidence of better film quality, enhanced charge transfer, and suppressed charge recombination in PSCs based on hydrothermally grown NiO nanostructures.

Heterojunctions of halogen-doped carbon nitride nanosheets and BiOI for sunlight-driven water-splitting.

A fluorine-doped, chlorine-intercalated carbon nitride (CNF-Cl) photocatalyst has been synthesized for simultaneous improvements in light harvesting capability along with suppression of charge recombination in bulk g-C3N4. The formation of heterojunctions of these CNF-Cl nanosheets with low bandgap, earth abundant bismuth oxyiodide (BiOI) was achieved, and the synthesized heterojunctions were tested as active photoanodes in photoelectrochemical water splitting experiments. BiOI/CNF-Cl heterojunctions exhibited extended light harvesting with a band-edge of 680 nm and generated photocurrent densities approaching 1.3 mA cm-2 under AM1.5 G one sun illumination. Scanning Kelvin probe force microscopy under optical bias showed a surface potential of 207 mV for the 50% BiOI/CNF-Cl nanocomposite, while pristine CNF-Cl and BiOI had surface photopotential values of 83 mV and 98 mV, respectively, which in turn, provided direct evidence of superior charge separation in the heterojunction blends. Enhanced charge carrier separation and improved light harvesting capability in BiOI/CNF-Cl hybrids were found to be the dominant factors in increased photocurrent, compared to the pristine constituent materials.

C3N5: A Low Bandgap Semiconductor Containing an Azo-Linked Carbon Nitride Framework for Photocatalytic, Photovoltaic and Adsorbent Applications.

Modification of carbon nitride based polymeric 2D materials for tailoring their optical, electronic and chemical properties for various applications has gained significant interest. The present report demonstrates the synthesis of a novel modified carbon nitride framework with a remarkable 3:5 C:N stoichiometry (C3N5) and an electronic bandgap of 1.76 eV, by thermal deammoniation of the melem hydrazine precursor. Characterization revealed that in the C3N5 polymer, two s-heptazine units are bridged together with azo linkage, which constitutes an entirely new and different bonding fashion from g-C3N4 where three heptazine units are linked together with tertiary nitrogen. Extended conjugation due to overlap of azo nitrogens and increased electron density on heptazine nucleus due to the aromatic π network of heptazine units lead to an upward shift of the valence band maximum resulting in bandgap reduction down to 1.76 eV. XRD, He-ion imaging, HR-TEM, EELS, PL, fluorescence lifetime imaging, Raman, FTIR, TGA, KPFM, XPS, NMR and EPR clearly show that the properties of C3N5 are distinct from pristine carbon nitride (g-C3N4). When used as an electron transport layer (ETL) in MAPbBr3 based halide perovskite solar cells, C3N5 outperformed g-C3N4, in particular generating an open circuit photovoltage as high as 1.3 V, while C3N5 blended with MA xFA1- xPb(I0.85Br0.15)3 perovskite active layer achieved a photoconversion efficiency (PCE) up to 16.7%. C3N5 was also shown to be an effective visible light sensitizer for TiO2 photoanodes in photoelectrochemical water splitting. Because of its electron-rich character, the C3N5 material displayed instantaneous adsorption of methylene blue from aqueous solution reaching complete equilibrium within 10 min, which is significantly faster than pristine g-C3N4 and other carbon based materials. C3N5 coupled with plasmonic silver nanocubes promotes plasmon-exciton coinduced surface catalytic reactions reaching completion at much low laser intensity (1.0 mW) than g-C3N4, which showed sluggish performance even at high laser power (10.0 mW). The relatively narrow bandgap and 2D structure of C3N5 make it an interesting air-stable and temperature-resistant semiconductor for optoelectronic applications while its electron-rich character and intrasheet cavity make it an attractive supramolecular adsorbent for environmental applications.

Enhanced charge separation in g-C3N4-BiOI heterostructures for visible light driven photoelectrochemical water splitting.

Heterojunctions of the low bandgap semiconductor bismuth oxyiodide (BiOI) with bulk multilayered graphitic carbon nitride (g-C3N4) and few layered graphitic carbon nitride sheets (g-C3N4-S) are synthesized and investigated as an active photoanode material for sunlight driven water splitting. HR-TEM and elemental mapping reveals formation of a unique heterostructure between BiOI platelets and the carbon nitride (g-C3N4 and g-C3N4-S) network that consisted of dendritic BiOI nanoplates surrounded by g-C3N4 sheets. The presence of BiOI in g-C3N4-S/BiOI and g-C3N4-S/BiOI nanocomposites extends the visible light absorption profile from 500 nm up to 650 nm. Due to excellent charge separation in g-C3N4/BiOI and g-C3N4-S/BiOI, evident from quenching of the carbon nitride photoluminescence (PL) and a decrease in the PL lifetime, a significant increase in photoelectrochemical performance is observed for both types of g-C3N4-BiOI heterojunctions. In comparison to heterojunctions of bulk g-C3N4 with BiOI, the nanocomposite consisting of few layered sheets of g-C3N4 and BiOI exhibits higher photocurrent density due to lower recombination in few layered sheets. A synergistic trap passivation and charge separation is found to occur in the g-C3N4-S/BiOI nanocomposite heterostructure which results in a higher photocurrent and a lower charge transfer resistance.

Behavior of α, ß tubulin in DMSO-containing electrolytes.

α, ß-tubulin is a cytoskeletal protein that forms cylindrical structures termed microtubules, which are crucial to the cell for a variety of roles. Microtubules are frequently modelled as one-dimensional bionanowires that act as ion transporters in the cell. In this work, we used dynamic light scattering (DLS) to measure the hydrodynamic diameter of tubulin in the presence of a polar aprotic co-solvent. We found that the hydrodynamic diameter increased with increasing DMSO volume fraction, almost doubling at 20% DMSO. To evaluate if this was due to an enlarged solvation shell, we performed reference interaction site model (RISM) simulations and found that the extent of solvation was unchanged. Using fluorescence microscopy, we then showed that tubulin was polymerization competent in the presence of colchicine, and thus inferred the presence of oligomers in the presence of DMSO, which points to its mechanism of action as a microtubule polymerization enhancing agent. Tubulin oligomers are known to form when microtubules depolymerize and are controversially implicated in microtubule polymerization. We show that DLS may be used to monitor early-state microtubule polymerization and is a viable alternative to fluorescence and electron microscopy-based methods. Our findings showing that DMSO causes tubulin oligomerization are thus of critical importance, both for creating bio-inspired nanotechnology and determining its biophysical roles in the cell.

Vapor growth of binary and ternary phosphorus-based semiconductors into TiO2 nanotube arrays and application in visible light driven water splitting.

We report successful synthesis of low band gap inorganic polyphosphide and TiO2 heterostructures with the aid of short-way transport reactions. Binary and ternary polyphosphides (NaP7, SnIP, and (CuI)3P12) were successfully reacted and deposited into electrochemically fabricated TiO2 nanotubes. Employing vapor phase reaction deposition, the cavities of 100 µm long TiO2 nanotubes were infiltrated; approximately 50% of the nanotube arrays were estimated to be infiltrated in the case of NaP7. Intensive characterization of the hybrid materials with techniques including SEM, FIB, HR-TEM, Raman spectroscopy, XRD, and XPS proved the successful vapor phase deposition and synthesis of the substances on and inside the nanotubes. The polyphosphide@TiO2 hybrids exhibited superior water splitting performance compared to pristine materials and were found to be more active at higher wavelengths. SnIP@TiO2 emerged to be the most active among the polyphosphide@TiO2 materials. The improved photocatalytic performance might be due to Fermi level re-alignment and a lower charge transfer resistance which facilitated better charge separation from inorganic phosphides to TiO2.

Resistance of Superhydrophobic Surface-Functionalized TiO2 Nanotubes to Corrosion and Intense Cavitation.

The availability of robust superhydrophobic materials with the ability to withstand harsh environments are in high demand for many applications. In this study, we have presented a simple method to fabricate superhydrophobic materials from TiO2 nanotube arrays (TNTAs) and investigated the resilience of the materials when they are subjected to harsh conditions such as intense cavitation upon ultrasonication, corrosion in saline water, water-jet impact, and abrasion. The TNTAs were prepared by anodization of Ti foil in buffered aqueous electrolyte containing fluoride ions. The hydrophilic TNTAs were functionalized with octadecylphosphonic acid (ODPA) or 1H, 1H', 2H, 2H'-perfluorodecyl phosphonic acid (PFDPA) to form a self-assembled monolayer on the TNTA surface to produce superhydrophobic ODPA@TNTA or PFDPA@TNTA surfaces. The superhydrophobic ODPA@TNTA and PFDPA@TNTA have contact angles of 156.0° ± 1.5° and 168° ± 1.5°, and contact angle hysteresis of 3.0° and 0.8°, respectively. The superhydrophobic ODPA@TNTA and PFDPA@TNTA were subjected to ultrasonication, corrosion in saline water, and water-jet impact and abrasion, and the resilience of the systems was characterized by electrochemical impedance spectroscopy (EIS), contact angle (CA) measurements, diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), and field-emission scanning electron microscopy (FESEM). The results presented here show that superhydrophobic ODPA@TNTA and PFDPA@TNTA are robust and resilient under the harsh conditions studied in this work, and indicate the potential of these materials to be deployed in practical applications.

Ultraviolet sensing using a TiO2 nanotube integrated high resolution planar microwave resonator device.

This paper presents a unique integrated UV light sensing concept and introduces a device with a detection limit of 1.96 nW cm-2. The combination of a high quality factor, a microwave planar resonator (Q ∼ 50 000) with a semiconducting nanomaterial enables a revolutionary potential paradigm for photodetection of low light intensities and small form factors. The presenting device employs a high-resolution microwave microstrip resonator as the signal transducer to convert the variant dielectric properties (permittivity and conductivity) of the nanotube membrane into electrical signals such as the resonant frequency, quality factor and resonant amplitude. The microwave resonator has an active feedback loop to improve the initial quality factor of the resonator from 200 to 50 000 and leads to boosting of the sensing resolution by orders of magnitude. Anatase TiO2 nanotubes are assembled on the surface of the microwave resonator. Upon exposure to UV light, electron-hole pair generation, trapping and recombination in the nanotubes are exploited as a unique signature to quantify the UV light intensity. The change of dielectric properties of the nanotube membrane is monitored using the underlying active microwave resonator. The proposed concept enables the detection and monitoring of UV light at high resolution, with very small exposure power and integrated form factors.

Core-shell titanium dioxide-titanium nitride nanotube arrays with near-infrared plasmon resonances.

Titanium nitride (TiN) is a ceramic with high electrical conductivity which in nanoparticle form, exhibits localized surface plasmon resonances (LSPRs) in the visible region of the solar spectrum. The ceramic nature of TiN coupled with its dielectric loss factor being comparable to that of gold, render it attractive for CMOS polarizers, refractory plasmonics, surface-enhanced Raman scattering and a whole host of sensing applications. We report core-shell TiO2-TiN nanotube arrays exhibiting LSPR peaks in the range 775-830 nm achieved by a simple, solution-based, low cost, large area-compatible fabrication route that does not involve laser-writing or lithography. Self-organized, highly ordered TiO2 nanotube arrays were grown by electrochemical anodization of Ti thin films on fluorine-doped tin oxide-coated glass substrates and then conformally coated with a thin layer of TiN using atomic layer deposition. The effects of varying the TiN layer thickness and thermal annealing on the LSPR profiles were also investigated. Modeling the TiO2-TiN core-shell nanotube structure using two different approaches, one employing effective medium approximations coupled with Fresnel coefficients, resulted in calculated optical spectra that closely matched the experimentally measured spectra. Modeling provided the insight that the observed near-infrared resonance was not collective in nature, and was mainly attributable to the longitudinal resonance of annular nanotube-like TiN particles redshifted due to the presence of the higher permittivity TiO2 matrix. The resulting TiO2-TiN core-shell nanotube structures also function as visible light responsive photocatalysts, as evidenced by their photoelectrochemical water-splitting performance under light emitting diode illumination using 400, 430 and 500 nm photons.

A review on photocatalytic CO2 reduction using perovskite oxide nanomaterials.

As the search for efficient catalysts for CO2 photoreduction continues, nanostructured perovskite oxides have emerged as a class of high-performance photocatalytic materials. The perovskite oxide candidates for CO2 photoreduction are primarily nanostructured forms of titanates, niobates, tantalates and cobaltates. These materials form the focus of this review article because they are much sought-after due to their nontoxic nature, adequate chemical stability, and tunable crystal structures, bandgaps and surface energies. As compared to conventional semiconductors and nanomaterial catalysts, nanostructured perovskite oxides also exhibit an extended optical-absorption edge, longer charge carrier lifetimes, and favorable band-alignment with respect to reduction potential of activated CO2 and reduction products of the same. While CO2 reduction product yields of several hundred µmol-1 h-1 are observed with many types of perovskite oxide nanomaterials in stand-alone forms, yield of such quantities are not common with semiconductor nanomaterials of other types. In this review, we present current state-of-the-art synthesis methods to form perovskite oxide nanomaterials, and procedures to engineer their bandgaps. This review also presents a comprehensive summary and discussion on crystal structures, defect distribution, morphologies and electronic properties of the perovskite oxides, and correlation of these properties to CO2 photoreduction performance. This review offers researchers key insights for developing advanced perovskite oxides in order to further improve the yields of CO2 reduction products.

Heterojunctions of mixed phase TiO2 nanotubes with Cu, CuPt, and Pt nanoparticles: interfacial band alignment and visible light photoelectrochemical activity.

Anodically formed, vertically oriented, self-organized cylindrical TiO2 nanotube arrays composed of the anatase phase undergo an interesting morphological and phase transition upon flame annealing to square-shaped nanotubes composed of both anatase and rutile phases. This is the first report on heterojunctions consisting of metal nanoparticles (NPs) deposited on square-shaped TiO2 nanotube arrays (STNAs) with mixed rutile and anatase phase content. A simple photochemical deposition process was used to form Cu, CuPt, and Pt NPs on the STNAs, and an enhancement in the visible light photoelectrochemical water splitting performance for the NP-decorated STNAs was observed over the bare STNAs. Under narrow band illumination by visible photons at 410 nm and 505 nm, Cu NP-decorated STNAs performed the best, producing photocurrents 80% higher and 50 times higher than bare STNAs, respectively. Probing the energy level structure at the NP-STNA interface using ultraviolet photoelectron spectroscopy revealed Schottky barrier formation in the NP-decorated STNAs, which assists in separating the photogenerated charge carriers, as also confirmed by longer charge carrier lifetimes in NP-decorated STNAs. While all the NP-decorated STNAs showed enhanced visible light absorption compared to the bare STNAs, only the Cu NPs exhibited a clear plasmonic behavior with an extinction cross section that peaked at 550 nm.

Response to Alternating Electric Fields of Tubulin Dimers and Microtubule Ensembles in Electrolytic Solutions.

Microtubules (MTs), which are cylindrical protein filaments that play crucial roles in eukaryotic cell functions, have been implicated in electrical signalling as biological nanowires. We report on the small-signal AC ("alternating current") conductance of electrolytic solutions containing MTs and tubulin dimers, using a microelectrode system. We find that MTs (212 nM tubulin) in a 20-fold diluted BRB80 electrolyte increase solution conductance by 23% at 100 kHz, and this effect is directly proportional to the concentration of MTs in solution. The frequency response of MT-containing electrolytes exhibits a concentration-independent peak in the conductance spectrum at 111 kHz (503 kHz FWHM that decreases linearly with MT concentration), which appears to be an intrinsic property of MT ensembles in aqueous environments. Conversely, tubulin dimers (42 nM) decrease solution conductance by 5% at 100 kHz under similar conditions. We attribute these effects primarily to changes in the mobility of ionic species due to counter-ion condensation effects, and changes in the solvent structure and solvation dynamics. These results provide insight into MTs' ability to modulate the conductance of aqueous electrolytes, which in turn, has significant implications for biological information processing, especially in neurons, and for intracellular electrical communication in general.

Optical anisotropy in vertically oriented TiO2 nanotube arrays.

Nanofabricated optically anisotropic uniaxial thin films with deep submicron feature sizes are emerging as potential platforms for low-loss all-dielectric metamaterials, and for Dyakonov surface wave-based subwavelength optical confinement and guiding at interfaces with isotropic media. In this context, we investigate the optical properties of one such uniaxial platform, namely self-organized titania nanotube arrays (TNTAs) grown by the bottom-up nanofabrication process of electrochemical anodization on silicon wafer substrates, and subsequently annealed at different temperatures, i.e. 500 °C and 750 °C. We performed detailed quantitative analysis of the structure of the TNTAs using x-ray diffraction and Raman spectroscopy, which revealed a measurable phonon confinement in TNTAs annealed at 500 °C. Variable angle spectroscopic ellipsometry was used to investigate the optical anisotropy in two kinds of TNTAs-those constituted by anatase-phase and those containing a mixture of anatase and rutile phases. Both kinds of TNTAs were found to have positive birefringence (Δn) exceeding 0.06 in the spectral region of interest while mixed phase TNTAs exhibited Δn as high as 0.15. The experimentally measured anisotropy in the refractive index of the TNTAs was compared with the predictions of two different effective medium approximations incorporating the uniaxial geometry. The measured value of Δn for TNTAs exceeded that of bulk anatase single crystals, indicating the potential of nanostructured dielectrics to outperform dielectric crystals of the same material with respect to the magnitude of the achievable directional refractive index contrast.

Halide perovskite solar cells using monocrystalline TiO2 nanorod arrays as electron transport layers: impact of nanorod morphology.

This is the first report of a 17.6% champion efficiency solar cell architecture comprising monocrystalline TiO2 nanorods (TNRs) coupled with perovskite, and formed using facile solution processing without non-routine surface conditioning. Vertically oriented TNR ensembles are desirable as electron transporting layers (ETLs) in halide perovskite solar cells (HPSCs) because of potential advantages such as vectorial electron percolation pathways to balance the longer hole diffusion lengths in certain halide perovskite semiconductors, ease of incorporating nanophotonic enhancements, and optimization between a high contact surface area for charge transfer (good) versus high interfacial recombination (bad). These advantages arise from the tunable morphology of hydrothermally grown rutile TNRs, which is a strong function of the growth conditions. Fluorescence lifetime imaging microscopy of the HPSCs demonstrated a stronger quenching of the perovskite PL when using TNRs as compared to mesoporous/compact TiO2 thin films. Due to increased interfacial contact area between the ETL and perovskite with easier pore filling, charge separation efficiency is dramatically enhanced. Additionally, solid-state impedance spectroscopy results strongly suggested the suppression of interfacial charge recombination between TNRs and perovskite layer, compared to other ETLs. The optimal ETL morphology in this study was found to consist of an array of TNRs ∼300 nm in length and ∼40 nm in width. This work highlights the potential of TNR ETLs to achieve high performance solution-processed HPSCs.

Reduced Ensemble Plasmon Line Widths and Enhanced Two-Photon Luminescence in Anodically Formed High Surface Area Au-TiO2 3D Nanocomposites.

Localized surface plasmon resonances (LSPR) in TiO2 nanorod and nanotube arrays decorated by gold nanoparticles can be exploited to improve photocatalytic activity, enhance nonlinear optical coefficients, and increase light harvesting in solar cells. However, the LSPR typically has a low quality factor, and the resonance is often obscured by the Urbach tail of the TiO2 band gap absorption. Attempts to increase the LSPR extinction intensity by increasing the density of gold nanoparticles on the surface of the TiO2 nanostructures invariably produce peak broadening due to the effects of either agglomeration or polydispersity. We present a new class of hybrid nanostructures containing gold nanoparticles (NPs) partially embedded in nanoporous/nanotubular TiO2 by performing the anodization of cosputtered Ti-Au thin films containing a relatively high ratio of Au:Ti. Our method of anodizing thin film stacks containing alternate layers of Ti and TiAu results in very distinctive LSPR peaks with quality factors as high as 6.9 and ensemble line widths as small as 0.33 eV even in the presence of an Urbach tail. Unusual features in the anodization of such films are observed and explained, including oscillatory current transients and the observation of coherent heterointerfaces between the Au NPs and anatase TiO2. We further show that such a plasmonic NP-embedded nanotube structure dramatically outperforms a plasmonic NP-decorated anodic nanotube structure in terms of the extinction coefficient, and achieves a strongly enhanced two-photon fluorescence due to the high density of gold nanoparticles in the composite film and the plasmonic local field enhancement.

Effect of phosphonate monolayer adsorbate on the microwave photoresponse of TiO2 nanotube membranes mounted on a planar double ring resonator.

In this study, the effects of a phosphonate molecular monolayer adsorbed on the surface of a free-standing self-organized TiO2 nanotube membrane, on the microwave photoresponse of the membrane are presented. This phenomenon is monitored using planar microwave sensors. A double ring resonator is utilized to monitor the permittivity and conductivity variation on the monolayer coated membrane and the sensor environment separately. It is shown that the rise time and subsequent decay of the amplitude (A), resonance frequency (f 0) and quality factor (Q) of the resonator depend on the existence and the type of the monolayer coating the membrane. Three different monolayers of n-decylphosphonic acid (DPA), 1H, 1H', 2H, 2H'-perfluorodecyl phosphonic acid (PFDPA) and 16-phosphonohexadecanoic acid adsorbed on the titania nanotube membrane are investigated while monitoring their microwave properties during the illumination time period and in the relaxation period, which demonstrate different behavior in comparison to each other and to the bare nanotube membrane layer. The effect of humidity on the TiO2 nanotube membrane with and without different monolayers is also studied and the results demonstrate distinguishable microwave responses. While each of the monolayer-coated membranes exhibited an attenuation of the photo-induced change in A, f 0 and Q with respect to the bare membrane, PFDPA-coated membranes showed the smallest relative change in the monitored microwave parameters upon ultraviolet illumination and upon the introduction of different levels of humidity. These effects are explained on the basis of surface trap passivation by the monolayers as well as the hydrophobicity of the monolayers. Our work also shows how the interactions of self-assembled monolayers with charge carriers and surface states on metal oxides may be used to indirectly sense their presence through measurement of the microwave response.

Rutile phase n- and p-type anodic titania nanotube arrays with square-shaped pore morphologies.

Rutile-phase TiO2 nanotube arrays without broken walls were formed by annealing of anodically formed nanotubes in a propane flame at 650 °C and in air at 750 °C. An unusual morphological transformation was observed from the ellipsoidal pore-shapes of titania nanotubes grown in aqueous electrolyte to a square-shaped pore structure subsequent to the anneals. 750 °C annealed nanotubes were found to be lightly p-type, rare in TiO2.

Anodic Cu2S and CuS nanorod and nanowall arrays: preparation, properties and application in CO2 photoreduction.

Copper sulfide semiconductors made from earth-abundant elements have an optical absorption edge at ca. 1.2 eV, nearly ideal for solar energy harvesting. We report the growth and formation mechanism of vertically oriented arrays of copper sulfide nanostructures formed by electrochemical anodization. Key parameters that affect the morphology and phase of the nanostructures are type and strength of electrolyte, anodization voltage and duration. Cu2S and CuS nanostructures were obtained on both copper foil and copper-coated flexible Kapton substrates, and depending on the anodization parameters, consisted of vertically oriented arrays of nanowalls, nanoleafs or rods with branched nanodendrites. The anodization parameters also controlled the phase and stoichiometry of the nanostructures. p-type conduction for Cu2S nanostructures and n-type conduction for CuS nanostructures were revealed by admittance spectroscopy and Mott Schottky analysis. We also observed a weak, but nevertheless promising and previously unnoticed, photocatalytic action in copper sulfide nanorod and platelet arrays for the sunlight-driven conversion of CO2 into CH4. Under irradiation by AM 1.5G simulated sunlight at room temperature, a CH4 production rate as high as 38 µmol m(-2) h(-1) was obtained using the copper sulfide nanostructure arrays as stand-alone photocatalysts for CO2 photoreduction.