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We investigate the optical properties of polycrystalline diamond membranes containing silicon-vacancy (SiV) color centers in combination with other nano-analytical techniques. We analyze the correlation between the Raman signal, the SiV emission, and the background luminescence in the crystalline grains and in the grain boundaries, identifying conditions for the addressability of single SiV centers. Moreover, we perform a scanning transmission electron microscopy (STEM) analysis, which associates the microscopic structure of the membranes and the evolution of the diamond crystal along the growth direction with the photoluminescence properties, as well as a time-of-flight secondary ion mass spectrometry (ToF-SIMS) to address the distribution of silicon in implanted and un-implanted membranes. The results of the STEM and ToF-SIMS studies are consistent with the outcome of the optical measurements and provide useful insight into the preparation of polycrystalline samples for quantum nano-optics., Comment: 21 pages, 8 figures

Au nanoparticles at the TiO$_2$ surface can enhance the photocatalytic H$_2$ generation performances owing to their electron transfer co-catalytic ability. Key to maximize the co-catalytic effect is a fine control over Au nanoparticle size and placement on the photocatalyst, in relation to parameters such as the TiO$_2$ morphology, illumination wavelength and pathway, and light penetration depth in the photocatalyst. Here we present an approach for site-selective intrinsic-decoration of anodic TiO$_2$ nanotubes (TNs) with Au nanoparticles: we produce, by Ti and Au co-sputtering, Ti-Au alloy layers that feature compositional gradients across their thickness; these layers, when anodized under self-ordering electrochemical conditions, can form Au-decorated TNs where the Au nanoparticle density and placement vary according to the Au concentration profile in the metal alloy substrates. Our results suggest that, the Au co-catalyst placement strongly affects the photocatalytic H$_2$ evolution performance of the TNs layers. We demonstrate that, when growing Au-decorated TNs, the use of Ti-Au substrates with a suitable Au compositional gradient can lead to higher H$_2$ evolution rates compared to TNs classically grown with a homogenous co-catalyst decoration. As a side effect, a proper placement of the co-catalyst nanoparticles allows for reducing the amount of noble metal without dumping the H$_2$ evolution activity.

Self-standing TiO$_2$ nanotube layers in the form of membranes are fabricated by self-organizing anodization of Ti metal and a potential shock technique. The membranes were then decorated by sputtering different Pt amounts i) only at the top, ii) only at the bottom or iii) at both top and bottom of the tube layers. The Pt-decorated membranes are transferred either in tube top up or in tube top down configuration onto FTO slides and investigated after crystallization as photocatalysts for H$_2$ generation using either front or back-side light irradiation. Double-side Pt-decoration of the tube membranes leads to higher H$_2$ generation rates (independent of tube and light irradiation configuration) compared to membranes decorated at only one side with similar overall Pt amounts. The results suggest that this effect is not ascribed to the overall amount of Pt cocatalyst as such but rather to its distribution at both tube extremities. This leads to optimized light absorption and electron diffusion/transfer dynamics: the central part of the membranes act as light harvesting zone and electrons therein generated can diffuse towards the Pt/TiO$_2$ active zones (tube extremities) where they can react with the environment and generate H$_2$ gas.

In present work, we report on the use of organized TiO$_2$ nanotube layers with a regular intertube spacing for the growth of highly defined $\alpha$-Fe$_2$O$_3$ nano-needles in the interspace. These $\alpha$-Fe$_2$O$_3$ decorated TiO$_2$ NTs are then explored for Li-ion battery applications and compared to classic close-packed NTs that are both decorated with various amounts of nanoscale $\alpha$-Fe$_2$O$_3$. We show that nanotubes with tube-to-tube spacing allow a uniform decoration of individual nanotubes with regular arrangements of hematite nano-needles. The tube spacing also facilitates the electrolyte penetration as well as yields better ion diffusion. While bare close-packed NTs show higher capacitance, e.g., 71 $\mu$Ah cm-2 than bare spaced NTs with e.g., 54 $\mu$Ah cm-2, the hierarchical decoration with secondary metal oxide, $\alpha$-Fe$_2$O$_3$, remarkably enhances the Li-ion battery performance. Namely, spaced nanotubes with $\alpha$-Fe$_2$O$_3$ decoration have an areal capacitance of 477 $\mu$Ah cm-2, i.e., show up to nearly ~8 times higher capacitance. However, the areal capacitance of close-packed NTs with $\alpha$-Fe$_2$O$_3$ decoration saturates at 208 $\mu$Ah cm-2, i.e., is limited to ~3 times increase.

In this study, we investigate noble metal free photocatalytic water splitting on natural anatase single crystal facets and on wafer slices of the [001] plane before and after these surfaces have been modified by high pressure hydrogenation (HPH) and hydrogen ion-implantation. We find that on the natural, intact low index planes photocatalytic H$_2$ evolution (in absence of noble metal co-catalyst) can only be achieved when the hydrogenation treatment is accompanied by the introduction of crystal damage, such as simple scratching, miscut in the wafer or by implantation damage. X-ray reflectivity (XRR), Raman, and optical reflection measurements show that plain hydrogenation leads to a ~ 1 nm thick black titania surface layer without activity, while a colorless, density modified and ~ 7 nm thick layer with broken crystal symmetry is present in the ion implanted surface. These results demonstrate that i) the H-treatment of an intact anatase surface needs to be combined with defect formation for catalytic activation, and ii) activation does not necessarily coincide with the presence of black color.

Solar driven photoelectrochemical water splitting (PEC-WS) using semiconductor photoelectrodes represents a promising approach for a sustainable and environmentally friendly production of renewable energy vectors and fuel sources, such as dihydrogen (H2). In this context, titanium dioxide (TiO$_2$) and iron oxide (hematite, $\alpha$-Fe$_2$O$_3$) are among the most investigated candidates as photoanode materials, mainly owing to their resistance to photocorrosion, non-toxicity, natural abundance, and low production cost. Major drawbacks are, however, an inherently low electrical conductivity and a limited hole diffusion length that significantly affect the performance of TiO$_2$ and $\alpha$-Fe$_2$O$_3$ in PEC devices. To this regard, one-dimensional (1D) nanostructuring is typically applied as it provides several superior features such as a significant enlargement of the material surface area, extended contact between the semiconductor and the electrolyte and, most remarkably, preferential electrical transport that overall suppress charge carrier recombination and improve TiO$_2$ and $\alpha$-Fe$_2$O$_3$ photo-electrocatalytic properties. The present review describes various synthetic methods, properties and PEC applications of 1D-photoanodes (nanotubes, nanorods, nanofibers, nanowires) based on titania, hematite, and on $\alpha$-Fe$_2$O$_3$/TiO$_2$ heterostructures. Various routes towards modification and enhancement of PEC activity of 1D photoanodes are also discussed including doping, decoration with co-catalysts and heterojunction engineering. Finally, the challenges related to the optimization of charge transfer kinetics in both oxides are highlighted.

In this work we describe the synthesis and electrochemical properties of nitridated hierarchical TiO$_2$ nanotubes as an electrode for supercapacitors. The hierarchical TiO$_2$ nanostructures are formed by a controlled layer-by-layer TiO2 nanoparticle decoration on self-organized spaced TiO$_2$ nanotubes. These structures are then annealed in NH$_3$ atmosphere at elevated temperature to convert the material to a nitride structure -- this drastically enhances their electron-transport properties. The areal capacitance of hierarchical structures can be tuned by changing the number of decorated TiO$_2$ nanoparticle layers. The capacitance enhancement of the hierarchical structures reaches a maximum when the surface area through nanoparticle deposition is highest and the conductivity via nitridation is optimized.

Gold-decorated TiO$_2$ nanotubes were used for the photocatalytic abatement of Hg(II) in aqueous solutions. The presence of dewetted Au nanoparticles induces a strong enhancement of photocatalytic reduction and scavenging performances, with respect to naked TiO$_2$. In the presence of chlorides, a massive formation of Hg2Cl2 nanowires, produced from Au nanoparticles, was observed using highly Au loaded photocatalysts to treat a 10 ppm Hg(II) solution. EDS and XPS confirmed the nature of the photo-produced nanowires. In the absence of chlorides and/or at lower Hg(II) starting concentrations, the scavenging of mercury proceeds through the formation of Hg-Au amalgams. Solar light driven Hg(II) abatements up to 90% were observed after 24h. ICP-MS analysis revealed that the removed Hg(II) is accumulated on the photocatalyst surface. Regeneration of Hg-loaded exhaust photocatalysts was easily performed by anodic stripping of Hg(0) and Hg(I) to Hg(II). After four catalytic-regeneration cycles only a 10% decrease of activity was observed.

Flat TiO$_2$ layers are deposited by magnetron sputtering on Ti/Si wafers. The TiO$_2$ surfaces are then sputter-coated with thin Au films of a nominal thickness of 0.5-10 nm that are converted by solid-state dewetting into Au nanoparticles of tuneable size and spacing; the Au nanoparticle size can be tuned over a broad range, i.e. ca. 3-200 nm. The Au-decorated TiO$_2$ surfaces enable plasmonic photo-electrochemical water splitting under visible light illumination (450-750 nm). The water splitting performance reaches a maximum for TiO$_2$ layers decorated with ~ 30 nm-sized Au particles. As expected, optical absorption measurements show a red shift of the plasmonic extinction band with increasing the Au nanoparticle size. However, the plasmonic photocurrent is found to peak at ~ 600 nm regardless of the size of the Au nanoparticles, i.e. the plasmonic photocurrent band position is size-independent. Such a remarkable observation can be ascribed to a hot electron injection cut-off effect.

Tantalum doped rutile nanorods were hydrothermally grown on FTO substrates using a new seeding approach. This approach allows the incorporation of high concentrations of up to 4.8 at% tantalum as active doping and results in a significant enhancement of photoelectrochemical water splitting rate (1.8 mA/cm2 at a potential of +1.5 V vs RHE) which corresponds to ca. 1% photocurrent conversion efficiency under AM 1.5, 100 mW/cm2 simulated sunlight irradiation.

In this work, we report on the electrochemical behavior of nitrided spaced TiO$_2$ nanotubes conformally coated with a nanocrystalline Nb$_2$O$_5$ layer and find for these hierarchical structures an excellent supercapacitor performance. Highly aligned conductive 1D electrodes were obtained by a three step process: i) growth of self-organized nanotubes with defined and adjustable intertube spacing, ii) conformal Nb$_2$O$_5$ decoration in the tube interspace (while providing full electrolyte access to the entire active area), and iii) high temperature nitridation. Key is the growth of a nanotube array with regular tube-to-tube interspacing that enables an optimized decoration with secondary materials such as Nb$_2$O$_5$. We observe an increase in electrode capacitance from 158 $\mu$F cm-2 for bare TiO$_2$ NTs, to 1536 $\mu$F cm-2 for TiO$_2$/Nb$_2$O$_5$ NTs, to finally 37 mF cm-2 for Nb$_2$O$_5$ decorated and then nitrided nanotubes. This drastic increase can be ascribed firstly to the defined spacing established between the tube arrays that then allows for a conformal coating with a secondary active coating. Secondly, nitridation causes a drastic increase of the electron conductivity of the entire scaffold and thus reduces resistive losses.

In this work, single crystalline $\alpha$-Fe$_2$O$_3$ nanoflakes (NFs) are formed in a highly dense array by Au seeding of a Fe substrate by a thermal oxidation technique. The NFs are conformally decorated with a thin FeOOH cocatalyst layer. Photoelectrochemical (PEC) measurements show that this photoanode with the $\alpha$-Fe$_2$O$_3$/FeOOH NFs rooted on the Au/Fe structure exhibits a significantly enhanced PEC water oxidation performance compared to the plain $\alpha$-Fe$_2$O$_3$ nanostructure on the Fe substrate. The $\alpha$-Fe$_2$O$_3$/FeOOH NFs on Au/Fe photoanode yields a photocurrent density of 3.1 mA cm-2 at 1.5 VRHE, and a remarkably low onset potential of 0.5-0.6 VRHE in 1 M KOH under AM 1.5G (100 mW cm-2) simulated sunlight illumination. The enhancement in PEC performance can be attributed to a synergistic effect of the FeOOH top decoration and Au under-layer. While FeOOH facilitates hole transfer at the interface of electrode/electrolyte, the Au layer provides a sink for the electron transport to the back contact: this leads overall to a drastically improved charge-separation efficiency in the single crystalline $\alpha$-Fe$_2$O$_3$ NF photoanode.

In the present work we grow anodic TiO$_2$ nanotube layer with tube diameter ~ 500 nm and an open tube mouth. We use this morphology in dye-sensitized solar cells (DSSCs) and show that these tubes allow the construction of hybrid hierarchical photoanode structures of nanotubes with a defined and wall-conformance TiO2 nanoparticles decoration. At the same time, the large diameter allows the successful establishment of an additional (insulating) blocking layer of SiO$_2$ or Al$_2$O$_3$. We show that this combination of hierarchical structure and blocking layer significantly enhances the solar cell efficiency by suppressing recombination reactions. In such a DSSC structure, the solar cell efficiency under back side illumination with AM1.5 illumination is enhanced from 5% neat tube to 7 %.

Effective co-catalysts are of key importance for photocatalytic H2 generation from aqueous environments. An attractive co-catalyst candidate are AuPt (metastable) alloys due to the synergistic electronic and chemical interaction of the constituents in the charge transfer and H2 evolution process. Here we introduce the fabrication of AuPt alloy nanoparticles with nanoporosity (pore size of 2-5 nm) fabricated on spaced TiO2 nanotubes. By dewetting a layered AgAuPt coating, we form AuPtAg alloy nanoparticles. From these alloys, Ag can selectively be dissolved leading to the desired nanoporous AuPt alloy particles with diameter in the range of 10-70 nm deposited as a gradient on the TiO2 nanotubes. A significant enhancement of photocatalytic H2 generation is obtained compared to the same loading of monometallic or nonporous alloy. The nanoporous AuPt particles provide not only a large surface area to volume ratio (and are thus more effective) but also show the intrinsic synergy of a AuPt alloy for H2 generation.

In this work, we demonstrate that a well-established and facile ball milling approach using mixtures of commercial anatase nanoparticles and TiH2 introduces noble-metal-free photocatalytic H2 activity to titania. We characterize this synergistic effect in view of the nature of defects, state of hydroxylation, and investigate the effect on the energetics and kinetics of electronic states and the resulting H2 evolution performance.

Photoelectrochemical (PEC) water splitting is a promising method for conversing solar energy into chemical energy stored in the form of hydrogen. Nanostructured hematite ($\alpha$-Fe$_2$O$_3$) is one of the most attractive materials for highly efficient charge carrier generation and collection due to its large specific surface area and shortening minority carrier diffusion length required to reach the surface. In the present work, PEC water splitting performance of $\alpha$-Fe$_2$O$_3$ prepared by anodization of thin iron layers on an FTO glass and subsequent annealing in low O$_2$-Ar ambient with only 0.03% O$_2$ was investigated. The key finding is that annealing the anodic nanostructures with low oxygen concentration provides a strongly enhanced PEC performance compared with classic air annealing. The photocurrent of the former at 1.5 V vs. RHE results in 1.1 mA/cm2, being 11 times higher than that of the latter. The enhancement of the PEC performance for $\alpha$-Fe$_2$O$_3$ annealed in low oxygen atmosphere can be attributed to controlled morphology, Sn doping, and introduction of oxygen vacancies, which contribute to the enhancement of the hole flux from the photogenerated site to the reactive surface and additionally lead to an enhanced hole transfer at the interface between the $\alpha$-Fe$_2$O$_3$ and the electrolyte. From the obtained results, it is evident that low oxygen annealing is a surprisingly effective method of defect engineering and optimizing $\alpha$-Fe$_2$O$_3$ electrodes for a maximized PEC water splitting performance.

Defined substoichiometric titanium oxides (Ti$_x$O$_{2x-1}$ with $3 < x < 10$) called Magneli phases have been investigated mostly for their unusual high conductivity and metal-like behavior. In photocatalysis, Magneli phase containing titania particles have been reported to provide favorable charge separation resulting in enhanced reaction efficiency. In the current work we describe a one-step synthesis of Magneli-containing mixed phase nanoparticles that carry directly integrated minute amounts of Pt. Phase optimized nanoparticles that contain only a few hundred ppm Pt are very effective photocatalysts for H$_2$ evolution (they provide a 50-100 times higher H$_2$ evolution than plain anatase loaded with a similar amount of Pt). These photocatalysts are synthesized in a setup combining a hot-wall reactor that is used for TiOx synthesis with a spark generator producing Pt nanoparticles. Different reactor temperatures result in various phase ratios between anatase and Magneli phases. The titania nanoparticles (ca. 24 - 53 nm) were characterized using XRD, HRTEM, XPS and EPR spectra as well as ICP-OES analysis. The best photocatalyst prepared at 900$^\circ$C (which consists of mixed phase particles of 32% anatase, 11% rutile and 57% Magneli phases loaded with 290 ppm of Pt) can provide a photocatalytic H$_2$ evolution rate of ca. 5432 micromol h$^{-1} g$^{-1}$ for UV and ca. 1670 micromol h$^{-1} g$^{-1}$ for AM1.5 illumination. For powders converted to higher amounts of Magneli phases (1000$^\circ$C and 1100$^\circ$C), a drastic loss of the photocatalytic H$_2$ generation activity is observed. Thus, the high photocatalytic efficiency under best conditions is ascribed to an effective synergy between multi-junctions of Magneli titania and Pt that enable a much more effective charge separation and reaction than conventional Pt/anatase junctions.

With a large-scale usage of portable electric appliances, a high demand for increasingly high density energy storage devices has emerged. MoO3 has, in principle, a large potential as negative electrode material in supercapacitive devices, due to high charge densities that can be obtained from its reversible redox reactions. Nevertheless, the extremely poor electrochemical stability of MoO3 in aqueous electrolytes prevents a practical use in high capacitance devices. In this work, we describe how to overcome this severe stability issue by forming amorphous molybdenum oxide/tantalum oxide nanotubes by anodic oxidation of a Mo-Ta alloy. The presence of a critical amount of Ta-oxide (> 20 at-%) prevents the electrochemical decay of the MoO3 phase and thus yields an extremely high stability. Due to the protection provided by tantalum oxide, no capacitance losses are measureable after 10000 charg-ing/discharging cycles.

Here we investigate the band-level energetics of "black" hydrogenated titania in different polymorphs using in-situ photoelectrochemical measurements and XPS valence band measurements. We find that the conduction band of black rutile is higher in energy than in black anatase by 0.4 eV. For photocatalytic hydrogen generation, in a polymorph hetero-junction such as in black Degussa P25, thus black rutile can act as a photosensitizer while black anatase provides charge-mediation catalysis onto H2O to generate H2. By optimizing the thermal reduction conditions of black anatase/rutile junctions the H2 production can be significantly increased.

Reduced titanium dioxide has recently attracted large attention, particularly for its unique co-catalyst-free H$_2$ heterogeneous photocatalytic application. The enhanced photocatalytic activity of the reduced TiO$_2$ was previously ascribed to the introduction of point crystal defects (mainly Ti$_3^+$ centers), which result in the formation of intrinsic co-catalytic centers and enhanced visible light absorption. In this work, we systematically investigate the effect of different defects in the TiO$_{2-x}$ lattice on photocatalytic H$_2$ evolution. To introduce different types of defects, thermal annealing in air (oxidative), Ar (inert), Ar/H$_2$ (reducing), and H$_2$ (reducing) atmospheres were performed on commercially available anatase nanopowder. Then, the powders were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) to clarify the effect of treatment on material properties. Furthermore, the defect types were characterized by electron paramagnetic resonance (EPR) spectroscopy. We show that thermal annealing in different atmospheres can form different amounts of different defect types in the TiO$_2$ structure. The highest photocatalytic activation is achieved by annealing the anatase powder in a reducing atmosphere for an appropriate temperature/annealing time. By combining the results from H$_2$ generation and EPR analysis we show that the simultaneous presence of two types of defects, i.e. surface exposed Ti$_3^+$ and lattice embedded Ti$_3^+$ centers, in an optimum low concentration, is the determining factor for an optimized photocatalytic H$_2$ evolution rate. In fact, annealing anatase powder under the so-reported optimized conditions in reducing atmosphere leads to the generation of a considerable amount of H$_2$, with rates as high as 338 $\mu$molh-1g-1.

"Black" TiO2 has gained increasing interest because of its outstanding properties and promising applications in a wide range of fields. Among the outstanding features of the material is that certain synthesis processes lead to the formation of an intrinsic co-catalytic center and thus enable noble-metal free photocatalytic H2 generation. In this work, we report "grey TiO2" by an appropriate hydrogenation treatment exhibits excellent photocatalytic hydrogen. In this case, by the employment of thermally stable and high-surface-area TiO2 nanoparticles as well as mesoporous particles as the hydrogenation precursor, the appropriate extent of reduction of TiO2 (coloration) and the formation of Ti3+ is the key for the efficient noble-metal-free photocatalytic H2 generation. The EPR results reveal that "grey TiO2" shows stronger Ti3+ feature at g ca. 1.93 than "black TiO2" contributing to the intrinsic catalytic center for H2 evolution.

Au and Pt do not form homogeneous bulk alloys as they are thermodynamically not miscible. However, we show that anodic TiO$_2$ nanotubes (NTs) can in-situ be uniformly decorated with homogeneous AuPt alloy nanoparticles (NPs) during their anodic growth. For this, a metallic Ti substrate containing low amounts of dissolved Au (0.1 at%) and Pt (0.1 at%) is used for anodizing. The matrix metal (Ti) is converted to oxide while at the oxide/metal interface direct noble metal particle formation and alloying of Au and Pt takes place; continuously these particles are then picked up by the growing nanotube wall. In our experiments the AuPt alloy NPs have an average size of 4.2 nm and, at the end of the anodic process, are regularly dispersed over the TiO$_2$ nanotubes. These alloyed AuPt particles act as excellent co-catalyst in photocatalytic H2 generation - with a H2 production of 12.04 {\mu}L h-1 under solar light. This represents a strongly enhanced activity as compared with TiO$_2$ NTs decorated with monometallic particles of Au (7 {\mu}L h-1) or Pt (9.96 {\mu}L h-1).

Magneli phases of titanium dioxide (such as Ti4O7, Ti5O9, etc.) provide electronic properties, namely a stable metallic behavior at room temperature. In this manuscript, we demonstrate that nanoscopic Magneli phases, formed intrinsically in anatase during a thermal aerosol synthesis, can enable significant photocatalytic H2 generation. This without the use of any extrinsic co-catalyst in anatase. Under optimized conditions, mixed phase particles of 30 percent anatase, 25 percent Ti4O7 and 20 percent Ti5O9 are obtained that can provide, under solar light, direct photocatalytic H2 evolution at a rate of 145 micromol h-1 g-1. These anatase particles contain 5-10 nm size inter-grown phases of Ti4O7 and Ti5O9. Key is the metallic band of Ti4O7 that induces a particle internal charge separation and transfer cascade with suitable energetics and favorable dimensions that are highly effective for H2 generation.

Noble metal cocatalysts are conventionally a crucial factor in oxide-semiconductor-based photocatalytic hydrogen generation. In the present work, we show that optimized high-temperature hydrogenation of commercially available strontium titanate (SrTiO3) powder can be used to engineer an intrinsic cocatalytic shell around nanoparticles that can create a photocatalyst that is highly effective without the use of any additional cocatalyst for hydrogen generation from neutral aqueous methanol solutions. This intrinsic activation effect can also be observed for SrTiO3[100] single crystal as well as Nb-doped SrTiO3 (100) single crystal. For all types of SrTiO3 samples (nanopowders and either of the single crystals), hydrogenation under optimum conditions leads to a surface-hydroxylated layer together with lattice defects visible by transmission electron microscopy, electron paramagnetic resonance (EPR), and photoluminescence (PL). Active samples provide states in a defective matrix -- this is in contrast to the inactive defects formed in other reductive atmospheres. In aqueous media, active SrTiO3 samples show a significant negative shift of the flatband potential (in photoelectrochemical as well as in capacitance data) and a lower charge-transfer resistance for photoexcited electrons. We therefore ascribe the remarkable cocatalyst-free activation of the material to a synergy between thermodynamics (altered interface energetics induced by hydroxylation) and kinetics (charge transfer mediation by suitable Ti3+ states).

Photocatalytic reactions on TiO2 have recently gained an enormous resurgence because of various new strategies and findings that promise to drastically increase efficiency and specificity of such reactions by modifications of the titania scaffold and chemistry. In view of geometry, in particular, anodic TiO2 nanotubes have attracted wide interest, as they allow a high degree of control over the separation of photogenerated charge carriers not only in photocatalytic reactions but also in photoelectrochemical reactions. A key advantage of ordered nanotube arrays is that nanotube modifications can be embedded site specifically into the tube wall; that is, cocatalysts, doping species, or junctions can be placed at highly defined desired locations (or with a desired regular geometry or pattern) along the tube wall. This allows an unprecedented level of engineering of energetics of reaction sites for catalytic and photocatalytic reactions, which target not only higher efficiencies but also the selectivity of reactions. Many recent tube alterations are of a morphologic nature (mesoporous structures, designed faceted crystallites, hybrids, or 1D structures), but a number of color-coded (namely, black, blue, red, green, gray) modifications have attracted wide interest because of the extension of the light absorption spectrum of titania in the visible range and because unique catalytic activity can be induced. The present Perspective gives an overview of TiO2 nanotubes in photocatalysis with an emphasis on the most recent advances in the use of nanotube arrays and discusses the underlying concepts in tailoring their photocatalytic reactivity.

The electrical transport properties of anodically grown TiO2 nanotubes was investigated. Amorphous nanotubes were anodically grown on titanium foil and transformed through annealing into the anatase phase. Amorphous and polycrystalline single nanotubes were isolated and contacted for measurements of the electrical resistance. Non-linear current-voltage characteristics were explained using the fluctuation induced tunneling conduction model. A clear enhancement of the conductance was induced in an insulating anatase nanotube through low-energy Ar/H ion irradiation. Confocal Raman spectroscopy shows that the annealed samples were in anatase phase and a blueshift due to phonon confinement was observed., Comment: 7 pages, 5 figures

In the present work we grow self-organized TiO2 nanotube arrays with a defined and controlled regular spacing between individual nanotubes. These defined intertube gaps allow to build up hierarchical 1D-branched structures, conformally coated on the nanotube walls using a layer by layer nanoparticle TiO2 decoration of the individual tubes, i.e. having not only a high control over the TiO2 nanotube host structure but also on the harvesting layers. After optimizing the intertube spacing, we build host-guest arrays that show a drastically enhanced performance in photocatalytic H2 generation, compared to any arrangement of conventional TiO2 nanotubes or conventional TiO2 nanoparticle layers. We show this beneficial effect to be due to a combination of increased large surface area (mainly provided by the nanoparticle layers) with a fast transport of the harvested charge within the passivated 1D nanotubes. We anticipate that this type of hierarchical structures based on TiO2 nanotubes with adjustable spacing will find even wider application, as they provide an unprecedented controllable combination of surface area and carrier transport.

We apply high-energy proton ion-implantation to modify TiO2 nanotubes selectively at their tops. In the proton-implanted region we observe the creation of intrinsic co-catalytic centers for photocatalytic H2-evolution. We find proton implantation to induce specific defects and a characteristic modification of the electronic properties not only in nanotubes but also on anatase single crystal (001) surfaces. Nevertheless, for TiO2 nanotubes a strong synergetic effect between implanted region (catalyst) and implant-free tube segment (absorber) can be obtained.

In the present work we introduce a path to the controlled construction of DSSCs based on hierarchically structured single walled, self-organized TiO2 layers. In a first step we describe a simple approach to selectively remove the inner detrimental shell of anodic TiO2 nanotubes (NTs). This then allows controlled well-defined layer-by-layer decoration of these TiO2-NT walls with TiO2 nanoparticles (this in contrast to conventional TiO2 nanotubes). We show that such defined multiple layered decoration can be optimized to build dye sensitized solar cells that (under back-side illumination conditions) can yield solar light conversion efficiencies in the range of 8 %. The beneficial effects observed can be ascribed to a combination of three factors : 1) improved electronic properties of the single walled tubes themselves, 2) a further improvement of the electronic properties by the defined TiCl4 treatment, and 3) a higher specific dye loading that becomes possible for the layer-by-layer decorated single walled tubes., Comment: arXiv admin note: text overlap with arXiv:1610.06437

In this work, we use a double-layered stack of TiO2 nanotubes (TiNTs) to construct a visible-light triggered drug delivery system. Key for visible-light drug release is a hydrophobic cap on the nanotubes containing Au nanoparticles (AuNPs). The AuNPs allow for a photocatalytic scission of the hydrophobic chain under visible light. To demonstrate the principle, we loaded antibiotic (ampicillin sodium (AMP)) in the lower part of the TiO2 nanotube stack, triggered visible light induced release, and carried out antibacterial studies. The release from the platform becomes most controllable if the drug is silane-grafted in hydrophilic bottom layer for drug storage. Thus visible-light photocatalysis can also determine the release kinetics of the active drug from the nanotube wall.

In the present work we show, how a high pressure hydrogenation of commercial anatase or anatase/rutile powder can create a photocatalyst for hydrogen evolution that is highly effective and stable without the need of any additional co-catalyst. This activation effect can not be observed for rutile. For anatase/rutile mixtures, however, a strong synergistic effect is found (similar to findings commonly observed for noble metal decorated TiO2). ESR measurements indicate the intrinsic co-catalytic activation of anatase TiO2 to be due to specific defect centers formed during hydrogenation.

Low-dose nitrogen implantation induces in TiO2 nanotubes a co-catalytic activity for photocatalytic H2-evolution. The use of an ion implantation process leads to a N-implanted zone only at the top part of the tubes. The coupling of this top layer and the underlying non-implanted part of the nanotubes strongly contributes to an efficient carrier separation and thus to a significantly enhanced H2 generation.

In this work, we design a TiO2 nanomembrane (TiNM) that can be used as a nanofilter platform for a selective enrichment of specific proteins. After use the photocatalytic properties of TiO2 allow to decompose unwanted remnant on the substrate and thus make the platform reusable. To construct this platform we fabricate a free-standing TiO2 nanotube array and remove the bottom oxide to form a both-end open TiNM. By pyrolysis of the natural tube wall contamination (C/TiNM), the walls become decorated with graphitic carbon patches. Owing to the large surface area, the amphiphilic nature and the charge adjustable character, this C/TiNM can be used to extract and enrich hydrophobic and charged biomolecules from solutions. Using human serum albumin (HSA) as a model protein as well as protein mixtures, we show that the composite membrane exhibits a highly enhanced loading capacity and protein selectivity and is reusable after a short UV treatment.

In the present work we demonstrate the self-organized formation of anodic Mo-oxide nanotube arrays grown on a Mo sheet under suitable electrochemical conditions in glycerol/NH4F electrolytes. The resulting amorphous tubes can be crystallized by annealing to MoO2 or MoO3. The tube walls then can be further sulfurized fully or partially to Mo-sulfide to form well-ordered arrays of vertically aligned MoOx/MoS2 nanotubes. Under optimized conditions, defined MoS2 sheets form on the oxide walls in a layer by layer low angle zig-zag arrangement that provide a high density of reactive stacking faults. These core-shell nanotube arrays, consisting of tubes with a conductive suboxide core and a functional high defect density MoS2 coating, are highly promising for applications such as electrocatalysis (hydrogen evolution) or ion insertion devices.

In the present work, a simple strategy is used to thermally oxidize TiN nanopowder (ca. 20 nm) to an anatase phase of a TiO2:Ti3+:N compound. In contrast to the rutile phase of such a compound this photocatalyst provides photocatalytic activity for hydrogen evolution under AM1.5 conditions - this without the use of any noble metal co-catalyst. Moreover the photocatalyst is active and stable over extended periods of time (tested for 4 months). Importantly, to achieve successful conversion to the active anatase polymorph, sufficiently small starting particles of TiN are needed. The key factor for catalysis is the stabilization of the co-catalytically active Ti3+ species against oxidation by nitrogen present in the starting material.

In this work, we introduce a facile procedure to graft a thin graphitic C3N4 (g-C3N4) layer on aligned TiO2 nanotube arrays (TiNT) by one-step chemical vapor deposition (CVD) approach. This provides a platform to enhance the visible-light response of TiO2 nanotubes for antimicrobial applications. The formed g- C3N4/TiNT binary nanocomposite exhibits excellent bactericidal efficiency against E. coli as a visiblelight activated antibacterial coating.

In the present work, we introduce the anodic growth of conical shaped TiO2 nanotube arrays. These titania nanocones provide a scaffold for dye-sensitized solar cell (DSSC) structures with significantly improved photon management, providing an optimized absorption profile compared with conventional cylindrical nanotube arrays. Finite difference time domain (FDTD) modelling demonstrates a drastically changed power-absorption characteristic over the tube length. When used in a back-side illumination DSSC configuration, nanocone structures can reach over 60 % higher solar cell conversion efficiency than conventional tubes. The resulting {\eta} of ca. 8 % represents one of the highest reported values for Graetzel type DSSCs used under back-side illumination.

In the present work we explore the front- and back-side performance of a photocatalytic platform consisting of self-organized TiO2 nanotube layers formed by complete anodization of Ti metal films evaporated on quartz slides. The adhesion and light transmission of the tube layers on the quartz surfaces are optimized by a suitable anodization procedure. After their growth, the nanotube arrays were converted into crystalline structures and sputter-coated with co-catalytic Pt nanoparticles. The optically transparent quartz substrates enable the use of the Pt-decorated tube layers for photocatalytic H2 generation under either front- or back-side illumination configurations. The nanotube films on quartz are characterized in view of their physico-chemical properties, including their light transmission features measured using different light sources. The results show that the front-side illumination under optimized factors, i.e., the amount of loaded co-catalyst, yields a maximized photocatalytic performance in terms of H2 generation.

In the present work we use TiO2 nanotube arrays, carrying a Pt coating that is optimally dewetted, as a photocatalyst to generate H2. In order to achieve a maximum H2-generation efficiency, on the one hand an ideal thermal dewetting of the Pt layer into nanoparticles is needed that requires an oxygen free heat treatment, and on the other hand an optimal crystallization of the TiO2 nanotubes into anatase with reduced defect density is achieved only by annealing in O2 containing environment. To overcome this issue, we combine adequate reducing and oxidizing conditions in a multiple annealing treatment, and obtain Pt-decorated anatase TiO2 nanotubes showing significantly enhanced photocatalytic H2 generation ability.

In the present review we try to give a comprehensive and most up to date view to the field, with an emphasis on the currently most investigated anodic TiO2 nanotube arrays. We will first give an overview of different synthesis approaches to produce TiO2 nanotubes and TiO2 nanotube arrays, and then deal with physical and chemical properties of TiO2 nanotubes and techniques to modify them. Finally, we will provide an overview of the most explored and prospective applications of nanotubular TiO2.

In the present work we grow self-organized Ta2O5 nanotube layers in a H2SO4/NH4F electrolyte at various elevated temperatures. Under optimized conditions we obtain 4 {\mu}m long nanotubes that are well adherent to the substrate and can be grown very homogenous over large surface areas. Moreover, the key advantage of this approach is that an open top morphology (initiation layer free) is obtained. After a suitable conversion treatment in NH3 atmosphere Ta3N5 nanotubes are obtained, that after (Co-Pi+Co(OH)x) modification provide, under AM 1.5G illumination conditions, a photoelectrochemical current response of 4.7 mA cm-2 at 1.23 V vs RHE.

TiO2 nanotube arrays grown by anodization were coated with thin layers of polydopamine as visible light sensitizer. The PDA-coated TiO2 scaffolds were used as photocatalyst for selective oxidation of benzyl alcohol under monochromatic irradiation at 473 nm. Benzaldehyde was selectively formed and no by-products could be detected. A maximized reaction yield was obtained in O2-saturated acetonitrile. A mechanism is proposed that implies firstly the charge carrier generation in polydopamine as a consequence of visible light absorption. Secondly, photo-promoted electrons are injected in TiO2 conduction band, and subsequently transferred to dissolved O2 to form oxygen radical anions. These radicals react with benzyl alcohol and lead to its selective dehydrogenation oxidation towards benzaldehyde.

We fabricate photo-anodes by transferring anodic TiO2 nanotube membranes in tube-top-down configuration on FTO glass, and use them for constructing frontside illuminated dye-sensitized solar cells. Prior to solar cell construction, the tube-based photo-anodes are crystallized at different temperatures (400-800{\deg}C), and the effects of tube electron transport properties on the photovoltaic performance of the solar cells are investigated. We show that improved solar cell efficiencies (up to ca. 8.0%) can be reached by high-temperature treatment of the tube membranes. Consistently with electron transport time measurements, remarkably enhanced electron mobility is enabled when tube membranes are crystallized at 600{\deg}C., Comment: Published 1 October 2015, 2016 IOP Publishing Ltd, Semiconductor Science and Technology, Volume 31, Number 1

We introduce the use of pure molten ortho-phosphoric acid (o-H3PO4) as an electrolyte for selforganizing electrochemistry. This electrolyte allows for the formation of self-organized oxide architectures (one-dimensional nanotubes, nanochannels, nanopores) on metals such as tungsten that up to now were regarded as very difficult to grow self-ordered anodic oxide structures. In this work, we show particularly the fabrication of thick, vertically aligned tungsten oxide nanochannel layers, with pore diameter of ca. 10 nm, and illustrate their potential use in some typical applications.

We optimize the deposition of CH3NH3PbI3 perovskite into mesoporous electrodes consisting of anodic TiO2 nanotube layers. By a simple spin coating approach, complete filling of the tube scaffolds is obtained, that leads to interdigitated perovskite structures in conformal contact with the TiO2 tube counterparts. Such assemblies can be used as solid state solar cells in hole-transporting material-free configuration, i.e., the tube scaffold serves as electron collector and blocking layer, while the perovskite acts as visible light absorber and hole transporting material. We show that the complete filling of the tube scaffold with the perovskite is essential to improve the solar cell efficiency.

In the present work we investigate various optical properties (such as light absorption and reflectance) of anodic TiO2 nanotubes layers directly transferred as self-standing membranes onto quartz substrates. This allows investigation in a transmission geometry which provides significantly more reliable data than measurements on the metallic Ti substrate. Light transmission and reflectance measurements were carried out for layers of thicknesses varying from 1.8 to 50 micrometer, and the layers were investigated in their amorphous and crystalline form. A series of wavelength-dependent light attenuation coefficients are extrapolated and found to match the photocurrent vs. irradiation wavelength behavior. However, a feature specific to anodic nanotubes is that their intrinsic carbon content causes a sub-bandgap response that is proportional to the carbon contamination content in the TiO2 nanotubes. Overall the extracted data provide valuable basis and understanding for the design of photo-electrochemical devices based on TiO2 nanotubes.