Mesoporous Metastable CuTe2 Semiconductor.

Binary metastable semiconductor materials offer exciting possibilities in the field of optoelectronics, such as photovoltaics, tunable photosensors, and detectors. However, understanding their properties and translating them into practical applications can sometimes be challenging, owing to their thermodynamic instability. Herein, we report a temperature-controlled crystallization technique involving electrochemical deposition to produce metastable CuTe2 thin films that can reliably function under ambient conditions. A series of in situ heating/cooling cycle tests from room temperature to 200 °C followed by spectral, morphological, and compound analyses (such as ultraviolet-visible light spectroscopy, X-ray diffraction (XRD) analysis, and X-ray photoelectron spectroscopy (XPS)) suggest that the seeding electrodes play a key role in the realization of the metastable phase in CuTe2 films. In particular, CuTe2 films deposited on Al electrodes exhibit superior crystallinity and long-term stability compared with those grown on a Au substrate. The XRD data of thermally annealed CuTe2 thin films deposited on Al show a markedly sharp peak, indicating significantly increased crystal-domain sizes. Our method can be used to achieve the metastable phase of CuTe2 with a bandgap of 1.67 eV and offers outstanding photoresponsivity under different illumination conditions.

Mesoporous Semiconductive Bi2Se3 Films.

Bi2Se3 is a semiconductive material possessing a bandgap of 0.3 eV, and its unique band structure has paved the way for diverse applications. Herein, we demonstrate a robust platform for synthesizing mesoporous Bi2Se3 films with uniform pore sizes via electrodeposition. Block copolymer micelles act as soft templates in the electrolyte to create a 3D porous nanoarchitecture. By controlling the length of the block copolymer, the pore size is adjusted to 9 and 17 nm precisely. The nonporous Bi2Se3 film exhibits a tunneling current in a vertical direction of 52.0 nA, but upon introducing porosity (9 nm pores), the tunneling current increases significantly to 684.6 nA, suggesting that the conductivity of Bi2Se3 films is dependent on the pore structure and surface area. The abundant porous architecture exposes a larger surface area of Bi2Se3 to the surrounding air within the same volume, thereby augmenting its metallic properties.

Intermetallic Compound TiM (M=Co, Fe) with a Layered Structure Prepared by Deoxidizing Ilmenite-type Oxides in Molten LiCl-CaH2 Mixtures.

CsCl-type intermetallic compounds TiM (M=Co, Fe) were obtained by deoxidizing trigonal ilmenite-type MTiO3 with a reducing agent CaH2 in molten LiCl at 600 °C. X-ray diffraction, nitrogen adsorption, scanning electron microscopy, and transmission electron microscopy with energy-dispersive X-ray, and X-ray photoelectron spectroscopy analyses revealed the formation of nanoscale layered structures, which enhanced specific surface areas (approximately 20 m2 /g) in the intermetallic compounds. In the initial deoxidation stage, Li2 TiO3 -like compounds were observed as an intermediate, suggesting the substitution of M in MTiO3 by Li from the molten LiCl. Compound MTiO3 has a layered structure perpendicular to the c axis of the trigonal structure, suggesting that the layered structures may originate from the crystal structure of the precursors. Formation of the Li2 TiO3 -like intermediate may help maintain the original layered structure during deoxidation and the subsequent alloying at temperatures as low as 600 °C.

Expeditious Electrochemical Synthesis of Mesoporous Chalcogenide Flakes: Mesoporous Cu2 Se as a Potential High-Rate Anode for Sodium-Ion Battery.

Nanostructured copper selenide (Cu2 Se) attracts much interest as it shows outstanding performance as thermoelectric, photo-thermal, and optical material. The mesoporous structure is also a promising morphology to obtain better performance for electrochemical and catalytic applications, thanks to its high surface area. A simple one-step electrochemical method is proposed for mesoporous chalcogenides synthesis. The synthesized Cu2 Se material has two types of mesopores (9 and 18 nm in diameter), which are uniformly distributed inside the flakes. These materials are also implemented for sodium (Na) ion battery (NIB) anode as a proof of concept. The electrode employing the mesoporous Cu2 Se exhibits superior and more stable specific capacity as a NIB anode compared to the non-porous samples. The electrode also exhibits excellent rate tolerance at each current density, from 100 to 1000 mA g-1 . It is suggested that the mesoporous structure is advantageous for the insertion of Na ions inside the flakes. Electrochemical analysis indicates that the mesoporous electrode possesses more prominent diffusion-controlled kinetics during the sodiation-desodiation process, which contributes to the improvement of Na-ion storage performance.

Plasma-Induced Nanocrystalline Domain Engineering and Surface Passivation in Mesoporous Chalcogenide Semiconductor Thin Films.

The synthesis of highly crystalline mesoporous materials is key to realizing high-performance chemical and biological sensors and optoelectronics. However, minimizing surface oxidation and enhancing the domain size without affecting the porous nanoarchitecture are daunting challenges. Herein, we report a hybrid technique that combines bottom-up electrochemical growth with top-down plasma treatment to produce mesoporous semiconductors with large crystalline domain sizes and excellent surface passivation. By passivating unsaturated bonds without incorporating any chemical or physical layers, these films show better stability and enhancement in the optoelectronic properties of mesoporous copper telluride (CuTe) with different pore diameters. These results provide exciting opportunities for the development of long-term, stable, and high-performance mesoporous semiconductor materials for future technologies.

Universal Electrochemical Synthesis of Mesoporous Chalcogenide Semiconductors: Mesoporous CdSe and CdTe Thin Films for Optoelectronic Applications.

Here we report the soft-template-assisted electrochemical deposition of mesoporous semiconductors (CdSe and CdTe). The resulting mesoporous films are stoichiometrically equivalent and contain mesopores homogeneously distributed over the entire surface. To demonstrate the versatility of the method, two block copolymers with different molecular weights are used, yielding films with pores of either 9 or 18 nm diameter. As a proof of concept, the mesoporous CdSe film-based photodetectors show a high sensitivity of 204 mW-1 cm2 at 680 nm wavelength, which is at least two orders of magnitude more sensitive than the bulk counterpart. This work presents a new synthesis route for nanostructured semiconductors with optical band gaps active in the visible spectrum.

A universal approach for the synthesis of mesoporous gold, palladium and platinum films for applications in electrocatalysis.

High-surface-area mesoporous materials expose abundant functional sites for improved performance in applications such as gas storage/separation, catalysis, and sensing. Recently, soft templates composed of amphiphilic surfactants and block copolymers have been used to introduce mesoporosity in various materials, including metals, metal oxides and carbonaceous compounds. In particular, mesoporous metals are attractive in electrocatalysis because their porous networks expose numerous unsaturated atoms on high-index facets that are highly active in catalysis. In this protocol, we describe how to create mesoporous metal films composed of gold, palladium, or platinum using block copolymer micelle templates. The amphiphilic block copolymer micelles are the sacrificial templates and generate uniform structures with tunable pore sizes in electrodeposited metal films. The procedure describes the electrodeposition in detail, including parameters such as micelle diameters, deposition potentials, and deposition times to ensure reproducibility. The micelle diameters can be controlled by swelling the micelles with different solvent mixtures or by using block copolymer micelles with different molecular weights. The deposition potentials and deposition times allow further control of the mesoporous structure and its thickness, respectively. Procedures for example applications are included: glucose oxidation, ethanol oxidation and methanol oxidation reactions. The synthetic methods for preparation of mesoporous metal films will take ~4 h; the subsequent electrochemical tests will take ~5 h for glucose sensing and ~3 h for alcohol oxidation reaction.

Electrochemical preparation system for unique mesoporous hemisphere gold nanoparticles using block copolymer micelles.

Gold nanoparticles (AuNPs) are widely used in various applications, such as biological delivery, catalysis, and others. In this report, we present a novel synthetic method to prepare mesoporous hemisphere gold nanoparticles (MHAuNPs) via electrochemical reduction reaction with the aid of polymeric micelle assembly as a pore-directing agent.

Electrochemical design of two-dimensional Au nanocone arrays using porous anodic alumina membranes with conical holes.

We report step-by-step electrochemical design of two-dimensional (2D) Au nanocone arrays by using novel porous anodic alumina membranes with conical holes. The cones with desirable aspect ratios can be fabricated by using the PAA templates with different aspect ratios. The Au nanocone arrays show high potentials as SERS (Surface Enhanced Raman Scattering)-active substrates and Au electrodes with high surface area.

Oriented growth of small mesochannels utilizing a porous anodic alumina substrate: preparation of continuous film with standing mesochannels.

Standing mesochannels: An "oriented growth on the mesoscale" is demonstrated for the formation of standing mesochannels. The standing mesochannels in the continuous film grow epitaxially from the mesochannels oriented along the straight holes of porous anodic alumina substrate.

Evolution of standing mesochannels on porous anodic alumina substrates with designed conical holes.

We report the formation of standing mesochannels simply by spin-coating a precursor solution onto a PAA (porous anodic alumina) substrate with designed conical holes, utilizing exactly the same precursors and reaction conditions that form two-dimensional (2D) hexagonal mesoporous SBA-15-type films. When the aspect ratios of the conical holes are lower, the sponge-like mesopores are generated within the conical holes. Such a formation of sponge-like mesostructures truly acts as a trigger for the evolution of perpendicularly oriented and tilted mesochannels. On the other hand, when the PAA substrates with high-aspect cones are used, the mesochannels are stacked like a doughnut within the conical holes, which leads to parallel orientations of the mesochannels in the continuous film region.

Pt fibers with stacked donut-like mesospace by assembling pt nanoparticles: guided deposition in physically confined self-assembly of surfactants.

A stacked donut-like mesospace is successfully introduced into Pt fibers by assembling Pt nanoparticles with uniform particle size, by utilizing the guided deposition of Pt nanoparticles in preferentially oriented liquid crystals. We clearly demonstrate that the collaboration of both LLC templating by electrochemical processes and hard templating utilizing a confined effect can lead to the genesis of new nanostructured metals. Such a unique metal-based nanoarchitecture enhances the surface area and enables the high-mass transportation of guest species. Preferentially oriented mesochannels should contribute significantly to the fine control and transport of electronic carriers through metal fibers.