Zn Nanocrystals Research Articles

TEM beam-induced generation of Zn nanocrystals from a polymer-encapsulated Zn(II) complex

A novel Zn(II) complex viz., [Zn(phen)(DTT)] (1) where DTT = 4-methyl-1,2-benzenedithiolate and phen = 1,10-phenanthroline was synthesized and characterized. The X-ray crystal structure of 1 indicated its dimeric nature with a distorted square pyramidal geometry around Zn(II). 1 was encapsulated within triblock P123 polymer to develop the micelle ZnMS. Dynamic light scattering data indicated the self-assembly of 1 with P123 in an aqueous solution with a low-dispersity parameter (0.63 ± 0.02). ZnMs on TEM beam irradiation (200 keV) generated Zn nanocrystals of size 90–150 nm. Energy-dispersive X-ray spectroscopy data indicated the presence of Zn, S, and O in the nanocrystals.

The Role of Zn Ions in the Structural, Surface, and Gas-Sensing Properties of SnO2:Zn Nanocrystals Synthesized via a Microwave-Assisted Route.

Although semiconducting metal oxide (SMOx) nanoparticles (NPs) have attracted attention as sensing materials, the methodologies available to synthesize them with desirable properties are quite limited and/or often require relatively high energy consumption. Thus, we report herein the processing of Zn-doped SnO2 NPs via a microwave-assisted nonaqueous route at a relatively low temperature (160 °C) and with a short treatment time (20 min). In addition, the effects of adding Zn in the structural, electronic, and gas-sensing properties of SnO2 NPs were investigated. X-ray diffraction and high-resolution transmission electron microscopy analyses revealed the single-phase of rutile SnO2, with an average crystal size of 7 nm. X-ray absorption near edge spectroscopy measurements revealed the homogenous incorporation of Zn ions into the SnO2 network. Gas sensing tests showed that Zn-doped SnO2 NPs were highly sensitive to sub-ppm levels of NO2 gas at 150 °C, with good recovery and stability even under ambient moisture. We observed an increase in the response of the Zn-doped sample of up to 100 times compared to the pristine one. This enhancement in the gas-sensing performance was linked to the Zn ions that provided more surface oxygen defects acting as active sites for the NO2 adsorption on the sensing material.

Palladium Zinc Nanocrystals: Nanoscale Amalgamation Enables Multifunctional Intermetallic Colloids

AbstractIntermetallic nanocrystals are emerging materials for energy, catalysis, and biomedical applications, but combining two or more metals at the nanoscale remains challenging. The amalgamation reaction represents a convenient method for hundreds of intermetallic compositions, as it relies on fast and efficient alloying of liquid metals into presynthesized metallic seeds. Here, Pd–Zn nanocrystals, prepared via Zn amide thermolysis on the surface of Pd nanocrystals and subsequent amalgamation alloying, are investigated. Size‐uniform nanocrystals and control over a wide range of Pd–Zn compositions are achieved. This allows deriving a phase diagram at the nanoscale, in which miscibility gaps and three phases with broad solid solutions are detected. Furthermore, the formation of homogeneous ZnO shells for Pd–Zn compositions extending beyond phase solubility limits is observed. Full chemistry control for Pd–Zn nanocrystals enables a rational choice of materials for selected energy applications, achieveing an extended lifetime of Zn‐ion batteries for Zn‐rich PdZn2 stoichiometry, superior electrocatalytic properties for nearly stoichiometric PdZn halite phase, and the stability and efficiency of high‐voltage cathodes benefiting from ZnO shell protection around Pd3Zn10 nanocrystals are reported. This paper exemplifies the multifunctionality of intermetallics Pd–Zn nanocrystals, while this methodology can be extended to many other bimetallic nanomaterials.

Precursor-Mediated Colloidal Synthesis of Compositionally Tunable Cu-Sb-M-S (M = Zn, Co, and Ni) Nanocrystals and Their Transport Properties.

The solution-based colloidal synthesis of multinary semiconductor compositions has allowed the design of new inorganic materials impacting a large variety of applications. Yet there are certain compositions that have remained elusive-particularly quaternary structures of transition metal-based (e.g., Co, Zn, Ni, Fe, Mn, and Cr) copper antimony chalcogenides. These are widely sought for tuning the electrical and thermal conductivity as a function of the size, composition, and crystal phase. In this work, a facile hot injection approach for the synthesis of three different tetrahedrite-substituted nanocrystals (NCs) (Cu10Zn2Sb4S13, Cu10Co2Sb4S13, and Cu10Ni1.5Sb4S13) and their growth mechanisms are investigated. We reveal that the interplay between the Zn, Ni, and Co precursors on the basis of thiophilicity is key to obtaining pure phase NCs with controlled size and shape. While all of the synthesized crystal phases display outstanding low thermal conductivity, the Cu10.5Sb4Ni1.5S13 system shows the most enhanced electrical conductivity compared to Cu10Zn2Sb4S13 and Cu10Co2Sb4S13. This study highlights an effective synthesis strategy for the growth of complex quaternary nanocrystals and their high potential for application in thermoelectrics.

Vanadium trapped by oblique nano-sheets to preserve the anisotropy in Co–V thin films at high temperature

In this study, oriented nano-sheets generated during the growth of cobalt-rich Co–V and Co–Zn thin films induced a large anisotropy in the magnetic and transport properties. The regular nano-sheets were tilted 52–54 deg. with respect to the substrate plane, ≈ 3.0–4.0 nm thick, ≈ 30–100 nm wide, and ≈ 200–300 nm long, with an inter-sheet distance of ≈ 0.9–1.2 nm. In spite of the different microstructures of the two kinds of samples where the Co–V films were amorphous, whereas the Co–Zn films showed a growth of Zn nanocrystals, the oblique nano-sheet morphology conferred noticeable shape anisotropy to both specimens. This anisotropy resulted in an in-plane uniaxial magnetic anisotropy. The changes in the nano-morphology caused by thermal treatments, and hence in their anisotropic properties, were studied. While the Co–V samples retained or increased their magnetic and transport anisotropies, this anisotropic behavior vanished for the annealed Co–Zn films. High resolution transmission electron microscopy, HRTEM, including chemical analysis at the nano-scale, and the dependence of the anisotropic resistance on temperature allowed to establish the nature and the activation energy spectra of the atomic relaxation processes during heating. These processes displayed a single peak at 1.63 eV for the Co–V and two peaks at 1.67 and 2.0 eV for the Co–Zn. These spectra and their singularities were associated to the changes induced in the nano-morphology of the films by thermal treatments. The Co–V films retained their nano-sheet morphology almost up to 500 ºC; the Co–Zn films lost their nano-sheets at 290 ºC. The thermal stability exhibited by the Co–V films makes them useful for applications in ultra high frequency, optical, magnetostrictive and magneto-electric devices.

Graphene–ZnO nanocomposite sensor for lead-ion detection

ABSTRACT Graphene–ZnO (G-ZnO) nanocomposites with different weight percentages of ZnO were prepared by one-step mechanical milling of graphite and Zn powder in an aqueous medium containing melamine as surfactant. The presence of water ensured oxidation of the Zn particles to ZnO. Melamine-assisted exfoliation led to the formation of triangular-shaped graphene sheets for 10 and 15 wt.% Zn and rod-like ZnO nanocrystals for 20 wt.% Zn loading. Cyclic voltammetric studies showed significantly higher sensitivity of the G-ZnO composites towards the detection of toxic lead (Pb2+) ions, primarily on account of band-gap engineering of the ZnO nanoparticles on the graphene sheets.

A low-dimensional crystal growth model on an isotropic and quasi-free sustained substrate**Project supported by the National Natural Science Foundation of China (Grant Nos. 11374082 and 51671048) and the Ten Thousand Talents Plan of Zhejiang Province of China (Grant No. 2018R52003).

A new crystal growth theoretical model is established for the low-dimensional nanocrystals on an isotropic and quasi-free sustained substrate. The driven mechanism of the model is based on the competitive growth among the preferential growth directions of the crystals possessing anisotropic crystal structures, such as the hexagonal close-packed and wurtzite structures. The calculation results are in good agreement with the experimental findings in the growth process of the low-dimensional Zn nanocrystals on silicone oil surfaces. Our model shows a growth mechanism of various low-dimensional crystals on/in the isotropic substrates.

Optical Properties of CdS Nanocrystals Doped with Zinc and Copper

Cadmium-sulfide nanocrystals are produced by the colloidal method. Doping with zinc and copper is conducted during nanocrystal growth. The optical absorption and photoluminescence spectra are studied. The maximum concentration of the optically active copper impurity is determined from a shift of the fundamental absorption edge to lower energies. It is shown that the long-wavelength luminescence of CdS and CdS:Zn nanocrystals is defined by optical transitions at donor–acceptor pairs. In CdS:Cu nanocrystals, optical absorption and photoluminescence in the visible spectral region are defined by recombination transitions involving the ground state of $${\text{Cu}}_{{{\text{Zn}}}}^{{2 + }}$$ ions. The infrared absorption and photoluminescence of CdS:Cu quantum dots are defined by intracenter transitions within $${\text{Cu}}_{{{\text{Zn}}}}^{{2 + }}$$ ions.

Synthesis of ZnO Nanocrystals in SiO2/Si Track Template: Effect of Electrodeposition Parameters on Structure

This paper presents a study of nanoclusters obtained by electrochemical deposition (ECD) of zinc in the a‐SiO2/Si‐n track template. The nanoporous SiO2 layer on Si substrate (track template) has been created by irradiation with swift Xe ions and further etching in HF solution. The morphology of SiO2/Si‐n track templates and precipitated Zn‐based clusters are examined using a scanning electron microscope JSM 7500F. The crystallographic structure of the Zn‐based precipitates was investigated by means of X‐ray diffraction (XRD). X‐ray analysis is carried out on a D8 ADVANCE ECO X‐ray diffractometer. The Bruker AXSDIFFRAC.EVAv.4.2 software and the international ICDD PDF‐2 database are used to identify the phases and study the crystal structure. From XRD data, it has been found the formation of three crystalline phases of zinc oxide nanocrystals electro‐deposited into SiO2/Si track template: wurtzite, sphalerite, and rock salt structures. Wurtzite is obtained on an amorphous surface of silicon dioxide. Possible mechanisms of ZnO formation instead of metal Zn nanocrystals are discussed.

Оптические свойства нанокристаллов CdS, легированных цинком и медью

AbstractCadmium-sulfide nanocrystals are produced by the colloidal method. Doping with zinc and copper is conducted during nanocrystal growth. The optical absorption and photoluminescence spectra are studied. The maximum concentration of the optically active copper impurity is determined from a shift of the fundamental absorption edge to lower energies. It is shown that the long-wavelength luminescence of CdS and CdS:Zn nanocrystals is defined by optical transitions at donor–acceptor pairs. In CdS:Cu nanocrystals, optical absorption and photoluminescence in the visible spectral region are defined by recombination transitions involving the ground state of $${\text{Cu}}_{{{\text{Zn}}}}^{{2 + }}$$ ions. The infrared absorption and photoluminescence of CdS:Cu quantum dots are defined by intracenter transitions within $${\text{Cu}}_{{{\text{Zn}}}}^{{2 + }}$$ ions.

Pd–Zn nanocrystals for highly efficient formic acid oxidation

Highly uniform Pd–Zn nanocrystals were facilely fabricated with coexisting noble metals and ascorbic acid, which exhibited superior electrocatalytic activity for formic acid oxidation.

High-Performance Zn-TiC-C Nanocomposite Alloy Anode with Exceptional Cycle Life for Lithium-Ion Batteries.

A Zn-based nanocomposite has been prepared through a facile, low-cost high-energy mechanochemical process and employed as an anode material for lithium-ion batteries. Structural characterization reveals that the micrometer-sized Zn-TiC-C nanocomposite is composed of Zn nanocrystals uniformly dispersed in a multifunctional TiC and conductive carbon matrix with a tap density of 1.3 g cm(-3). The Zn-TiC-C nanocomposite exhibits high reversible volumetric capacity (468 mA h cm(-3)), excellent cyclability over 800 cycles (79.2% retention), and good rate performance up to 12.5C (75% of its capacity at 0.25C rate). The enhanced electrochemical performance is mainly due to the presence of the well-mixed TiC+C matrix that plays an important role in providing high conductivity as well as mechanical buffer that mitigates the huge volume expansion and contraction during prolonged cycling. In addition, it prevents the particle growth by uniformly dispersing nanosized Zn within itself during cycling, maintaining high utilization (∼100%) and fast reaction kinetics of Zn anode.

Influence of Co2+ on structural and electromagnetic properties of Mg–Zn nanocrystals synthesized via co-precipitation route

Co-precipitation method was used to synthesize the nanoparticles of cobalt substituted zinc–magnesium ferrites having formula “Mg0.6−0.5xZn0.4−0.5xCoxFe2O4” where 0.00≤x≤0.25. Fabricated samples were annealed at 750°C for 6h. The cubic spinel structure of Mg0.6−0.5xZn0.4−0.5xCoxFe2O4 nanocrystals was confirmed by Fourier transformed infra-red (FTIR) and X-ray diffraction (XRD). Lattice parameter, crystalline size, cell volume, X-ray density, bulk density and porosity were also determined using XRD data. Lattice parameter exhibits overall decreasing trend (0.824–0.817nm) with cobalt content; it is due to the substitution of cobalt (having smaller ionic radii) with magnesium and zinc ions. Cation distribution among A and B sites were studied by FTIR spectrum. Vibrating sample magnetometery (VSM) was used to investigate magnetic properties of as prepared nanoparticles. Coercivity exhibits the inverse relation to crystalline size. Lowest value of coercivity (47.722Oe) was obtained for the sample having x=0.15. Dielectric constant, dielectric loss and dielectric tan loss were inversely related with the frequency.

Photocatalytic activity of MTiO3 (M = Ca, Ni, and Zn) nanocrystals for water decomposition to hydrogen

Abstract

Wet chemical synthesis of intermetallic Pt3Zn nanocrystals via weak reduction reaction together with UPD process and their excellent electrocatalytic performances

Platinum based alloy nanocrystals are promising catalysts for a variety of important practical process. However, it remains a great challenge to synthesize platinum-based intermetallic compound nanocrystals with well-defined surface structures. In this communication, taking the synthesis of concave cubic intermetallic Pt3Zn nanocrystals with {hk0} facets as an example, we proposed a new synthesis strategy for intermetallic compounds by reduction of noble metal precursors via a slow reduction process and reduction of transition metal ions via an underpotential deposition (UPD) process in wet chemical synthesis. The as-prepared intermetallic Pt3Zn nanocrystals exhibited superior CO poisoning tolerance and high electro-catalytic activity in both methanol and formic acid oxidation reactions in comparison with solid solution Pt3Zn nanocrystals and Pt/C.

Visualizing the electrochemical reaction of ZnO nanoparticles with lithium by in situ TEM: two reaction modes are revealed

The lithiation reaction of ZnO as an anode in a lithium-ion battery (LIB) is unclear. The electrochemical behavior of ZnO was investigated inside a transmission electron microscope (TEM) by constructing a nano-LIB using an individual ZnO/graphene sheet as the electrode. The lithiation reaction of ZnO/graphene was monitored by simultaneous determination of the structure with high-resolution TEM, electron diffraction pattern and electron energy-loss spectroscopy. Two kinds of reaction modes were revealed in terms of different reaction rates. One was the violent reaction mode, in which one particle can evolve into an aggregate of many nanoparticles within the Li2O matrix in 1–2 min. The other was the peaceful evolution mode, in which each ZnO nanoparticle evolves into a core–shell particle with multi-domains constituted of Zn and LiZn nanograins. Abnormally large Zn nanocrystals grow quickly in the violent reaction mode, which can suppress the formation of LiZn and impair the reversible capacity. Our observations give direct evidence and important insights for the lithiation mechanism of metal oxide anodes in LIBs.

Metal oxides nanoparticles from complexes on SBA-15 for glycerol conversion

Metal oxides nanoparticles dispersed on SBA-15 were synthesized by functionalization of metalloporphyrins onto modified SBA-15, for confining the growth of Ru, Cu, Zn or Co oxides nanocrystals. The composites were evaluated in the dehydration of glycerol at 250°C and 1atm. Among the solids studied, best results were achieved for RuSBA-15 and CoSBA-15 due to the resistance shown by nanoparticles to sintering. On the other hand, ZnSBA-15 and CuSBA-15, which possessed a lesser basic strength, led to parallel reaction instead of the dehydration of glycerol, by forming heavy compounds; this resulted in the catalysts deactivation by coking.

Blue Luminescent of ZnO:Zn Nanocrystal Prepared by One Step Spray Pyrolysis Method

A blue luminescent of ZnO:Zn nanocrystal has been successfully prepared by one step spray pyrolysis method without reducing gas atmosphere. Zinc acetate dihydrate aqueous solutions (0.05 M) were atomized by ultrasonic atomizer. The atomizer used an air as carrier gas with 1, 3 and 5 L/min flowrate. The tubular reactor was set at 500, 600 and 700oC. As prepared samples were characterized by means of x-ray diffraction spectroscopy and scanning electron microscope-energy dispersive x-ray spectroscopy (SEM-EDS). The crystal size of as prepared particles calculated by Scherrer’s equation give 10-20 nm. The luminescent properties of as prepared particles were measured using spectrofluorophotometer. The highest photoluminescent intensity of particles irradiated with excited wavelength of 250 nm was obtained from samples prepared using 5 L/min carrier gas with temperature of tubular reactor 700oC. High intensity of blue luminescent was obtained due to oxygen vacancy in ZnO:Zn.

Synthesis, Shape Control, and Methanol Electro-oxidation Properties of Pt–Zn Alloy and Pt3Zn Intermetallic Nanocrystals

We report the first synthesis of highly monodisperse Pt(3)Zn nanocrystals (NCs). Shape-controlled synthesis generates cubic and spherical Pt-Zn NCs. Reaction temperature is the key to incorporate Zn into Pt, even in the absence of a strong reducing agent. The Pt-Zn NCs are active toward methanol oxidation, with the spherical NCs exhibiting higher activity than the cubic NCs. The Pt-Zn alloy phase can be transformed into the Pt(3)Zn intermetallic phase, upon annealing. The intermetallic Pt(3)Zn shows better performance than the alloy phase Pt-Zn. Besides the activity toward methanol oxidation, Pt-Zn NCs show excellent poisoning tolerance. With activities comparable to the commercial Pt catalyst, enhanced poisoning tolerance and lower cost, Pt-Zn and Pt(3)Zn NCs are a promising new family of catalysts for direct methanol fuel cells.

Y2O3: Eu,Zn nanocrystals as a fluorescent probe for the detection of biotin

We report on the application of nanocrystals (NCs) of the type Y2O3: Eu,Zn as a probe for the fluorescent detection of biotin in aqueous solution. The NCs were dispersed in water in the presence of various surface modifiers including mercaptoethanol (ME), monoethanolamine and ethylene glycol. Both the absorbance of surfactant and the stability of the suspensions were investigated in order to optimize the experimental conditions. ME is found to be the most suitable surfactant for stabilization of the suspended NCs. Their photoluminescence intensity is found to be quenched by biotin. The Stern-Volmer constant for the quenching process is 7.6 × 103 M−1. This NC probe can be applied to the detection of biotin in the 1–60 μM concentration range with detection limit of 1.89 μM. The possible mechanisms of quenching also are discussed.