Electron-conducting quantum dot solids: novel materials based on colloidal semiconductor nanocrystals

We review the optical and electrical properties of solids that are composed of semiconductor nanocrystals. Crystals, with dimensions in the nanometre range, of II-VI, IV-VI and III-V compound semiconductors, can be prepared by wet-chemical methods with a remarkable control of their size and shape, and surface chemistry. In the uncharged ground state, such nanocrystals are insulators. Electrons can be added, one by one, to the conduction orbitals, forming artificial atoms strongly confined in the nanocrystal. Semiconductor nanocrystals form the building blocks for larger architectures, which self-assemble due to van der Waals interactions. The electronic structure of the quantum dot solids prepared in such a way is determined by the orbital set of the nanocrystal building blocks and the electronic coupling between them. The opto-electronic properties are dramatically altered by electron injection into the orbitals. We discuss the optical and electrical properties of quantum dot solids in which the electron occupation of the orbitals is controlled by the electrochemical potential.     

Effect of metal ions on photoluminescence, charge transport, magnetic and catalytic properties of all-inorganic colloidal nanocrystals and nanocrystal solids

Colloidal semiconductor nanocrystals (NCs) provide convenient "building blocks" for solution-processed solar cells, light-emitting devices, photocatalytic systems, etc. The use of inorganic ligands for colloidal NCs dramatically improved inter-NC charge transport, enabling fast progress in NC-based devices. Typical inorganic ligands (e.g., Sn(2)S(6)(4-), S(2-)) are represented by negatively charged ions that bind covalently to electrophilic metal surface sites. The binding of inorganic charged species to the NC surface provides electrostatic stabilization of NC colloids in polar solvents without introducing insulating barriers between NCs. In this work we show that cationic species needed for electrostatic balance of NC surface charges can also be employed for engineering almost every property of all-inorganic NCs and NC solids, including photoluminescence efficiency, electron mobility, doping, magnetic susceptibility, and electrocatalytic performance. We used a suite of experimental techniques to elucidate the impact of various metal ions on the characteristics of all-inorganic NCs and developed strategies for engineering and optimizing NC-based materials.     

Structural,thermal, and electrical properties of carbonaceous films containing palladium nanocrystals

Carbonaceous films containing Pd nanocrystals can be applied as active layers in gas sensor applications. In this article we show results of studies of C-Pd films, obtained with two different methods: (1) physical and (2) physical + chemical deposition. First type of film prepared by physical vapor deposition (PVD) process was composed of fullerenes, amorphous carbon, and palladium nanograins. In the second method PVD film was modified in chemical vapor deposition (CVD) process forming a foam-like structure. Both types of films were studied by SEM, TEM, TGA, and electrical characterization (measurement of resistivity versus composition of gaseous hydrocarbons mixture).     

Wetting properties of passivated metal nanocrystals at liquid-vapor interfaces: a computer simulation study

Molecular dynamics simulations have been employed to determine the contact angles of alkylthiol passivated gold nanocrystals adsorbed at the air-water interface. Simulations were performed using butane-, dodecane-, and octadecanethiol passivated nanoparticles. We demonstrate how the length of the surfactant chain can profoundly influence the wetting behavior of these nanoparticles. All particles were found to be stable at the air-water interface, possessing large, well-defined contact angles. We find that the shape of the dodecane- and octadecanethiol particles is strongly perturbed by the interface. We also present an analysis of the orientational ordering of water molecules at the dodecane-water interface and around butane- and dodecanethiol passivated nanoparticles. The orientational ordering translates into an electrostatic field around the nanoparticles, the magnitude of which corresponds with that of the water liquid-vapor interface.     

Morphological changes towards enhancing piezoelectric properties of PVDF electrical generators using cellulose nanocrystals

For the first time, a nanocomposite of poly(vinylidene fluoride)/cellulose nanocrystal (PVDF/CNC) is developed as a piezoelectric energy harvester. This is implemented through electrospinning of PVDF solutions containing different levels of CNC loading, i.e., 0, 1, 3 and 5 % with respect to PVDF weight. Analytical techniques including DSC, FTIR and WAXD are conducted to monitor the polymorphism evolution within electrospun nanocomposites as the CNC content is varied. The results imply that CNCs at the optimum concentration (3 and 5 %) can effectively nucleate β crystalline phases. The nucleation of α crystalline phases is also prevented when CNCs are present within the structure of PVDF electrospun fibers. These changes in polymorphism give PVDF/CNC nanocomposites enhanced piezoelectric characteristics compared to pure PVDF nanofibers. We have demonstrated that the developed nanocomposites can charge a 33-μF capacitor over 6 V and light up a commercial LED for more than 30 s. It is envisaged that the PVDF/CNC nanocomposites provide the opportunity for the development of efficient electrical generators as self-powering devices to charge portable electronics.     

Size-dependent chemistry: properties of nanocrystals

Properties of materials determined by their size are indeed fascinating and form the basis of the emerging area of nanoscience. In this article, we examine the size dependent electronic structure and properties of nanocrystals of semiconductors and metals to illustrate this aspect. We then discuss the chemical reactivity of metal nanocrystals which is strongly dependent on the size not only because of the large surface area but also a result of the significantly different electronic structure of the small nanocrystals. Nanoscale catalysis of gold exemplifies this feature. Size also plays a role in the assembly of nanocrystals into crystalline arrays. While we owe the beginnings of size-dependent chemistry to the early studies of colloids, recent findings have added a new dimension to the subject.     

Controlled growth and photocatalytic properties of CdS nanocrystals implanted in layered metal hydroxide matrixes

Layered double hydroxide Cd(1)(-)(x)()Al(x)()(OH)(2)(DS)(x)().3.0H(2)O (CdAlDS) and a related hydroxide salt compound Cd(2)(OH)(3)(DS).2.5H(2)O (CdDS), where DS stands for dodecyl sulfate sandwiched between two adjacent inorganic layers, have been synthesized and used as precursors for CdS nanoparticle growth. Through a gas/solid reaction, CdS nanocrystals implanted in the layer matrixes of the layered double hydroxides are grown, and the sizes of the nanocrystals vary in the range of 3-6 nm in diameter. The presence of trivalent Al cations in the layered double hydroxide can be taken advantage of to control the size of the CdS nanocrystals, and it also helps to prevent the formed nanocrystals from extraction from the solid matrixes. The nano-CdS implanted composite exhibits high photocatalytic activity for degradation of the nonbiodegradable rhodamine B under both UV and visible irradiations.     

Structural,optical, electrical,and photocatalytic properties of manganese doped zinc oxide nanocrystals

Manganese-doped and undoped ZnO nanocrystals were synthesized via wet-chemical methods. The structure, physico-chemical, electrical and optical properties of the as-prepared products were characterized by using the X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PLS) and electrochemical impedance spectroscopy (EIS) techniques. The photocatalytic activity of Mn-doped ZnO nanocrystal (mixed phases) has been examined under the visible-irradiation by using photocatalytic oxidation of rhodamine B (RhB) dye as a model reaction, and compared with that of known system such as pure ZnO nanocrystal (single-phase). The results showed that Mn doped ZnO nanocrystals bleaches RhB much faster than undoped ZnO upon its exposure to the visible light. The enhancement of the photocatalytic activity was discussed as an effect due to the Mn doping in the Mn-doped ZnO semiconductors, which shifts the optical absorption edge to the visible region and alters the electron-hole pair separation conditions. These factors are responsible for the higher photocatalytic performance of Mn/ZnO composites.     

Oligothiophene-functionalized CdSe nanocrystals: preparation and electrochemical properties

The preparation of new molecular hybrids consisting of CdSe semiconductor nanocrystals, surface-functionalized with conductive and electrochemically active oligothiophene ligands, is described. Specially synthesized aniline-terminated oligoalkylthiophenes containing one, two, or four thiophene units were used for the grafting on CdSe nanocrystals, previously surface-functionalized with 4-formyldithiobenzoate. The electrochemical activity of both the inorganic and the organic parts of the hybrid was investigated by cyclic voltammetry. The oxidative doping of the organic part of the hybrid is irreversible, contrary to the case of the “free” non-grafted ligand which shows reversible doping. Furthermore, the electrochemical doping of the surface ligands, occurring at lower potentials than the oxidation of the nanocrystals, perturbs the latter process via charging of the ligands followed by slow relaxation processes. The first two authors contributed equally to this work Correspondence: Peter Reiss, Adam Pron, DSM/DRFMC/SPrAM (UMR 5819 CEA-CNRS-Université Joseph Fourier 1)/LEMOH CEA Grenoble, 17 rue des Martyrs, F-38054 Grenoble Cedex 9, France     

Formation and properties of metal clusters isolated in helium droplets

The unique conditions forming atomic and molecular complexes and clusters using superfluid helium nanodroplets have opened up an innovative route for studying the physical and chemical properties of matter on the nanoscale. This review summarizes the specific characteristics of the formation of atomic clusters partly generated far from equilibrium in the helium environment. Special emphasis is on the optical response, electronic properties as well as dynamical processes which are mostly affected by the surrounding quantum matrix. Experiments include the optical induced response of isolated cluster systems in helium under quite different excitation conditions ranging from the linear regime up to the violent interaction with a strong laser field leading to Coulomb explosion and the generation of highly charged atomic fragments. The variety of results on the outstanding properties in the quantum size regime highlights the peculiar capabilities of helium nanodroplet isolation spectroscopy.     

Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties

Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen)₂]₂{[Cu(phen)]₂ [SiMo₁₂O₄₀(VO)₂]} (1), {[Zn(phen)₂]₂[GeMo₁₂O₄₀(VO)₂]}{[Zn(phen)₂(H₂O)]₂ [GeMo₁₂O₄₀(VO)₂]}·3H₂O (2) and {[Co(phen)₂]₂[PMo₁₂O₄₀(VO)₂]}{[Co(phen)₂(OH)]₂ [PMo₁₂O₄₀(VO)₂]}·2.5H₂O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo₁₂O₄₀(VO)₂] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo₁₂O₄₀(VO)₂]²⁻ linked to two [Cu(phen)]⁺ complexes with two [Cu(phen)₂]⁺ countercations. Compound 2 contains two bicapped Keggin anions [GeMo₁₂O₄₀(VO)₂]⁴⁻, one linked to two [Zn(phen)₂(H₂O)]²⁺ cations and the other one linked to two [Zn(phen)₂]²⁺ cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo₁₂O₄₀(VO)₂]⁴⁻ connected by [Co(phen)₂]²⁺ cations. Discrete bicapped Keggin anions [PMo₁₂O₄₀(VO)₂] linked to two [Co(phen)₂(OH)]⁺ cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions.     

Synthesis and properties of metal phthalocyanines based on disulfophthalic acid

Octasulfo-substituted cobalt phthalocyaninate was synthesized from 3,5-disulfophthalic acid, and its ammonium salt was converted into the corresponding sulfonyl chloride by the action of chlorosulfonic acid. Treatment of the chlorosulfonyl-substituted phthalocyanine complex with aliphatic amines gave octaalkyl-sulfamoyl derivatives. The products were characterized by IR and electronic absorption spectra.     

Formation of PbSe nanocrystals: A growth toward nanocubes

In this paper we report an electron microscopic observation of crystal shape development when PbSe nanocrystals were synthesized using a dynamic injection technique at different temperatures in the presence of oleic acid. A two-step evolution mechanism was proposed, indicating that the shape evolution of PbSe nanocrystals is dependent on the growth time, whereas the crystalline size can be tuned by varying the growth temperature under the studied conditions. It also implies that a higher growth rate in the 111 direction compared to that in the 100 direction results in the formation of nanocubes.     

Monodisperse lanthanide fluoride nanocrystals: synthesis and luminescent properties

Three types of high-quality, monodisperse lanthanide fluoride colloidal nanocrystals (NCs) including LnF(3) (Ln = La-Pr), NaLnF(4) (Ln = Sm-Er), and Na(5)Ln(9)F(32) (Ln = Tm-Lu) with two crystal phases (hexagonal and cubic) and a rich variety of morphologies have been synthesized in high boiling organic solvents oleic acid and 1-octadecene, via a thermal decomposition pathway. The as-synthesized NCs were well characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FT-IR), and photoluminescence (PL) spectra, respectively. It is found that the as-synthesized NCs consist of monodisperse nanoparticles with diverse shapes and narrow size distribution, which can easily disperse in nonpolar cyclohexane solvent. Additionally, a possible mechanism of NC nucleation and growth has been proposed. The results reveal that the formation of monodisperse NCs closely correlates with the inherent nature of lanthanide series from La to Lu. Under 980 nm NIR excitation, as-synthesized Yb(3+)/Ln(3+) (Ln = Er, Tm, Ho)-doped NaGdF(4) and Na(5)Lu(9)F(32) colloidal NCs show the respective characteristic up-conversion (UC) emissions of Er(3+), Tm(3+), and Ho(3+), which are promising for applications in biolabels, bioimaging, displays, and other optical technologies.     

Dual metal atom catalysts: Advantages in electrocatalytic reactions

The dual-metal-atom catalysts(DACs) have aroused much attention as they possess the advantages of single-atom and metal alloy catalysts. And the DACs have exhibited enhanced performance in various electrocatalytic reactions, such as hydrogen/oxygen evolution and oxygen/carbon dioxide/nitrogen reduction. In this review, we mainly overview the latest understanding of the advantages of DACs for these reactions. This review will start with the familiar characterization methods for DACs, then the pri...     

Hierarchical CdSe-gold hybrid nanocrystals: synthesis and optical properties

The synthesis of hybrid nanostructures with controlled size, shape, composition and morphology has attracted increasing attention due to the fundamental and applicable interest. Here, we demonstrate the synthesis and optical properties of hierarchical CdSe-Au hybrid nanostructures with zinc blende (ZB) CdSe nanocrystals (NCs). For 3.5 nm ZB CdSe NCs, one Au cluster was deposited on each CdSe NC. Nevertheless, several Au clusters were selectively deposited on the apexes of 5 nm and 8 nm ZB CdSe NCs, resulting from the different reactivity of crystal facets. Furthermore, hierarchical CdSe-Au nanostructures with complex morphology were organized with the isolated CdSe-Au hybrid NCs by the coalescence of Au domains on the CdSe-Au hybrid NCs. UV-Vis spectra revealed a red tail upon the deposition of Au clusters. The chemical joint of Au on CdSe NCs was further confirmed by fluorescence quenching. The optical limiting performance of CdSe-Au hybrid NCs dispersed in toluene was investigated at 532 nm using a Nd:YAG laser with the pulse width of 8 ns.     

金属-氧化物超晶格纳米结构催化剂(英文)

正Supported metal catalysts such as Pt-Sn/Al2O3, Cu/ZnO/ Al2O3, and Pt-Rh/CeO2-Al2O3 have been industrially applied for petrochemical and environmental related reactions. The com-mon feature of these supported catalysts is that 1 to 10 nm metal nanoparticles are highly dispersed on high surface area porous oxides. The microstructure of the catalyst on the na-noscale in terms of size, morphology, and interface strongly     

The electrical properties of schungite-containing compositions based on polypropylene and high-density polyethylene

Variations in the dc and ac conductivities of schungite-containing compositions based on polypropylene-high-density polyethylene (PP-PE) blends were studied depending on the composition of the polymeric blend, the volume concentration of the filler, and the order of the introduction of the composition components during the preparation of compositions. It was shown that the conductivities of the compositions could depend on the order of the introduction of the components. The structure of initial and schungite-containing PP-PE blends of different compositions was studied by atomic-force microscopy. It was shown that the structure of the compositions depended on the composition of the initial PP-PE blends and the order of the introduction of the components into schungite-filled PP-PE compositions.     

Recent advances in nonmetallic atom-doped metal nanocrystals: Synthesis and catalytic applications

Metal nanocrystals have been recognized as the main catalytic materials in many fields, but insufficient activity and stability, as well as high prices, have limited their large-scale potential applications. As one of the extremely promising alternatives toward metal in boosting their catalytic performance, nonmetallic atoms-doped metal nanocrystals have recently received extensive attention because of their high efficiency, chemical and structural durability, abundant reserve, and low cost. In this review, we highlight the most recent progress in this field and provide insights into their catalytic applications. The metal-nonmetal nanocrystals prepared by doping metal nanocrystals with nonmetallic atoms are introduced and classified based on the types of nonmetallic atoms, including metal hydrides, borides, carbides, nitrides, oxides, phosphides, and chalcogenides. Besides, their applications in catalysis, especially in electrocatalysis and organic catalysis, have been summarized and discussed. Finally, the conclusions and perspectives are given for the catalysis-driven rational design of metal-nonmetal nanocrystals in this minireview.