A core-shell copper oxides-cobalt oxides heterostructure nanowire arrays for nitrate reduction to ammonia with high yield rate

Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.

Hierarchical Self-assembly of Well-Defined Louver-Like P-Doped Carbon Nitride Nanowire Arrays with Highly Effcient Hydrogen Evolution

Self-assembled nanostructure arrays integrating the advantages of the intrinsic characters of nanostructure as well as the array stability are appealing in advanced materials.However,the precise bottom-up synthesis of nanostructure arrays without templates or substrates is quite challenging because of the general occurrence of homogeneous nucleation and the difficult manipulation of noncovalent interactions.Herein,we first report the precisely manipulated synthesis of well-defined louver-like P-doped carbon nitride nanowire arrays(L-PCN)via a supramolecular self-assembly method by regulating the noncovalent interactions through hydrogen bond.With this strategy,CN nanowires align in the outer frame with the separation and spatial location achieving ultrastability and outstanding photoelectricity properties.Significantly,this self-assembly L-PCN exhibits a superior visible light-driven hydrogen evolution activity of 1872.9μmol h^−1 g^−1,rendering a^25.6-fold enhancement compared to bulk CN,and high photostability.Moreover,an apparent quantum efficiency of 6.93%is achieved for hydrogen evolution at 420±15 nm.The experimental results and first-principles calculations demonstrate that the remarkable enhancement of photocatalytic activity of L-PCN can be attributed to the synergetic effect of structural topology and dopant.These findings suggest that we are able to design particular hierarchical nanostructures with desirable performance using hydrogen-bond engineering.

Preparation and characterization of highly ordered NiO nanowire arrays by sol-gel template method

Highly ordered nickel monoxide （NiO） nanowire arrays were fabricated by sol-gel synthesis within the pores of anodic alumina membrane （AAM）. Scanning electron microscopy （SEM）, high resolution transmission electron microscopy （HRTEM） and X-ray diffraction （XRD） were used to characterize the topography and crystalloid structure of NiO nanowire arrays. The length and diameter of the NiO nanowires depended on the thickness of the AAM and the diameter of the pores. The results indicated that the NiO nanowires were uniformly assembled into the ordered nanopores of the AAM and paralleled to each other. Nickel monoxide nanotubes were also fabricated with the same method by changing the immersing time. This new method to prepare NiO nanowire arrays may be important from gas sensors to various engineering materials.

Nickel and indium core-shell co-catalysts loaded silicon nanowire arrays for efficient photoelectrocatalytic reduction of CO_(2) to formate

Developing an efficient artificial photosynthetic system for transforming carbon dioxide and storing solar energy in the form of chemical bonds is one of the greatest challenges in modern chemistry.However,the limited choice of catalysts with wide light absorption range,long-term stability and excellent selectivity for CO_(2) reduction makes the process sluggish.Here,a core-shell-structured nonnoble-metal Ni@In co-catalyst loaded p-type silicon nanowire arrays(SiNWs)for efficient CO_(2) reduction to formate is demonstrated.The formation rate and Faradaic efficiency of formate over the Ni@In/SiNWs catalyst reach 58μmol h^(-1) cm^(-2) and 87% under the irradiation of one simulated sunlight(AM 1.5 G,100 mW cm^(-2)),respectively,which are about 24 and 12 times those over the pristine SiNWs.The enhanced photoelectrocatalytic performance for CO_(2) reduction is attributed to the rational combination of Ni capable of effectively extracting the photogenerated electrons and In responsible for the selective activation of CO_(2).

Mechanical property and deformation mechanism of gold nanowire with non-uniform distribution of twinned boundaries:A molecular dynamics simulation study

The mechanical property and deformation mechanism of twinned gold nanowire with non-uniform distribution of twinned boundaries(TBs)are studied by the molecular dynamics(MD)method.It is found that the twin boundary spacing(TBS)has a great effect on the strength and plasticity of the nanowires with uniform distribution of TBs.And the strength enhances with the decrease of TBS,while its plasticity declines.For the nanowires with non-uniform distribution of TBs,the differences in distribution among different TBSs have little effect on the Young's modulus or strength,and the compromise in strength appears.But the differences have a remarkable effect on the plasticity of twinned gold nanowire.The twinned gold nanowire with higher local symmetry ratio has better plasticity.The initial dislocations always form in the largest TBS and the fracture always appears at or near the twin boundaries adjacent to the smallest TBS.Some simulation results are consistent with the experimental results.

Seed Free Growth of Aligned ZnO Nanowire Arrays on AZO Substrate

In the absence of commonly used seed layer, we can still successfully synthesized aligned ZnO nanowire arrays by the hydrothermal method. By using aluminum-doped zinc oxide(AZO) glass as a substrate, high-density and vertically aligned ZnO nanowires were synthesized directly on the substrate in the absence of the ZnO seed layer. The current-voltage curve indicated that the sample grown on AZO glass substrate in the absence of seed layer possesses better conductivity than that synthesized on FTO glass substrate with ZnO seed layer. Thus, a simplified, seed-free and low-cost experimental protocol was reported here for large-scale production of high quality ZnO nanowire arrays with promoted conductivity.

Direct Z-scheme WO_(3-x) nanowire-bridged TiO_(2) nanorod arrays for highly efficient photoelectrochemical overall water splitting

All-solid-state Z-scheme photocatalysts for overall water splitting to evolve H_(2) is a promising strategy for efficient conversion of solar energy.However,most of these strategies require redox mediators.Herein,a direct Z-scheme photoelectrocatalytic electrode based on a WO_(3-x)nanowire-bridged TiO_(2)nanorod array heterojunction is constructed for overall water splitting,producing H_(2).The as-prepared WO_(3-x)/TiO_(2)nanorod array heterojunction shows photoelectrochemical(PEC)overall water splitting activity evolving both H_(2) and O_(2)under UV-vis light irradiation.An optimum PEC activity was achieved over a 1.67-WO_(3-x)/TiO_(2)photoelectrode yielding maximum H_(2) and O_(2)evolution rates roughly 11 times higher than that of pure TiO_(2)nanorods without any sacrificial agent or redox mediator.The role of oxygen vacancy in WO_(3-x)in affecting the H_(2) production rate was also comprehensively studied.The superior PEC activity of the WO_(3-x)/TiO_(2)electrode for overall water splitting can be ascribed to an efficient Z-scheme charge transfer pathway between the WO_(3-x)nanowires and TiO_(2)nanorods,the presence of oxygen vacancies in WO_(3-x),and a bias potential applied on the photoelectrode,resulting in effective spatial charge separation.This study provides a novel strategy for developing highly efficient PECs for overall water splitting.

Low-overpotential selective reduction of CO2 to ethanol on electrodeposited CuxAuy nanowire arrays

Direct electrochemical reduction of CO2 to multicarbon products is highly desirable, yet challenging. Here, we present a potentiostatic pulse-electrodeposition of high-aspect-ratio CuxAuy nanowire arrays (NWAs) as high-performance electrocatalysts for the CO2 reduction reaction (CO2RR). The surface electronic structure related to the Cu:Au ratio in the CuxAuy NWAs could be facilely modulated by controlling the electrodeposition potential and the as-fabricated CuxAuy NWAs could be directly used as the catalytic electrode for the CO2RR. The morphology of the high-aspect-ratio nanowire array significantly lowers the onset potential of the alcohol formation due to the diffusion-induced enhancement of the local pH and CO concentration near the nanowire surface. Besides, the properly adjusted surface electronic structure of the CuxAuy NWA enables the adsorption of CO and facilitates the subsequent CO reduction to ethanol via the C-C coupling pathway. Owing to the synergistic effect of morphology and electronic structure, the optimized CuxAuy NWA selectively reduces CO2 to ethanol at low potentials of -0.5——0.7 V vs. RHE with a highest Faradaic efficiency of 48%. This work demonstrates the feasibility to optimize the activity and selectivity of the Cu-based electrocatalysts toward multicarbon alcohols for the CO2RR via simultaneous adjustment of the electronic structure and morphology of the catalysts.

Superior surface electron energy level endows WP_(2) nanowire arrays with N_(2) fixation functions

Nitrogen reduction reaction(NRR)under ambient conditions is always a long-standing challenge in science,due to the extreme difficulty in breaking the strong N≡N triple bond.The key to resolving this issue undoubtedly lies in searching superior catalysts to efficiently activate and hydrogenate the stable nitrogen molecules.We herein evaluate the feasibility of WP_(2) for N2 activation and reduction,and first demonstrate WP_(2) with an impressive ammonia yield rate of 7.13 lg h^(-1)cm^(-2),representing a promising W-based catalyst for NRR.DFT analysis further reveals that the NRR catalysis on WP_(2) proceeds in a distal reaction pathway,and the exceptional NRR activity is originated from superior surface electron energy level matching between WP_(2) and NRR potential which facilitates the interfacial proton-coupled electron transfer dynamics.The successfully unraveling the intrinsic catalytic mechanism of WP_(2) for NRR could offer a powerful platform to manipulate the NRR activity by tuning the electron energy levels.

Preparation and characterization of La-Co alloy nanowire arrays by electrodeposition in AAO template under nonaqueous system

La-Co alloy nanowires can be made in pulse reversal current(PRC) and direct current(DC) electrodepositions under nonaqueous system, with the porous anodic aluminum oxide(AAO) as template. This membrane is subject to the dual-oxidation (two-step) anodizing. Scanning electron microscope(SEM) examination shows that all of the nanowires have uniform diameter about 200 nm, and their diameters are determined by the pore diameter of applied AAO template. X-ray energy dispersion analysis indicates that the chemical composition of La and Co elements is very close to 1-2 in stoichiometry. X-ray diffraction pattern investigation demonstrates that La-Co nanowire is the face-centered cubic(FCC) LaCo13.

Ag-modified hydrogen titanate nanowire arrays for stable lithium metal anode in a carbonate-based electrolyte

In the investigation of the next-generation battery anode,Li metal has attracted increasing attention owing to its ultrahigh specific capacity and low reduction potential.However,its low columbic efficiency,limited cycling life,and serious safety hazards have hindered the practical application of rechargeable Li metal batteries.Although several strategies have been proposed to enhance the electrochemical performance of Li metal anodes,most are centered around ether-based electrolytes,which are volatile and do not provide a sufficiently large voltage window.Therefore,we aimed to attain stable Li deposition/stripping in a commercial carbonate-based electrolyte.Herein,we have successfully synthesized hydrogen titanate(HTO)nanowire arrays decorated with homogenous Ag nanoparticles(NPs)(Ag@HTO)via simple hydrothermal and silver mirror reactions.The 3 D cross-linked array structure with Ag NPs provides preferable nucleation sites for uniform Li deposition,and most importantly,when assembled with the commercial LiNi_(0.5)Co0.2Mn_(0.3)O_(2) cathode material,the Ag@HTO could maintain a capacity retention ratio of 81.2% at 1 C after 200 cycles,however the pristine Ti foil failed to do so after only 60 cycles.Our research therefore reveals a new way of designing current collectors paired with commercial high voltage cathodes that can create high energy density Li metal batteries.

Micromagnetic simulation on the dynamic susceptibility spectra of cobalt nanowires arrays:the effect of magnetostatic interaction

Micromagnetic simulations have been performed to obtain the dynamic susceptibility spectra of 4×4 cobalt nanowire arrays with different spatial configurations and geometries. The susceptibility spectra of isolated wires have also been simulated for comparison purposes. It is found that the susceptibility spectrum of nanowire array bears a lot of similarities to that of an isolated wire, such as the occurrences of the edge mode and the bulk resonance mode. The simulation results also reveal that the susceptibility spectrum of nanowire array behaves like that of single isolated wire as the interwire distance grows to an extent, which is believed due to the decrease of magnetostatic interaction among nanowires, and can be further confirmed by the static magnetic hysteresis simulations. In comparison with single nanowire, magnetostatic interaction may increase or decrease the resonance frequencies of nanowire arrays assuming a certain interwire distance when the length of array increases. Our simulation results are also analysed by employing the Kittel equation and recent theoretical studies.

Growth of high-crystallinity uniform GaAs nanowire arrays by molecular beam epitaxy

The self-catalyzed growth of Ga As nanowires(NWs)on silicon(Si)is an effective way to achieve integration between group III–V elements and Si.High-crystallinity uniform Ga As NW arrays were grown by solid-source molecular beam epitaxy(MBE).In this paper,we describe systematic experiments which indicate that the substrate treatment is crucial to the highly crystalline and uniform growth of one-dimensional nanomaterials.The influence of natural oxidation time on the crystallinity and uniformity of Ga As NW arrays was investigated and is discussed in detail.The Ga As NW crystallinity and uniformity are maximized after 20 days of natural oxidation time.This work provides a new solution for producing high-crystallinity uniform III–V nanowire arrays on wafer-scale Si substrates.The highly crystalline uniform NW arrays are expected to be useful for NW-based optical interconnects and Si platform optoelectronic devices.

Study of Shifted UV Emission Peak of ZnO Nanowire Arrays

We have obtained vertically aligned ZnO nanowire arrays synthesized by microwave-assisted heating method with different growth time.From the room-temperature PL measurement,the strong deep-level emission and weak near band edge(NBE)emission can be seen.The deep-level emissions became weaker and deep-level emissions became stronger when the samples were annealed at 300℃for 30 min,meanwhile,the NBE emission peaks get red-shifted with growth time,and the longer the growth time,the more the peak shifting.This phenomenon can be attributed that the diameter of ZnO nanowires increases with growth time.This PL emission phenomenon is important in research of optoelectronic application.

Mechanically tunable broadband terahertz modulator based on high-aligned Ni nanowire arrays

We present a mechanically tunable broadband terahertz(THz) modulator based on the high-aligned Ni nanowire(NW)arrays. The modulator is a sandwich structure consisting of two polydimethylsiloxane layers and a central layer of highaligned Ni NW arrays. Our experimental measurements reveal the transmittance of THz wave can be effectively modulated by mechanical stretching. The NW density in arrays increases with the strain increasing, which induced an enhancement in the absorption of THz wave. When the strain increases from 0 to 6.5%, a linear relationship is observed for the variation of modulation depth(MD) of THz wave regarding the strain, and the modulated range is from 0 to 85% in a frequency range from 0.3 THz to 1.8 THz. Moreover, the detectable MD is about 15% regarding the 1% strain change resolution. This flexible Ni NW-based modulator can be promised many applications, such as remote strain sensing, and wearable devices.

CdS/SiO_2 nanowire arrays and CdS nanobelt synthesized by thermal evaporation

CdS/SiO2 nanowire arrays and CdS nanobelts were synthesized by thermal evaporation of CdS and CdO mixture powders, with highly selective etching occurring on the silicon substrate surfaces. Study of the growth mechanism of CdS/SiO2 nanowire arrays and the growth process of CdS nanobelts showed that the growth of CdS dendrites plays an important role in the formation of CdS/SiO2 nanowire arrays, and that the mechanism of CdS/SiO2 nanowire arrays growth was in good agreement with “self-assembling nanoelectrochemistry”. In the thermal evaporation process, an interaction between Si from silicon substrate and Cd took place.

The Effect of Silver-Plating Time on Silicon Nanowires Arrays Fabricated by Wet Chemical Etching Method

MACE (Metal-Assisted Chemical Etching) approach has drawn a lot of attentions due to its ability to create highly light-absorptive silicon surface. This method can generate numerous cylindrical shape microstructure on the surface of silicon like a forest, which is called “silicon nanowires arrays”. This structure can dramatically suppress both reflection and transmission at the wavelength range from 400 nm to near-infrared 1800 nm by increasing the propagation path of light. In this paper, ordered silicon nanowires arrays with a large area are prepared by wet chemical etching. It is demonstrated that the SiNWs (Silicon nanowires) arrays with different morphologies can be fabricated from monocrystalline silicon of a given orientation by changing silver-plating time. Excellent anti-reflection performance in broadband wavelengths and incident angle is obtained. The fabrication method and potential application of such SiNWs in the field of photoelectric detection have great value and can provide reference for further research in this field.

Effect of Polyethyleneimine Assisting the Growth of Eu-doped ZnO Nanowire Arrays in Mannich Reaction

In study on the growth reaction mechanism of Eu-doped ZnO nanowire（NW）, the intermedium of reaction is characterized by measures such as FTIR. Besides, the influences of polyethyleneimine（PEI） on morphology, structure and photoelectric property of NW are observed by SEM, TEM, XRD, UV-vis and PL spectrum. According to the result, it manifests that Eu-doped ZnO NW array growth response experiences six mutually associated reaction processes in PEI-HMTA system：（a） chelation reaction of PEI and Zn^2＋ ＆ Eu^3＋;（b） protonation reaction of PEI and NH_3;（c） decomposition reaction of hexamethylenetetramine（HMTA）;（d） Mannich reaction of HCHO and PEI;（e） formation of precursor of Eu-doped ZnO;（f） dehydration condensation of Eu-doped ZnO precursors, further forming a doped ZnO NW array. Among them, PEI is the key factor of the whole doping growth reaction process. It both plays a role in modifying the growth of ZnO NW and makes it become longer and thinner. In the meantime, it also facilitates doping of Eu and enables ZnO NW to capture more photoelectrons and higher transmission rate, which is critical to improve photovoltaic performance of optoelectronic devices.

Bi-based Nanowire and Nanojunction Arrays:Fabrication and Physical Properties

This article reviews the recent developments in the fabrication and properties of one-dimensional （1D） Bi-based nanostructures, including Bi, Sb, BixSb1-x and Bi2Te3 nanowire arrays, and Bi-Bi and Bi-Sb nanojunction arrays. In this article, we present an efiective method to fabricate Bi nanowire arrays with difierent diameters in anodic alumina membrane （AAM） with a single pore size by the pulsed electrodeposition. The fabrication of the high-filling and ordered Bi1-xSbx and Bi2Te3 single crystalline nanowire arrays, the Bi nanowire metalsemiconductor homojunction and Bi-Sb nanowire metal-semiconductor heterojunction arrays by the pulsed electrodeposition are reported. The factors controlling the composition, diameter, growth rate and orientation of the nanowires are analyzed, and the growth mechanism of the nanowire and nanojunction arrays are discussed together with the study of the electrical and thermal properties of Bi-based nanowires and nanojunctions.Finally, this review is concluded with some perspectives on the research directions and focuses in the Bi-based nanomaterials fields.

An effective surface-enhanced Raman scattering template based on gold nanoparticle/silicon nanowire arrays

A large-scale Si nanowire array （SiNWA） is fabricated with gold （Au） nanoparticles by simple metal-assisted chemical etching and metal reduction processes. The three-dimensional nanostructured Au/SiNWA is evaluated as an active substrate for surface-enhanced Raman scattering （SERS）. The results show that the detection limit for rhodamine 6G is as low as 10-7 M, and the Raman enhancement factor is as large as 105 with a relative standard deviation of less than 25%. After the calibration of the Raman peak intensifies of rhodamine 6G and thiram, organic molecules could be quantitatively detected. These results indicate that Au/SiNWA is a promising SERS-active substrate for the detection of biomolecules present in low concentrations. Our findings are an important advance in SERS substrates to allow fast and quantitative detection of trace organic contaminants.