Alexander Birkner

Methanol synthesis over ZnO: A structure-sensitive reaction?

In order to identify active sites on ZnO powdered catalysts in methanol synthesis a total of five ZnO samples with different degrees of crystallinity were characterized by means of N2 physisorption, XRD, TEM, and EXAFS. With respect to catalysis, high-pressure methanol synthesis was performed as a test reaction. A linear area-activity relationship for the highly crystalline materials was obtained, but at high BET surface areas a strong deviation from linearity was found. The observed phenomena provide evidence for a structure-sensitivity, suggesting that a specific active site is favored for methanol formation. Based on earlier work with polycrystalline ZnO powder and with respect to the current theoretical and experimental work with ZnO single crystals, the polar ZnO faces are assumed to be highly relevant for the catalytic activity under methanol synthesis conditions.

Synthesis of CdSe nanoparticles using various organometallic cadmium precursors

Investigations into replacing Me2Cd as a common precursor for the synthesis of CdSe nanoparticles by pyrolysis in a hot coordinating solvent have proven that more stable, less volatile or even crystalline organometallic cadmium compounds can be used instead of Me2Cd. Dineopentylcadmium, bis(3-diethylaminopropyl)cadmium and (2,2′-bipyridine)dimethylcadmium have been used successfully as cadmium sources for the preparation of tri-n-octylphosphine oxide (TOPO)-capped CdSe nanoparticles. The resulting nanocrystallites have been characterized by UV–VIS and IR spectroscopy, photoluminescence spectroscopy (PL), mass spectrometry and transmission electron microscopy (TEM). They consist of separated, well defined spherical particles and show a small size distribution as well as a characterisitic blue shift due to quantum confinement in their optical spectra. The replacement of Me2Cd by less dangerous organometallic precursors thus results in nanocrystallites that show no reduction in quality when compared to the standard method.

Chemical Activity of Thin Oxide Layers: Strong Interactions with the Support Yield a New Thin‐Film Phase of ZnO

Small Cu particles supported on and most likely activated by a ZnO substrate are the active component in the industrial catalyst used to convert syngas (H2, CO, CO2) into methanol, the third most important chemical product worldwide. Although a topic of intense research, the nature of the active site is still under debate. Recently, it has been pointed out that Zn atoms present at the surfaces of the Cu particles exhibit pronounced chemical activity and could explain some of the experimental findings. Another interesting suggestion is the presence of a thin layer of ZnOx species which forms on the surface of the Cu particles under reaction conditions. The importance of such thin oxide layers on the surface of metals under reaction conditions has already been pointed out in other contexts, where it was found that their chemical properties may differ substantially from those of the corresponding bulk oxides. In the case of ZnO this question is particularly interesting, since strong interactions between ZnO and the supporting metal have been reported for ZnO/ Cu and in recent work thin layers of ZnO have been shown to adopt a depolarized, graphitic structure, ZnO(gr), different from the wurtzite-type bulk. The properties of oxide thin films supported on metal substrates have been successfully studied in a number of cases, for example, for thin aluminum oxide films grown by oxidation of Ni/Al alloys. In contrast, the chemical activity of ZnO thin films supported on Cu single crystals has been investigated in a few cases only. Maroie et al. have investigated the adsorption and oxidation processes for single-crystal brass(110), brass(100), and brass(111) surfaces by X-ray photoelectron spectroscopy (XPS). Brass(110) and brass(111) show the same behavior with regard to the interaction with oxygen: the dissociative adsorption of oxygen on the surface is followed by the growth of thin ZnO layers. Wiame et al. reported that after oxidation of (111)-oriented Cu0.7Zn0.3 samples at room temperature the surface is covered by ZnO islands; it was suggested that these islands have (0001) and (0001) surface terminations. A more detailed characterization of the chemical properties of the thin ZnO layers was not carried out in this early work. In the present paper we report a detailed multitechnique investigation of a brass(111) single-crystal substrate (Cu/Zn ratio 9:1) subjected to different oxidation procedures using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) under ultrahigh vacuum (UHV) conditions. The experimental findings are then interpreted by comparison with the results of a rather extensive set of density functional theory (DFT) calculations. Our results reveal the growth of thin ZnO adlayers with chemical properties that are markedly different from those of normal, wurtzite-type ZnO substrates. XPS data recorded for the brass(111) surface before and after different oxidation procedures for two different exit angles of the photoelectrons are shown in Figure 1. Since it is difficult to discriminate between Cu and Cu on the basis of XPS data, also the corresponding results from Auger electron spectroscopy (AES) are shown. For the clean brass(111) substrate the data indicate a Zn atom concentration of 5%, clearly lower than the 10% expected based on the bulk Cu/Zn ratio. Upon oxidation, the XPS data reveal an increase of the surface Zn concentration. Since it is a crucial question whether, in addition to Zn, also Cu or Cu is present, we have carefully analyzed the XPS and AES data. Neither in the Cu2p XPS data nor in the Cu L3M45M45 Auger data were the characteristic signatures of Cu or Cu species resulting from an oxidation of copper atoms detected. Cu exhibits a L3M45M45 peak at electron kinetic energies of 915 eV– 917 eV, which is clearly absent in the present data (see Figure 1). This observation, which agrees with the conclusions presented in a previous study by Rameshan et al., is expected, since in the presence of the less noble Zn one would expect the formation of ZnO to precede that of CuxO. Oxidation at elevated temperatures results in a substantial increase of the Zn signal, revealing the formation of thicker ZnO adlayers. The thickness of these thin ZnO layers was determined from the intensity of the Zn2p3/2 and Cu2p3/2 XPS signals. Exposure of the samples to 500 L of O2 at room temperature yields a ZnO adlayer with an average thickness of about 1.7 , consistent with the presence of a monolayer. More extended exposures to oxygen at room temperature did not result in a significant further increase of the thickness of the ZnO layer. Even the oxidation of the brass substrate at [*] Dr. V. Schott, Dr. A. Birkner, Dr. M. Xu, Dr. Y. Wang Chair of Physical Chemistry Ruhr-University Bochum (Germany)

Investigations on InN whiskers grown by chemical vapour deposition

Abstract Nanostructures of compound semiconductors of group-III nitrides are ideal building blocks for nanoscale optoelectronic devices. InN has a low decomposition temperature and the growth of nanoscale crystalline InN material at low temperatures is difficult. One of the approaches is to design single molecule precursors that decompose at low temperatures. Single molecule precursors of the type N 3 In[(CH 2 ) 3 NMe 2 ] 2 were developed and the growth of dense crystalline InN layers with preferred orientation was achieved using this compound. However, employing specific CVD process parameters we were able to grow InN whiskers consistently by CVD using a cold wall CVD reactor on bare sapphire substrates at a growth temperature of 500°C. These whiskers were characterised by XRD, SEM, EDX, XPS, RBS, TEM and SAED measurements.

Template-mediated synthesis of polycyclic aromatic hydrocarbons: Cyclodehydrogenation and planarization of a hexaphenylbenzene derivative at a copper surface

The deposition of polycyclic aromatic hydrocarbons on substrate surfaces is a key step for using such disklike molecules in nanoelectronic devices. An alternative to the (frequently problematic) preparation by evaporation or deposition from solution is to use the substrate surface as a template for the planarization that accompanies the cyclodehydrogenation (see picture).

Synthesis and characterization of silica MCM-48 as carrier of size-confined nanocrystalline metal oxides particles inside the pore system

Abstract The interpenetrating 3-dimensional channel system of silica MCM-48 has been selected for the deposition of Cu/Zn/O mixed metal oxide particles. With the wet impregnation technique aqueous solutions of metal acetates have been used to load the calcined form of the mesoporous silica. Successive impregnation yielded metal contents of ca. 9 wt.%. Calcination of the composite transformed the acetates to the metal oxides. X-ray powder diffraction and solid-state MAS NMR showed the uptake of the metal salt inside the pore system. N 2 -adsorption, X-ray diffraction and TEM confirmed the mesoporous structure. XPS measurements and EXAFS analysis (Cu K- and Zn K-edges) confirmed the metal uptake. Whereas nano-disperse CuO particles have been obtained ZnO shows no regular structure and seems to have reacted with the silicate channel surface by coating the channel wall.

Low-temperature approach to high surface ZnO nanopowders and a non-aqueous synthesis of ZnO colloids using the single-source precursor [MeZnOSiMe3]4 and related zinc siloxides

We present the temperature-dependent thermolysis of siloxy-substituted ZnO single-source precursors into zinc and zinc oxide, respectively. The solid-state pyrolysis at low temperatures leads to the formation of ZnO powder with a very high surface area whereas the thermolysis in solution yields ZnO colloids. The materials are characterized by UV/VIS, photoluminescence, X-Ray Diffraction (XRD), and Transmission Electron Microscopy (TEM).

Nano-brass colloids: synthesis by co-hydrogenolysis of [CpCu(PMe3)] with [ZnCp*2] and investigation of the oxidation behaviour of α/β-CuZn nanoparticles

A novel, non-aqueous organometallic access to colloidal copper and copper/zinc (brass) nanoparticles is described. Hydrogenolysis of the precursor [CpCu(PMe3)] (1) in mesitylene at 150 °C and 3 bar H2 quantitatively gives elemental Cu. Analogously, a solution of [ZnCp*2] (2) reacts with H2 to give elemental Zn in 100% yield. Co-hydrogenolysis of 1 and 2 in exactly equimolar quantities selectively yields the intermetallic phase β-CuZn characterised by powder X-ray diffraction (PXRD). Deep red colloidal solutions of nano-Cu as well as red to violet colloids of nano-brass alloys (α/β-CuZn) are obtained by co-hydrogenolysis of 1 and 2 in the presence of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) as surfactant. All samples of the general formula Cu1−xZnx (0.09 ≤ x ≤ 0.50) were characterised by means of elemental analysis, PXRD, transmission electron microscopy (TEM, EDX and SAED) and UV-Vis absorption spectroscopy. The presence and alloying of metallic Cu and Zn in the β-CuZn sample as a representative example of the series was confirmed by extended X-ray absorption fine structure spectroscopy (EXAFS). The oxidation behaviour of the nanoparticles was investigated by EXAFS, PXRD and UV-Vis spectroscopy indicating, that CuOx@Cu core–shell type particles were formed for pure copper particles, while in the case of brass particles preferential oxidation of the Zn component takes place, which results in core–shell particles of the type (ZnO)δ@Cu1−xZnx−δ.

Organic molecular-beam deposition of perylene on Cu(110): Results from near-edge x-ray absorption spectroscopy, x-ray photoelectron spectroscopy, and atomic force microscopy

The growth of the polycyclic aromatic hydrocarbon perylene on (110) oriented copper substrates has been studied by means of x-ray photoelectron spectroscopy, near-edge x-ray absorption spectroscopy, and atomic force microscopy. In the monolayer regime, the molecules are orientated with their molecular plane parallel to the substrate, whereas they adopt a tilted arrangement in multilayer films. For multilayers with thicknesses exceeding 10 nm, the molecules grow in a bulk-like structure with their long axes orientated upright to the substrate surface.

Electrochemically deposited Pd islands on an organic surface: the presence of Coulomb blockade in STM I(V) curves at room temperature

Palladium islands with a thickness of a few monolayers were deposited on top of a self-assembled monolayer (SAM) fabricated from 4-mercaptopyridine. In the I(V) curves obtained using the scanning tunneling microscope (STM) clearly the signature of Coulomb blockade is observed, explicitly demonstrating that these islands are coupled to the underlying gold substrate only via a tunneling barrier; this spectroscopic feature also allows to distinguish the palladium islands from similar morphological features present on the gold substrate prior to palladium deposition.