Inorganic chemistry in a nanoreactor: Au/TiO2 nanocomposites by photolysis of a single-source precursor in miniemulsion.

An original synthetic route, based on the combination of a single-source precursor, UV-photodegradation and inverse w/o miniemulsion, is used to prepare Au nanoparticles (NPs) dispersed on titania. The source of the nanocomposite materials is the photolabile single-source precursor AuCl4(NH4)7[Ti2(O2)2(cit)(Hcit)]2·12H2O, which is suspended in a w/o miniemulsion consisting of different surfactant/hydrocarbon/water formulations (surfactant: sodium dodecylsulfate (SDS) or Triton X-100) and subsequently irradiated with a UV lamp to promote its decomposition in the confined space of the droplets. Gold NPs that form at room temperature are found to be crystalline, while titanium dioxide occurs as an amorphous phase. Moreover, the average crystallite size of gold NPs ranges between 20 and 24 nm when using SDS and between 26 and 40 nm in the case of Triton X-100, after 4 and 8 hours of irradiation time, respectively. Scanning and transmission electron microscopies (SEM and TEM) are used to get information about the nanocomposite morphology and nanostructure, revealing that gold NPs are uniformly distributed on the titanium oxide surface. Furthermore, X-ray photoelectron spectroscopy (XPS) outcomes, besides confirming the formation of both metallic gold and titania, provide information about the high dispersion of Au NPs on the TiO2 surface. In fact, the Au : Ti atomic ratio is found to be 0.45-1.5 (1 : 2-1.5 : 1), which is higher than the value determined by starting from the precursor stoichiometry (0.25). Catalytic testing in the oxidation of 2-propanol shows that decomposition of the precursor in a miniemulsion provides a nanocomposite with enhanced activity compared to the decomposition in the aqueous phase.

Silicium dioxide nanoparticles as carriers for photoactivatable CO-releasing molecules (PhotoCORMs).

Silicium dioxide nanoparticles of about 20 nm diameter containing azido groups at the surface were prepared by emulsion copolymerization of trimethoxymethylsilane and (3-azidopropyl)triethoxysilane and studied by transmission electron microscopy (TEM). A photoactivatable CO-releasing molecule (PhotoCORM) based on [Mn(CO)(3)(tpm)](+) (tpm = tris(pyrazolyl)methane) containing an alkyne-functionalized tpm ligand was covalently linked to the silicium dioxide nanoparticles via the copper-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC "click" reaction). The surface functionalization of the particles with azido groups and manganese CORMs was analyzed by UV-vis, IR, (1)H and (13)C CP-MAS NMR spectroscopies as well as energy-dispersive X-ray spectroscopy (EDX). The myoglobin assay was used to demonstrate that the CORM-functionalized nanoparticles have photoinducible CO-release properties very similar to the free complex. In the future, such functionalized silicium dioxide nanoparticles might be utilized as delivery agents for CORMs in solid tumors.

Stability and growth behavior of transition metal nanoparticles in ionic liquids prepared by thermal evaporation: how stable are they really?

Recently we developed an access to metal- and metal-oxide colloids based on thermal evaporation of metals into ionic liquids (ILs). Here we present systematic studies on the long-time stability of gold and copper nanoparticles (NPs) in different ILs. The influence of metal concentration and temperature on the ripening of the as-prepared gold NPs in different ILs was investigated by transmission electron microscopy (TEM) and UV-vis absorption measurements. Short alkyl chain-length-methyl-imidazolium salts with weakly coordinating perfluorinated counter anions (PF(6), BF(4) or Tf(2)N, bis(trifluoromethanesulfonyl)amide) were found to be better stabilizers compared to ILs with cations bearing long alkyl chains (trihexyltetradecylphosphonium, 1-octyl-3-methylimidazolium) and anions of higher coordination strength (DCA, dicyanamide). In the latter ILs fast particle growth and agglomeration was observed. In the well-stabilizing ILs initially very small NPs form which undergo a similar ripening process at room temperature as at higher temperatures. The final particle size depends largely on the used IL and the metal and to a minor extent on the temperature. The metal concentration seems to be an unimportant factor.

Influence of OH groups on charge transport across organic-organic interfaces: a systematic approach employing an "ideal" device.

The charge transport across a pentacene/SAM interface has been studied by scanning tunnelling spectroscopy (STS) as a function of temperature and film thickness in order to obtain information on the transport mechanisms and in particular on the importance of interfacial OH-groups on n-transport in organic semiconductors. The current-voltage (I-V) characteristics of pentacene thin films deposited on a mercaptoundecanol self-assembled monolayer (SAM) on Au(111) reveal an asymmetric behaviour. At positive sample bias the onset currents shift towards higher voltages for decreasing temperatures, whereas such changes are not seen at negative bias. For lower temperatures, the variation of current onset with layer thickness is absent. These observations are explained by OH-groups at the SAM-surface effectively acting as charge traps. When electrons are caught in these traps at the organic-organic interface, charge transport is severely affected. Imaging of the SAM after loading the traps suggests that the attachment of electrons to the OH-groups exposed at the organic surface is a reversible process.

A gold-containing TiO complex: a crystalline molecular precursor as an alternative route to Au/TiO2 composites.

The gold-containing titanium peroxo-complex AuCl4(NH4)7[Ti4(O2)4(Hcit)2(cit)2].12H2O 1 allows an easy reproducible access to pure Au/TiO2 composites.

Adsorption of atomic hydrogen on ZnO(1010): STM study.

The adsorption of atomic hydrogen on a single crystal ZnO(1010) surface has been studied by scanning tunneling microscopy (STM) under ultrahigh vacuum conditions at room temperature and at elevated temperatures. High resolution STM images indicate that a well-ordered (1x1) H adlayer is formed on the ZnO(1010) surface. The STM data strongly indicate that the hydrogen adsorbs on top of the oxygen atoms forming hydroxyl species. Scanning tunneling spectroscopy (STS) studies reveal a H atom induced metallization at room temperature. In contrast to the clean surface for the hydrogen-covered surface distinct defects structures consisting of missing O and Zn atoms could be identified.

A novel preparation of nano-Cu/ZnO by photo-reduction of Cu(OCH(Me)CH2NMe2)2 on ZnO at room temperature.

Room-temperature preparation of nano-Cu on ZnO by UV light induced photo-reduction of Cu(OCH(Me)CH2NMe2)2 precursor was achieved, indicating a novel method of nano-Cu/ZnO synthesis from an organometallic copper precursor in non-aqueous media without further chemical reduction.

A non-aqueous organometallic route to highly monodispersed copper nanoparticles using [Cu(OCH(Me)CH2NMe2)2].

Good quality, highly monodispersed capped copper metal nanoparticles have been synthesised in a non-hydrolytic approach using thermal decomposition of the Cu(II) precursor [Cu(OCH(Me)CH2NMe2)2] in a hot coordinating solvent without further reducing agents; the copper nanoparticles have been characterised by optical spectroscopy (UV/VIS), electron microscopy (TEM), electron diffraction (SAED), and dynamic light scattering (DLS).