A highly ordered metal nanohole array (platinum and gold) was fabricated by a two-step replication of the honeycomb structure of anodic porous alumina. Preparation of the negative porous structure of porous alumina followed by the formation of the positive structure with metal resulted in a honeycomb metallic structure. The metal hole array of the film has a uniform, closely packed honeycomb structure approximately 70 nanometers in diameter and from 1 to 3 micrometers thick. Because of its textured surface, the metal hole array of gold showed a notable color change compared with bulk gold.

https://science.sciencemag.org/content/sci/268/5216/1466.full.pdf

Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb Structures of Anodic Alumina

Dilute magnetic semiconductors and wide gap oxide semiconductors are appealing materials for magnetooptical devices. From a combinatorial screening approach looking at the solid solubility of transition metals in titanium dioxides and of their magnetic properties, we report on the observation of transparent ferromagnetism in cobalt-doped anatase thin films with the concentration of cobalt between 0 and 8%. Magnetic microscopy images reveal a magnetic domain structure in the films, indicating the existence of ferromagnetic long-range ordering. The materials remain ferromagnetic above room temperature with a magnetic moment of 0.32 Bohr magnetons per cobalt atom. The film is conductive and exhibits a positive magnetoresistance of 60% at 2 kelvin.

https://science.sciencemag.org/content/sci/291/5505/854.full.pdf

Room-Temperature Ferromagnetism in Transparent Transition Metal-Doped Titanium Dioxide

This paper reviews recent progress made in identifying electrocatalysts for carbon dioxide (CO2) reduction to produce low-carbon fuels, including CO, HCOOH/HCOO−, CH2O, CH4, H2C2O4/HC2O4−, C2H4, CH3OH, CH3CH2OH and others. The electrocatalysts are classified into several categories, including metals, metal alloys, metal oxides, metal complexes, polymers/clusters, enzymes and organic molecules. The catalyts' activity, product selectivity, Faradaic efficiency, catalytic stability and reduction mechanisms during CO2 electroreduction have received detailed treatment. In particular, we review the effects of electrode potential, solution–electrolyte type and composition, temperature, pressure, and other conditions on these catalyst properties. The challenges in achieving highly active and stable CO2 reduction electrocatalysts are analyzed, and several research directions for practical applications are proposed, with the aim of mitigating performance degradation, overcoming additional challenges, and facilitating research and development in this area.

A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels

The electrochemical reduction of CO2 into hydrocarbons and alcohols would allow renewable energy sources to be converted into fuels and chemicals. However, no electrode catalysts have been developed that can perform this transformation with a low overpotential at reasonable current densities. In this work, we compare trends in binding energies for the intermediates in CO2 electrochemical reduction and present an activity “volcano” based on this analysis. This analysis describes the experimentally observed variations in transition-metal catalysts, including why copper is the best-known metal electrocatalyst. The protonation of adsorbed CO is singled out as the most important step dictating the overpotential. New strategies are presented for the discovery of catalysts that can operate with a reduced overpotential.

Activity Descriptors for CO2 Electroreduction to Methane on Transition-Metal Catalysts

Nanotubular material surfaces produced by the electrochemical formation of self-organized porous structures on materials such as aluminum and silicon have attracted significant interest in recent years. While scientific thrust is often directed towards the elucidation of the principles of the self-organization phenomena, technological efforts target applications based on the direct use of the high surface area, for example, for sensing 6] or controlled catalysis, exploit the optical properties in photonic crystals, waveguides, or in 3D arranged Bragg-stack type of reflectors. The highly organized structures may be used indirectly as templates for the deposition of other materials such as metals, semiconductors, or polymers. Over the past few years, nanoporous TiO2 structures have also been formed by electrochemical anodization of titanium. Although several applications have been proposed, a wider impact of these structures has been hampered by the fact that the layers could only been grown to a limiting thickness of a few hundreds of nanometers. Herein we demonstrate for the first time how high-aspectratio, self-organized, TiO2 films can be grown by tailoring the electrochemical conditions during titanium anodization. Figure 1 shows scanning electron microscope (SEM) images of self-organized porous titanium oxide formed to a thickness of approximately 2.5 mm in 1m (NH4)2SO4 electrolyte containing 0.5 wt.% NH4F. From the SEM images it is evident that the self-organized regular porous structure consists of pore arrays with a uniform pore diameter of approximately 100 nm and an average spacing of 150 nm. It is also clear that pore mouths are open on the top of the layer while on the bottom of the structure the tubes are closed by presence of an about 50-nm thick barrier layer of TiO2. The key to achieve high-aspect-ratio growth is to adjust the dissolution rate of TiO2 by localized acidification at the pore bottom while a protective environment is maintained along the pore walls and at the pore mouth. In our previous work in HF and NaF solutions it was established that the thickness of the porous layer is essentially the result of an equilibrium between electrochemical formation of TiO2 at the pore bottom and the chemical dissolution of this TiO2 in an F ion containing solution (Figure 2). The solubility of TiO2 in HF, forming [TiF6] 2 , is essential for pore formation, however, it is also the reason that previous attempts to form porous layers in HF electrolytes always resulted in layer thicknesses in the range of some 100 nm. We tackled the problem by controlling the self-induced acidification of the pore bottom that is caused by the electrochemical dissolution of the metal (Figure 2 a–c). Main reason for the localized acidification is the oxidation and hydrolysis of elemental titanium [Eq. (1), in Figure 2]. The chemical dissolution rate of TiO2 is highly dependent on the pH value (see Figure 2 d). Using a numerical simulation of the relevant ion fluxes we can construct the pH profile in the pore (such as in Figure 2b), in other words, the ideal ion flux for the desired pH profile can then be determined. Furthermore we can tune the dissolution rate by the dissolution current. In other words, using a buffered neutral solution as electrolyte and adjusting the anodic current flow to an ideal value, acid can be created where it is needed, that is, at the pore bottom, while higher pH values are established at the pore mouth as a result of migration and diffusion effects of the pH buffer species (NH4F, (NH4)2SO4). Assuming equilibrium, the flux of dissolving species (leading to acidification at the pore bottom) and the flux of buffering species are equal. The calculations show that for the experimental conditions given in Figure 1 the pH value at the pore bottom is around 2 and increase to about 5 at the pore mouth, this corresponds to a drop in the local chemical etch rate of about 20 times. We used a voltage-sweep technique to achieve a steadystate current and to establish the desired pH profile. The reason to use a voltage-sweep technique rather than a Figure 1. SEM images of porous titanium oxide nanotubes. The crosssectional (a), top (b), and bottom (c) views of a 2.5-mm thick selforganized porous layer. The titanium sample was anodized up to 20 V in 1m (NH4)2SO4 + 0.5 wt. % NH4F using a potential sweep from open-circuit potential to 20 V with sweep rate 0.1 Vs . The average pore diameter is approximately 100 nm and the average pore spacing is approximately 150 nm.

High‐Aspect‐Ratio TiO2 Nanotubes by Anodization of Titanium

We have investigated the influence of HF concentration on the initial stages of electroless deposition for various metals (Al, Au, Cu, Sn, and Pd) onto silicon using atomic force microscopy. As the HF concentration in the plating solution increased, the rate of metal deposition correspondingly increased for Au, Cu, and Pd. In the case of Au and Cu, uniformly sized nuclei comprised the first deposited layer. However for Al and Sn, deposition occurred only at sporadic sites on the surface and was independent of HF concentration. For all of the metal ion studied, deposition initiated preferentially at flaws on the surface. The electroless process indicates a direct displacement mechanism which results in the simultaneous dissolution of Si as the metal ion is reduced at the surface. For all the metal ions deposited in this manner, metal adhesion to the Si surface was poor.

Effects of HF solution in the electroless deposition process on silicon surfaces

Influence of sputtering parameters on electrochemical CO2 reduction in sputtered Au electrode

It was observed that scanning the surface of palladium (Pd) for imaging with a scanning tunneling microscope (STM) caused the morphological change of the surface: The morphology of Pd was transformed from a rough surface to a flat one. This observation suggests that the surface was changed so as to reduce the surface energy. In the case of platinum, the morphology also changed to a certain degree. However, the change was not as drastic as compared with that of Pd. It is supposed that this morphological transformation was due to an electrostatic force (image force) between the STM tip and the metal surface.

Takashi Ohmori

Papers

Effects of HF solution in the electroless deposition process on silicon surfaces

Influence of sputtering parameters on electrochemical CO2 reduction in sputtered Au electrode

Morphological Transformation of Palladium Caused by Measurement of a Scanning Tunneling Microscope

Fabrication of Pt microporous electrodes from anodic porous alumina and immobilization of GOD into their micropores

Development of high throughput evaluation for photocatalyst thin-film