arXiv subjects

Patrik Schmuki

Publications and source records attributed to Patrik Schmuki.

At least 37 records · Page 2Linked to original sources

arXiv2020

Nanoporous AuPt and AuPtAg alloy co-catalysts formed by dewetting-dealloying on ordered TiO2 nanotube surface lead to significantly enhanced photocatalytic H2 generation

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.

physics.app-ph↗

arXiv2020

Effect of Low Oxygen Annealing on Photoelectrochemical Water Splitting Properties of $α$-Fe$_2$O$_3$

Photoelectrochemical (PEC) water splitting is a promising method for conversing solar energy into chemical energy stored in the form of hydrogen. Nanostructured hematite ($α$-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 $α$-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 $α$-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 $α$-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 $α$-Fe$_2$O$_3$ electrodes for a maximized PEC water splitting performance.

physics.chem-ph↗

arXiv2020

Influence of Ti$_3^+$ Defect-type on Heterogeneous Photocatalytic H$_2$ Evolution Activity of TiO$_2$

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 $μ$molh-1g-1.

physics.chem-ph↗

arXiv2020

Noble metal free photocatalytic H$_2$ generation on black TiO$_2$: On the influence of crystal facets vs. crystal damage

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.

physics.app-ph↗

arXiv2020

TiO$_2$ nanotubes with different spacing, Fe$_2$O$_3$ decoration and their evaluation for Li-ion battery application

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 $α$-Fe$_2$O$_3$ nano-needles in the interspace. These $α$-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 $α$-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 $μ$Ah cm-2 than bare spaced NTs with e.g., 54 $μ$Ah cm-2, the hierarchical decoration with secondary metal oxide, $α$-Fe$_2$O$_3$, remarkably enhances the Li-ion battery performance. Namely, spaced nanotubes with $α$-Fe$_2$O$_3$ decoration have an areal capacitance of 477 $μ$Ah cm-2, i.e., show up to nearly ~8 times higher capacitance. However, the areal capacitance of close-packed NTs with $α$-Fe$_2$O$_3$ decoration saturates at 208 $μ$Ah cm-2, i.e., is limited to ~3 times increase.

physics.app-ph↗

arXiv2020

Photocatalysis with TiO2 Nanotubes: Colorful Reactivity and Designing Site-Specific Photocatalytic Centers into TiO2 Nanotubes

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.

physics.app-ph↗

arXiv2017

Electrical Transport Properties of Polycrystalline and Amorphous TiO2 Single Nanotubes

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.

cond-mat.mes-hall↗

arXiv2016

Black TiO2 nanotubes formed by high energy proton implantation show noble-metal-co-catalyst free photocatalytic H2-evolution

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.

physics.chem-ph↗

arXiv2016

TiO2 nanotubes with laterally spaced ordering enable optimized hierarchical structures with significantly enhanced photocatalytic H2 generation

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.

cond-mat.mtrl-sci↗

arXiv2016

Hierarchical DSSC structures based on single walled TiO2 nanotube arrays reach back-side illumination solar light conversion efficiency of 8%

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.

cond-mat.mtrl-sci↗

arXiv2016

Hydrogenated anatase: Strong photocatalytic H2 evolution without the use of a co-catalyst

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.

physics.chem-ph↗

arXiv2016

Stable Co-Catalyst-Free Photocatalytic H2 Evolution From Oxidized Titanium Nitride Nanopowders

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.

cond-mat.mtrl-sci↗

arXiv2016

Visible Light Triggered Drug Release from TiO2 Nanotube Arrays: A Novel Controllable Antibacterial Platform

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.

physics.chem-ph↗

arXiv2016

TiO2 nanotubes: N-ion implantation at low-dose provides noble-metal-free photocatalytic H2-evolution activity

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.

physics.chem-ph↗

arXiv2016

Self-ordered Mo-oxide Nanotube Arrays as Precursor for Aligned MoOx/MoS2 Core-Shell Nanotubular Structures with a High Density of Reactive Sites

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.

cond-mat.mtrl-sci↗

arXiv2016

Graphitic C3N4 Sensitized TiO2 Nanotube Layers: A Visible Light Activated Efficient Antimicrobial Platform

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.

physics.bio-ph↗

arXiv2016

Carbon Decorated TiO2 Nanotube Membranes: A Renewable Nanofilter for Size- and Charge Selective Enrichment of Proteins

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.

cond-mat.mtrl-sci↗

arXiv2016

Conical-Shaped Titania Nanotubes for Optimized Light Management in DSSCs Reach Back-side Illumination Efficiencies > 8%

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 η of ca. 8 % represents one of the highest reported values for Graetzel type DSSCs used under back-side illumination.

physics.chem-ph↗