In situ scanning tunneling microscopy studies of nanometer size palladium particles on highly oriented pyrolytic graphite

A special electrodeposition process of palladium was studied by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS) and in situ scanning tunneling microscopy (STM). A kind of palladium(IV) complex was attached to the highly oriented pyrolytic graphite (HOPG) electrode surface by electro-oxidation of palladium(II) complex first, and was then reduced to palladium particles. The surface complexes and particles of palladium were both characterized by in situ STM and XPS. The Pd particles are in the nanometer range of size and exhibit electrocatalytic activity towards the oxidation of hydrazine and hydroxylamine.

Tip-induced dynamic characterization of multilayers and variable morphologies of cytochrome c molecules on highly oriented pyrolytic graphite revealed by in-situ scanning tunnelling microscopy

The dynamic states of cytochrome c multilayers on electrochemically pretreated highly oriented pyrolytic graphite (HOPG) have been studied by in-situ scanning tunnelling microscopy (STM) under potential control of both the tip and the substrate in cytochrome c and phosphate buffer solution. The dynamic characterization of cytochrome c multilayers and relatively stable adsorbed single cytochrome c molecules scattered on HOPG imply that physically adsorbed multilayers were more easily influenced by the STM tip than those of chemically adsorbed single molecules. In-situ STM images of chemically adsorbed cytochrome c molecules with discernible internal structures on HOPG revealed that morphologies of cytochrome c molecules also suffered tip influence; possible tip-sample-substrate interactions have been discussed.

Crystallization of syndiotactic polypropylene (sPP) from oriented melts

The influence of the syndiotacticity on the crystallization behaviour of syndiotactic polypropylene (sPP) has been investigated. The syndiotacticity has been measured by C-13-NMR spectroscopy and the phase formation has been observed by electron diffraction of oriented samples. It is shown that the crystal phase formation depends strongly on the perfection of the tacticity of the macromolecules.

Effect of lamellar thickness on the epitaxial crystallization of PE on oriented iPP films

The effects of lamellar thickness on the epitaxial crystallization of polyethylene on the oriented isotatic polypropylene have been studied by means of transmission electron microscopy. The results obtained from the bright field electron microscopy and electron diffraction show that the epitaxial orientation of the PE crystals on the iPP substrate depends not only on the thickness of the oriented iPP lamellae, but also on the lamellar thickness of PE crystals. No epitaxial orientation relationship between PE crystal and iPP substrate can be found, when the PE crystals are thicker than the lamellar thickness of iPP along the matching direction. This suggests, that the epitaxial nucleation of PE in the PE/iPP epitaxial system is controlled not only by the chain-row matching, but also by a secondary nucleation process.

STM image of tungstosilicic acid molecular layer on highly oriented pyrolytic graphite

Molecular layer of tungstosilicic acid (H4SiW12O40) deposited on freshly-cleaved highly oriented pyrolytic graphite (HOPG) was observed by scanning tunneling microscopy (STM) in air at room temperature. The molecular dimension (11.5 Angstrom) of H4SiW12O40 measured by STM is consistent with known crystallographic parameter. We also imaged the boundary of H4SiW12O40 molecular layer on HOPG showing that molecular layer of H4SiW12O40 was formed. It has been proved that individual tungstosilicic acid species is imaged. The probable reason for the formation of the molecular layer is also discussed.

EFFECTS OF ANODIC-OXIDATION ON THE SURFACE-STRUCTURE OF HIGHLY ORIENTED PYROLYTIC-GRAPHITE REVEALED BY IN-SITU ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY IN H2SO4 SOLUTION

Effects of the potential of anodic oxidation and of potential cycling on the surface structure of a highly oriented pyrolytic graphite (HOPG) electrode were observed by in situ electrochemical scanning tunnelling microscopy (ECSTM) in dilute H2SO4 solution with atomic resolution. With potential cycling between -0.1 V and 1.8 V vs. Ag/AgCl (sat. KCI), some atoms on the top layer of HOPG protrude out of the base plane, and the graphite lattice of these protrusions is still intact but is strained and expanded. With further potential cycling, some protrusions coalesced and some grew larger, and an anomalous superperiodic feature was observed (spacing 90 Angstrom with a rotation 30 degrees relative to atomic corrugations) which superimposed on the atomic corrugation of HOPG. On the topmost of these protrusions, some atoms form oxides and others are still resolved by the ECSTM image. With potential cycling between -0.1 V and + 2.0 V vs. Ag/AgCl (sat. KCl), damage to freshly cleaved HOPG surface is more serious and fast, some ridges are observed, the atomic structure of the HOPG surface is partially and then completely damaged due to the formation of oxide. We also found that anodic oxidation occurred nonuniformly on the surface of HOPG near defects during potential cycling.

EPITAXIAL BEHAVIOR OF HDPE ON THE BOUNDARY OF HIGHLY ORIENTED IPP SUBSTRATES

The epitaxial crystallization behavior of high-density polyethylene on the boundary of highly oriented isotactic polypropylene (iPP) substrates has been investigated by means of atomic force microscopy (AFM) and transmission electron microscopy (TEM). The results obtained from AFM and TEM indicate that the epitaxial nucleation of HDPE on the highly oriented iPP substrates occurs earlier than that in the pure HDPE phase, i.e., homogeneous nucleation. Therefore the epitaxially grown HDPE lamellae can grow across the boundary of the iPP substrate into the HDPE spherulitic phase with the epitaxial orientation relationship remaining.

IN-SITU SCANNING-TUNNELING-MICROSCOPY IMAGE OF A HIGHLY ORIENTED PYROLYTIC-GRAPHITE ELECTRODE MODIFIED WITH POTASSIUM BIS(11-MOLYBDOSILICATO) DYSPROSATE(III) IN SODIUM-SULFATE SOLUTION

The variation in molecule adsorption mode on pretreated highly oriented pyrolytic graphite electrodes, modified with the title complex K10H3[Dy(SiMo11O39)(2)] by cyclic voltammetry in the title complex solution, was observed in situ by electrochemical scanning tunnelling microscopy (ECSTM) with molecular resolution in sodium sulphate solution. According to the ECSTM images and the known molecular structure we conclude that the adsorption mode of the title complex modified electrode changed during potential cycling from ''vertical'' to ''inclined'' and then ''horizontal'' or ''flat'' mode, i.e. the title complex adsorbed on the surface of electrode by one ligand of the complex at first, then began to incline and was finally adsorbed by two ligands of the complex. This result indicates that the adsorption mode on the modified electrode surface changed during potential cycling in the sulphate solution and a much more stable molecular layer was formed. The change in adlattice of adsorbates on the modified electrode surface from hexagonal to rectangular was also observed by ECSTM. A plausible model was given to explain this process.

STM OF FOLDED AND UNFOLDED HEMOGLOBIN MOLECULES ELECTROCHEMICALLY DEPOSITED ON HIGHLY ORIENTED PYROLYTIC-GRAPHITE

The structural characterization of folded and unfolded haemoglobin has been performed by scanning tunnelling microscopy (STM) for the first time. STM images show an oval-shaped pattern for the folded structure of this protein, and moreover two dimers consisting of one haemoglobin molecule can be clearly discerned. The dimensions of a folded molecule were determined as 6.4 x 5.4 x 0.7 nm(3), which are in good agreement with the known size obtained from X-ray analysis. We have found that unfolding of haemoglobin molecules on the surface of highly oriented pyrolytic graphite (HOPG) can be achieved by electrochemical deposition. The STM analysis indicates clearly that the tertiary structure of the protein was lost by electrochemical deposition, and most of the haemoglobin molecules were almost fully extended and exhibited a twisted rope-like or a rod-like aggregated structure. Our investigation demonstrates the capability of the electrochemical method in denaturing this redox protein and in preparing stable biological samples for use in STM imaging.

EFFECTS OF CRYSTALLIZATION RATES ON INTERFACE LAYER THICKNESS OF EPITAXIAL HDPE ON ORIENTED IPP

The effect of crystallization rate on the epitaxial interface layer thickness of high-density polyethylene (HDPE) in the epitaxial system with oriented isotactic polypropylene (iPP) has been investigated by electron microscopy. The results of bright-field

INFLUENCE OF ESTER GROUP-SIZE IN PMAS ON BETA-PHASE CRYSTALLIZATION OF PVF2 IN HIGHLY ORIENTED FILMS OF PVF2/PMAS BLENDS

Influence of ester group size in polymethacrylates (PMAs) , including PMMA, PEMA and PBMA, on beta phase crystallization of poly(vinylidene fluoride) (PVF2) in highly oriented films of PVF2/PMAs=80/20 blends has been investigated by FTIR and TEM. The melt-drawn films of pure PVF2 consist of highly oriented lamellae, in which the alpha phase is predominant. Adding a given amount of PMAs (20 wt%) into PVF2 results in formation of fibrillar crystals and increase of relative amount of the beta phase. The influence extent is in order of PMMA > PEMA > PBMA, regarding the ester group size in the PMAs.

EPITAXIAL CRYSTALLIZATION OF TRANS-1,4-POLYBUTADIENE ON HIGHLY ORIENTED ISOTACTIC POLY(PROPYLENE) FILMS

Epitaxial crystallization of trans-1,4-polybutadiene (PBD) on highly oriented isotactic poly(propylene) (iPP) has been investigated at different crystallization temperatures and rates. From electron microscopy and electron diffraction, it is confirmed that epitactic growth of the low-temperature modification (monoclinic) with microcrystals of PBD on the iPP films takes place with their chain directions about +/- 50-degrees apart. No epitaxial relationship occurs between the high-temperature modification (hexagonal) of PBD and the iPP substrate. Thermal analyses of PBD-PP layered films indicate that the epitaxy has an important effect on the formation of the high-temperature modification of PBD.