Controlled synthesis of germanium nanowires and nanotubes with variable morphologies and sizes

We report on the controlled growth of germanium (Ge) nanostructures in the form of both nanowire (NW) and nanotube (NT) with ultrahigh aspect ratios and variable diameters. The nanostructures are grown inside a porous anodic aluminum oxide (AAO) template by low-temperature chemical vapor deposition (CVD) assisted by an electrodeposited metal nanorod catalyst. Depending on the choice of catalytic metals (Au, Ni, Cu, Co) and germane (GeH(4)) concentration during CVD, either Ge NWs or NTs can be synthesized at low growth temperatures (310-370 °C). Furthermore, Ge NWs and NTs with two or more branches can be grown from the same stem while using AAO with branched channels as templates. Transmission electron microscopy studies show that NWs are single crystalline and that branches grow epitaxially from the stem of NWs with a crystalline direction independent of diameter. As-grown NTs are amorphous but can crystallize via postannealing at 400 °C in Ar/H(2) atmosphere, with a wall thickness controllable between 6 and 18 nm in the CVD process. The yield and quality of the NTs are critically dependent on the choice of the catalyst, where Ni appears the best choice for Ge NT growth among Ni, Cu, Co, and Au. The synthesis of structurally uniform and morphologically versatile Ge nanostructures may open up new opportunities for integrated Ge-nanostructure-based nanocircuits, nanodevices, and nanosystems.     

The effective density and transport properties of compacted carbon nanotubes and nanowhiskers

We have studied the effective density, electric conductivity, and thermo emf of compacted carbon nanotubes (NTs) and nanowhiskers (NWs). The effective densities of NTs and NWs are 1.6 and 2.8 g/cm³ respectively. The thermo emf of compacted NWs (33 μV/K) and NTs (7–8μV/K) make it possible to use these materials in sensors of molecular gases and biological objects. It is also recommended to introduce NWs and NTs as fillers into glue compositions possessing increased strength and electric conductivity, which are necessary for gluing metals.     

Fabrication of a Stable New Polymorph Gold Nanowire with Sixfold Rotational Symmetry

Gold is known as the most noblest metal with only face‐centered cubic (fcc) structure in ambient conditions. Here, stable hexagonal non‐close‐packed (ncp) gold nanowires (NWs), having a diameter of about 50 nm and aspect ratios of well over 400, are reported. Au NWs are grown in the confined system of nanotubular TiO₂ arrays via photoelectrochemical reduction of HAuCl₄ precursors. Some of the resulting Au NWs are proved to have sixfold rotational symmetry, observed by transmission electron microscopy tilting experiments. This new polymorph is identified as a hexagonal ncp‐structure with lattice parameters of a = 2.884 Å and c = 7.150 Å, showing quite a large interplanar spacing (c/a ≈ 2.48). That is, Au atoms are close‐packed along the ab plane, but each plane is not closely stacked along the c axis like in graphite. The structure is usually expected to be unstable, but the present ncp‐2H gold is stable under ambient conditions and intense electron beam irradiation, and shows thermal stability up to 400 °C. Moreover, the resulting physical properties as a result of the corresponding change in electronic structures are investigated by comparing the optical properties of fcc and ncp‐2H Au NWs.     

High‐Yield Synthesis of Crystal‐Phase‐Heterostructured 4H/fcc Au@Pd Core–Shell Nanorods for Electrocatalytic Ethanol Oxidation

Noble‐metal nanomaterials are attracting increasing research interest due to their promising applications in electrochemical catalysis, for example. Although great efforts have been devoted to the size‐, shape‐, and architecture‐controlled synthesis of noble‐metal nanomaterials, their crystal‐phase‐controlled synthesis is still in its infancy. Here, for the first time, this study reports high‐yield synthesis of Au nanorods (NRs) with alternating 4H/face‐centered cubic (fcc) crystal‐phase heterostructures via a one‐pot wet‐chemical method. The coexistence of 4H and fcc phases is relatively stable, and the 4H/fcc Au NRs can serve as templates for crystal‐phase‐controlled epitaxial growth of other metals. As an example, bimetallic 4H/fcc Au@Pd core–shell NRs are synthesized via the epitaxial growth of Pd on 4H/fcc Au NRs. Significantly, the 4H/fcc Au@Pd NRs show superior mass activity toward the ethanol oxidation reaction, i.e., 6.2 and 4.9 times those of commercial Pd black and Pt/C catalysts, respectively. It is believed that this new synthetic strategy can be used to prepare other novel catalysts for various promising applications.     

Two‐Dimensional Self‐Organization of an Ordered Au Silicide Nanowire Network on a Si(110)‐16 × 2 Surface

A well‐ordered two‐dimensional (2D) network consisting of two crossed Au silicide nanowire (NW) arrays is self‐organized on a Si(110)‐16 × 2 surface by the direct‐current heating of ≈1.5 monolayers of Au on the surface at 1100 K. Such a highly regular crossbar nanomesh exhibits both a perfect long‐range spatial order and a high integration density over a mesoscopic area, and these two self‐ordering crossed arrays of parallel‐aligned NWs have distinctly different sizes and conductivities. NWs are fabricated with widths and pitches as small as ≈2 and ≈5 nm, respectively. The difference in the conductivities of two crossed‐NW arrays opens up the possibility for their utilization in nanodevices of crossbar architecture. Scanning tunneling microscopy/spectroscopy studies show that the 2D self‐organization of this perfect Au silicide nanomesh can be achieved through two different directional electromigrations of Au silicide NWs along different orientations of two nonorthogonal 16 × 2 domains, which are driven by the electrical field of direct‐current heating. Prospects for this Au silicide nanomesh are also discussed.     

High‐Responsivity Photodetection by a Self‐Catalyzed Phase‐Pure p‐GaAs Nanowire

Defects are detrimental for optoelectronics devices, such as stacking faults can form carrier‐transportation barriers, and foreign impurities (Au) with deep‐energy levels can form carrier traps and nonradiative recombination centers. Here, self‐catalyzed p‐type GaAs nanowires (NWs) with a pure zinc blende (ZB) structure are first developed, and then a photodetector made from these NWs is fabricated. Due to the absence of stacking faults and suppression of large amount of defects with deep energy levels, the photodetector exhibits room‐temperature high photoresponsivity of 1.45 × 10⁵ A W^?1 and excellent specific detectivity (D*) up to 1.48 × 10¹⁴ Jones for a low‐intensity light signal of wavelength 632.8 nm, which outperforms previously reported NW‐based photodetectors. These results demonstrate these self‐catalyzed pure‐ZB GaAs NWs to be promising candidates for optoelectronics applications.     

Growth Mechanism of Metal Clusters on a Graphene/Ru(0001) Template

Using first‐principles calculations combined with scanning tunneling microscopy experiments, we investigated the adsorption configurations, electronic structures and the corresponding growth mechanism of several transition metal (TM) atoms (Pt, Ru, Ir, Ti, Pd, Au, Ag, and Cu) on a graphene/Ru(0001) moiré template (G/Ru(0001)) at low coverage. We find that Pt, Ru, Ir, and Ti selectively adsorb on the fcc region of G/Ru(0001) and form ordered dispersed metal nanoclusters. This behavior is due to the unoccupied d orbital of the TM atoms and the strong sp³ hybridization of carbon atoms in the fcc region of G/Ru(0001). Pd, Au, Ag, and Cu form nonselective structures because of the fully occupied d orbital. This mechanism can be extended to metals on a graphene/Rh(111) template. By using Pt as an example, we provide a layer by layer growth path for Pt nanoclusters in the fcc region of the G/Ru(0001). The simulations of growth mechanism agree well with the experimental observations. Moreover, they also provide guidance for the selection of suitable metal atoms to form ordered dispersed metal nanoclusters on similar templates.     

Size‐Dependent Phase Transformation of Noble Metal Nanomaterials

As an important aspect of crystal phase engineering, controlled crystal phase transformation of noble metal nanomaterials has emerged as an effective strategy to explore novel crystal phases of nanomaterials. In particular, it is of significant importance to observe the transformation pathway and reveal the transformation mechanism in situ. Here, the phase transformation behavior of face‐centered cubic (fcc) Au nanoparticles (fcc‐AuNPs), adhering to the surface of 4H nanodomains in 4H/fcc Au nanorods, referred to as 4H‐AuNDs, during in situ transmission electron microscopy imaging is systematically studied. It is found that the phase transformation is dependent on the ratio of the size of the monocrystalline nanoparticle (NP) to the diameter of 4H‐AuND. Furthermore, molecular dynamics simulation and theoretical modeling are used to explain the experimental results, giving a size‐dependent phase transformation diagram which provides a general guidance to predict the phase transformation pathway between fcc and 4H Au nanomaterials. Impressively, this method is general, which is used to study the phase transformation of other metal NPs, such as Pd, Ag, and PtPdAg, adhering to 4H‐AuNDs. The work opens an avenue for selective phase engineering of nanomaterials which may possess unique physicochemical properties and promising applications.     

Germanium nanowires with 3-nm-diameter prepared by low temperature vapour-liquid-solid chemical vapour deposition

We report the growth of germanium nanowires (Ge NWs) with single-step temperature method via vapour-liquid-solid (VLS) mechanism in the low pressure chemical vapour deposition (CVD) reactor at 300 degrees C, 280 degrees C, and 260 degrees C. The catalyst used in our experiment was Au nanoparticles with equivalent thicknesses of 0.1 nm (average diameter approximately 3 nm), 0.3 nm (average diameter approximately 4 nm), 1 nm (average diameter approximately 6 nm), and 3 nm (average diameter approximately 14 nm). The Gibbs-Thomson effect was used to explain our experimental results. The Ge NWs grown at 300 degrees C tend to have tapered structure while the Ge NWs grown at 280 degrees C and 260 degrees C tend to have straight structure. Tapering was caused by the uncatalysed deposition of Ge atoms via CVD mechanism on the sidewalls of nanowire and significantly minimised at lower temperature. We observed that the growth at lower temperature yielded Ge NWs with smaller diameter and also observed that the diameter and length of Ge NWs increases with the size of Au nanoparticles for all growth temperatures. For the same size of Au nanoparticles, Ge NWs tend to be longer with a decrease in temperature. The Ge NWs grown at 260 degrees C from 0.1-nm-thick Au had diameter as small as approximately 3 nm, offering an opportunity to fabricate high-performance p-type ballistic Ge NW transistor, to realise nanowire solar cell with higher efficiency, and also to observe the quantum confinement effect.     

Size-Defined Ru Nanoclusters Supported by TiO2 Nanotubes Enable Low-Concentration Nitrate Electroreduction to Ammonia with Suppressed Hydrogen Evolution

Anthropogenic nitrate pollution has an adverse impact on the environment and human health. As part of a sustainable nitrate management strategy, electrochemical denitrification is studied as an innovative strategy for nutrients recycling and recovering. It is, however, challenging to selectively electro-reduce nitrate with low-concentration for ammonia. Herein, the photo-deposition of size-defined Ru nanoclusters (NCs, average size: ≈1.66 nm) on TiO₂ nanotubes (NTs) is demonstrated, which show improved performance for nitrate-to-ammonia electroreduction with a maximum yield rate of ≈600 µg h⁻¹ cm⁻² and a faradic efficiency (FE) of > 90.0% across a broad range of potentials in comparison with electrodeposited Ru nanoparticles (NPs, average size: ≈23.78 nm) on TiO₂ NTs. Experimental and theoretical evidence further suggests the small-size Ru NCs with the intrinsically enhanced selectivity and activity because of the strong metal/substrate interaction and unsaturated coordination state. The findings highlight the size effect on Ru-based catalyst supported on metal oxides, a versatile catalytic model, which allows the regulation of hydrogen adsorption to favor ammonia production over the competing hydrogen evolution reaction.     

Fabrication of patterned boron carbide nanowires and their electrical, field emission, and flexibility properties

Large-area patterned boron carbide nanowires (B₄C NWs) have been synthesized using chemical vapor deposition (CVD). The average diameter of B₄C NWs is about 50 nm, with a mean length of 20 ??m. The B₄C NWs have a single-crystal structure and conductivities around 5.1 × 10^?2 ??^?1·cm^?1. Field emission measurements of patterned B₄C NWs films show that their turn-on electric field is 2.7 V/??m, lower than that of continuous B₄C NWs films. A single nanowire also exhibits excellent flexibility under high-strain bending cycles without deformation or failure. All together, this suggests that B₄C NWs are a promising candidate for flexible cold cathode materials.      

Kinetic-Modulated Crystal Phase of Ru for Hydrogen Oxidation

Crystal-phase-engineering provides a powerful strategy for regulating the catalytic performance yet remains great challenge. Herein, the kinetic-modulated crystal-phase-control of Ru nanosheet assemblies (Ru NAs) is demonstrated by simply altering the concentration of citric acid (CA). Detailed experimental results reveal that high concentration of CA retards the growth kinetics and thus leads to the formation of metastable face-centered cubic (fcc) Ru NAs, while low concentration of CA results in the fast growth kinetics and the preferential formation of Ru NAs with stable hexagonal close packed (hcp) phase. Moreover, Ru NAs with different phases are used as catalyst for hydrogen oxidation reaction (HOR) to evaluate the effects of crystal phase on catalytic performance. Impressively, Ru NAs with fcc phase display a mass activity of 2.75 A mg_Ru⁻¹ at 50 mV, which is much higher than those of Ru NAs with fcc/hcp (1.02 A mg_Ru⁻¹) and hcp (0.74 A mg_Ru⁻¹) phases. Theoretical calculations show that fcc Ru NAs display weaker adsorption toward ^*H and lower energy barrier toward the rate-determining step (RDS) during HOR. This work provides a facile strategy for regulating the crystal phase of Ru nanocrystals, which may attract rapid interests of researchers in materials, chemistry, and catalysis.     

Bigger is Surprisingly Better: Agglomerates of Larger RuP Nanoparticles Outperform Benchmark Pt Nanocatalysts for the Hydrogen Evolution Reaction

Although metallic ruthenium (Ru) is a potential electrocatalyst for the hydrogen evolution reaction (HER) to replace platinum (Pt) at a cost of only ≈4% of Pt, the persistent dissolution of Ru under operation conditions remains a challenge. Here, it is reported that agglomerates of large ruthenium phosphide (RuP) particles (L‐RP, ≈32 nm) show outstanding HER performance in pH‐universal electrolytes, which particularly demonstrates a surprisingly higher intrinsic activity and durability than small nanoparticles of RuP (S‐RP, ≈3 nm) or metallic Ru on carbon supports. This is especially true in basic media, achieving electrocatalytic activity comparable to or even outperforming that of Pt/C, as reflected by lower overpotential at 10 mA cm^?2, smaller Tafel slope, larger exchange current density, and higher turnover frequency while maintaining 200 h stable operation. Calculations suggest that ΔG_H* of RuP is much closer to zero than that of metallic Ru, and phosphorous doping is proven to enhance the rate of proton transfer in HER, contributing in part to the improved activity of RuP. The better performance of L‐RP than that of S‐RP is ascribed largely to the stabilization of the P species due to the lowered surface energy of large particles. Furthermore, the relatively low‐cost materials and facile synthesis make L‐RP/C a highly attractive next‐generation HER electrocatalyst.     

Tuning Nanowires and Nanotubes for Efficient Fuel‐Cell Electrocatalysis

Developing new synthetic methods for the controlled synthesis of Pt‐based or non‐Pt nanocatalysts with low or no Pt loading to facilitate sluggish cathodic oxygen reduction reaction (ORR) and organics oxidation reactions is the key in the development of fuel‐cell technology. Various nanoparticles (NPs), with a range of size, shape, composition, and structure, have shown good potential to catalyze the sluggish cathodic and anodic reactions. In contrast to NPs, one‐dimensional (1D) nanomaterials such as nanowires (NWs), and nanotubes (NTs), exhibit additional advantages associated with their anisotropy, unique structure, and surface properties. The prominent characteristics of NWs and NTs include fewer lattice boundaries, a lower number of surface defect sites, and easier electron and mass transport for better electrocatalytic activity and lower vulnerability to dissolution, Ostwald ripening, and aggregation than Pt NPs for enhanced stability. An overview of recent advances in tuning 1D nanostructured Pt‐based, Pd‐based, or 1D metal‐free nanomaterials as advanced electrocatalysts is provided here, for boosting fuel‐cell reactions with high activity and stability, including the oxygen reduction reaction (ORR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR). After highlighting the different strategies developed so far for the synthesis of Pt‐based 1D nanomaterials with controlled size, shape, and composition, special emphasis is placed on the rational design of diverse NWs and NTs catalysts such as Pt‐based NWs or NTs, non‐Pt NTs, and carbon NTs with molecular engineering, etc. for enhancing the ORR, MOR, and EOR. Finally, some perspectives are highlighted on the development of more efficient fuel‐cell electrocatalysts featuring high stability, low cost, and enhanced performance, which are the key factors in accelerating the commercialization of fuel‐cell technology.     

Hierarchical Metal/Semiconductor Nanostructure for Efficient Water Splitting

A hierarchically patterned metal/semiconductor (gold nanoparticles/ZnO nanowires) nanostructure with maximized photon trapping effects is fabricated via interference lithography (IL) for plasmon enhanced photo‐electrochemical water splitting in the visible region of light. Compared with unpatterned (plain) gold nanoparticles‐coated ZnO NWs (Au NPs/ZnO NWs), the hierarchically patterned Au NPs/ZnO NWs hybrid structures demonstrate higher and wider absorption bands of light leading to increased surface enhanced Raman scattering due to the light trapping effects achieved by the combination of two different nanostructure dimensions; furthermore, pronounced plasmonic enhancement of water splitting is verified in the hierarchically patterned Au NPs/ZnO NWs structures in the visible region. The excellent performance of the hierarchically patterned Au NPs/ZnO NWs indicates that the combination of pre‐determined two different dimensions has great potential for application in solar energy conversion, light emitting diodes, as well as SERS substrates and photoelectrodes for water splitting.     

Localized Synthesis of Iron Oxide Nanowires and Fabrication of High Performance Nanosensors Based on a Single Fe2O3 Nanowire

A composed morphology of iron oxide microstructures covered with very thin nanowires (NWs) with diameter of 15–50 nm has been presented. By oxidizing metallic Fe microparticles at 255 °C for 12 and 24 h, dense iron oxide NW networks bridging prepatterned Au/Cr pads are obtained. X‐ray photoelectron spectroscopy studies reveal formation of α‐Fe₂O₃ and Fe₃O₄ on the surface and it is confirmed by detailed high‐resolution transmission electron microscopy and selected area electron diffraction (SAED) investigations that NWs are single phase α‐Fe₂O₃ and some domains of single phase Fe₃O₄. Localized synthesis of such nano‐ and microparticles directly on sensor platform/structure at 255 °C for 24 h and reoxidation at 650 °C for 0.2–2 h, yield in highly performance and reliable detection of acetone vapor with fast response and recovery times. First nanosensors on a single α‐Fe₂O₃ nanowire are fabricated and studied showing excellent performances and an increase in acetone response by decrease of their diameter was developed. The facile technological approach enables this nanomaterial as candidate for a range of applications in the field of nanoelectronics such as nanosensors and biomedicine devices, especially for breath analysis in the treatment of diabetes patients.     

Synthesis of vertically oriented GaN nanowires on a LiAlO2 substrate via chemical vapor deposition

Vertically oriented nanowires (NWs) of single-crystalline wurtzite GaN have been fabricated on γ-LiAlO₂ (100) substrate coated with a Au layer, via a chemical vapor deposition process at 1000 °C using gallium and ammonia as source materials. The GaN NWs grow along the nonpolar [100] direction with steeply tapering tips, and have triangular cross-sections with widths of 50–100 nm and lengths of up to several microns. The GaN NWs are formed by a vapor-liquid-solid growth mechanism and the tapering tips are attributed to the temperature decrease in the final stage of the synthesis process. The aligned GaN NWs show blue-yellow emission originating from defect levels, residual impurities or surface states of the GaN NWs, and have potential applications in nanotechnology.     

Gold Nanocages: Engineering Their Structure for Biomedical Applications

The galvanic replacement reaction between a Ag template and HAuCl₄ in an aqueous solution transforms 30–200 nm Ag nanocubes into Au nanoboxes and nanocages (nanoboxes with porous walls). By controlling the molar ratio of Ag to HAuCl₄, the extinction peak of resultant structures can be continuously tuned from the blue (400 nm) to the near‐infrared (1200 nm) region of the electromagnetic spectrum. These hollow Au nanostructures are characterized by extraordinarily large cross‐sections for both absorption and scattering. Optical coherence tomography measurements indicate that the 36 nm nanocage has a scattering cross‐section of ～ 0.8 × 10^–15 m² and an absorption cross‐section of ～ 7.3 × 10^–15 m². The absorption cross‐section is more than five orders of magnitude larger than those of conventional organic dyes. Exposure of Au nanocages to a camera flash resulted in the melting and conversion of Au nanocages into spherical particles due to photothermal heating. Discrete‐dipole‐approximation calculations suggest that the magnitudes of both scattering and absorption cross‐sections of Au nanocages can be tailored by controlling their dimensions, as well as the thickness and porosity of their walls. This novel class of hollow nanostructures is expected to find use as both a contrast agent for optical imaging in early stage tumor detection and as a therapeutic agent for photothermal cancer treatment.     

Novel UV–Visible Photodetector in Photovoltaic Mode with Fast Response and Ultrahigh Photosensitivity Employing Se/TiO2 Nanotubes Heterojunction

A feasible strategy for hybrid photodetector by integrating an array of self‐ordered TiO₂ nanotubes (NTs) and selenium is demonstrated to break the compromise between the responsivity and response speed. Novel heterojunction between the TiO₂ NTs and Se in combination with the surface trap states at TiO₂ help regulate the electron transport and facilitate the separation of photogenerated electron–hole pairs under photovoltaic mode (at zero bias), leading to a high responsivity of ≈100 mA W^?1 at 620 nm light illumination and the ultrashort rise/decay time (1.4/7.8 ms). The implanting of intrinsic p‐type Se into TiO₂ NTs broadens the detection range to UV–visible (280–700 nm) with a large detectivity of over 10¹² Jones and a high linear dynamic range of over 80 dB. In addition, a maximum photocurrent of ≈10⁷ A is achieved at 450 nm light illumination and an ultrahigh photosensitivity (on/off ratio up to 10⁴) under zero bias upon UV and visible light illumination is readily achieved. The concept of employing novel heterojunction geometry holds great potential to pave a new way to realize high performance and energy‐efficient optoelectronic devices for practical applications.     

Modulating Electronic Structure of PtCo-Ptrich Nanowires with Ru atoms for Boosted Hydrogen Evolution Catalysis

Rational design and development of highly efficient hydrogen evolution reaction (HER) electrocatalysts is of great significance for the development of green water electrolysis hydrogen production technology. Ru-engineered 1D PtCo-Pt_rich nanowires (Ru-Pt_richCo NWs) are fabricated by a facile electrodeposition method. The rich Pt surface on 1D Pt₃Co contributes to the fully exposed active sites and enhanced intrinsic catalytic activity (co-engineered by Ru and Co atoms) for HER. The incorporation of Ru atoms can not only accelerate the water dissociation in alkaline condition to provide sufficient H^* but also modulate the electronic structure of Pt to achieve optimized H^* adsorption energy. As a result, Ru-Pt_richCo NWs have exhibited ultralow HER overpotentials (η) of 8 and 112 mV to achieve current densities of 10 and 100 mA cm⁻² in 1 m KOH, respectively, which far exceed those of commercial Pt/C catalyst (η₁₀ = 29 mV, η₁₀₀ = 206 mV). Density functional theory (DFT) calculations further demonstrate that the incorporated Ru atoms possess strong water adsorption capacity (−0.52 vs −0.12 eV for Pt), facilitating water dissociation. The Pt atoms in the outermost Pt-rich skin of Ru-Pt_richCo NWs achieve optimized H^* adsorption free energy (ΔG_H*) of −0.08 eV, boosting hydrogen generation.