Adnan Sarfraz

High‐Concentration Graphene Dispersions with Minimal Stabilizer: A Scaffold for Enzyme Immobilization for Glucose Oxidation

Modified acrylate polymers are able to effectively exfoliate and stabilize pristine graphene nanosheets in aqueous media. Starting with pre-exfoliated graphite greatly promotes the exfoliation level. The graphene concentration is significantly increased up to 11 mg mL(-1) by vacuum evaporation of the solvent from the dispersions under ambient temperature. TEM shows that 75 % of the flakes have fewer than five layers with about 18 % of the flakes consisting of monolayers. Importantly, a successive centrifugation and redispersion strategy is developed to enable the formation of dispersions with exceptionally high graphene-to-stabilizer ratio. Characterization by high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy shows the flakes to be of high quality with very low levels of defects. These dispersions can act as a scaffold for the immobilization of enzymes applied, for example, in glucose oxidation. The electrochemical current density was significantly enhanced to be approximately six times higher than an electrode in the absence of graphene, thus showing potential applications in enzymatic biofuel cells.

Zinc oxide as a defect-dominated material in thin films for photovoltaic applications – experimental determination of defect levels, quantification of composition, and construction of band diagram

In the present work, thin ZnO layers were synthesized by the sol-gel method with subsequent spin-coating on Si(100). We show that the detailed analysis of lab-recorded photoemission spectra in combination with Kelvin probe data yielded the work function, ionization energy, and valence band - Fermi level separation - and hence enabled the construction of band diagrams of the examined layers. With small modifications in preparation, very different films can be obtained. One set shows a homogeneous depth-dependent n carrier distribution, and another a significant carrier concentration gradient from n-type conductivity to almost metal-like n(+) character. Likewise, the surface morphology can be tuned from a uniform, compact surface with spherical single-nm sized grain-like features to a structured surface with 5-10 nm tall crystallites with (002) dominating crystal orientation. Based on the band-bending and the energy levels observed, defects of contradictory nature, i.e. acceptor-donor-trap (ADT) properties, were identified. These defects may be groups of point defects, with opposite character. The ADT states affect the energy levels of the oxide layers and due to their nature cannot be considered in the photoemission experiment as mutually independent. The versatile nature of the synthesis provides us with the opportunity to tune the properties with a high degree of freedom, at low processing costs, yielding layers with an exotic electronic structure. Such layers are interesting candidates for applications in photovoltaic and nanoelectronic devices.

First seconds in a building's life-in situ synchrotron X-ray diffraction study of cement hydration on the millisecond timescale.

Setting cement: highly dynamic hydration processes that occur during the first seconds of cement hydration were studied by time-resolved synchrotron X-ray diffraction. Polycarboxylate ether additives were found to influence the formation of the initial crystalline hydration products on a molecular level.

Synthesis of Ultrathin Poly(methyl methacrylate) Model Coatings Bound via Organosilanes to Zinc and Investigation of Their Delamination Kinetics

Polymer coatings are widely used to protect metals from corrosion. Coating adhesion to the base material is critical for good protection, but coatings may fail because of cathodic delamination. Most of the experimental studies on cathodic delamination use polymers to study the corrosion behavior under conditions where the interfacial chemistry at the metal(oxide)/polymer interface is not well-defined. Here, ultrathin linear and cross-linked poly(methyl methacrylate) [PMMA] coatings that are covalently bound to oxide-covered zinc via a silane linker have been prepared. For preparation, zinc was functionalized with vinyltrimethoxysilane (VTS), yielding a vinyl monomer-covered surface. These samples were subjected to thermally initiated free radical polymerization in the presence of methyl methacrylate (MMA) to yield surface-bound ultrathin PMMA films of 10-20 nm thickness, bound to the surface via Zn-O-Si bonds. A similar preparation was also carried out in the presence of different amounts of the cross-linkers ethylene glycol diacrylate and hexanediol diacrylate. Functionalized and polymer-coated zinc samples were characterized by infrared (IR) spectroscopy, secondary ion mass spectrometry (SIMS), ellipsometry, and X-ray photoelectron spectroscopy (XPS). Coating stability toward cathodic delamination has been evaluated by scanning Kelvin probe (SKP) experiments. In all cases, the covalently linked coatings show lower delamination rates of 0.02-0.2 mm h(-1) than coatings attached to the surface without covalent bonds (rates ∼10 mm h(-1)). Samples with a higher fraction of cross-linker delaminate slower, with rates down to 0.03-0.04 mm h(-1), compared to ∼0.3 mm h(-1) without cross-linker. Samples with longer hydrophobic alkyl chains also delaminate slower, with the lowest observed delamination rate of 0.028 mm h(-1) using hexanediol diacrylate. For the coatings studied here, delamination kinetics is not diffusion limited, but the rate is controlled by a chemical reaction. Several possibilities for the nature of this reaction are discussed; radical side reactions of the oxygen reduction are the most likely path of deadhesion.

A wall-free climate unit for acoustic levitators

Acoustic levitation represents the physical background of trapping a sample in a standing acoustic wave with no contact to the wave generating device. For the last three decades, sample holders based on this effect have been commonly used for contact free handling of samples coupled with a number of analytical techniques. In this study, a wall-free climate unit is presented, which allows the control of the environmental conditions of suspended samples. The insulation is based on a continuous cold/hot gas flow around the sample and thus does not require any additional isolation material. This provides a direct access to the levitated sample and circumvents any influence of the climate unit material to the running analyses.

Surface Functionalization of Oxide-Covered Zinc and Iron with Phosphonated Phenylethynyl Phenothiazine.

Phenothiazines are redox-active, fluorescent molecules with potential applications in molecular electronics. Phosphonated phenylethynyl phenothiazine can be easily obtained in a four-step synthesis, yielding a molecule with a headgroup permitting surface linkage. Upon modifying hydroxylated polycrystalline zinc and iron, both covered with their respective native oxides, ultrathin organic layers were formed and investigated by use of infrared (IR) reflection spectroscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), contact angle measurement, and ellipsometry. While stable monolayers with upright oriented organic molecules were formed on oxide-covered iron, multilayer formation is observed on oxide-covered zinc. ToF-SIMS measurements reveal a bridging bidentate bonding state of the organic compound on oxide-covered iron, whereas monodentate complexes were observed on oxide-covered zinc. Both organically modified and unmodified surfaces exhibit reactive wetting, but organic modification makes the surfaces initially more hydrophobic. Cyclic voltammetry (CV) indicates redox activity of the multilayers formed on oxide-covered zinc. On the other hand, the monolayers on oxide-covered iron desorb after electrochemical modifications in the state of the oxide, but are stable at open circuit conditions. Exploiting an electronic coupling of phenothiazines to oxides may thus assist in corrosion protection.

Optical absorption spectroscopy at interfaces

This chapter summarises the physical principles of optical absorption spectroscopy and its use for the characterisation of surfaces and interfaces. After a brief discussion of the fundamentals of absorption spectroscopy and its relation to quantum mechanics, the chapter discusses the basics of optics at interfaces, focusing on the absorption of light by molecules in the interfacial region. Because of fundamental similarities, the chapter will touch on spectroscopy of both electronic and vibrational transitions, with a strong focus on infrared absorption experiments. There is a brief discussion, with reference to examples, of experiments in internal and external reflection geometry, including a brief discussion of the measurement of spectra on different classes of substrates (metallic vs. transparent).

Towards monomaterial p-n junctions: Single-step fabrication of tin oxide films and their non-destructive characterisation by angle-dependent X-ray photoelectron spectroscopy

The application of a non-destructive method for characterization of electronic structure of an ultra-thin SnO1<x<2 layer synthesized by spin coating on Si wafers was demonstrated. Utilizing angle dependent XPS, we quantified stoichiometry changes inside the SnO1<x<2 layers of thickness comparable with the electron attenuation length. The O/Sn concentration varied from 1.25 near the SnOx surface to 1.10 near the substrate/overlayer interface. Deviations from ideal stoichiometry are caused by defects, and defect levels affect the band structure of the SnOx layers. By investigation of the valence band region, followed by main core level position tracking, changes of electronic parameters like energy levels shift were identified. The results indicated a downward energy levels shift by 0.45 eV in SnOx layers at the SiO2/SnOx interface. In combination with the detected upward energy levels shift in the substrates electronic structure, these results suggest a negative charge displacement across the SiO2 layer. ...

Gradient in defect density of ZnO nanorods grown by cathodic delamination, a corrosion process, leads to end-specific luminescence

ZnO nanorods were grown on a zinc substrate via cathodic delamination of a polymer coating, a tailored corrosion process, at room temperature. A comparison between in situ Raman spectra and post mortem cross sectional analysis by Raman spectroscopy, photoluminescence spectroscopy and scanning electron microscopy shows that in the initial stages of the synthesis, preferentially defect rich ZnO grows. At later stages, crystalline wurtzite ZnO growth dominates. The result is nanorod arrays consisting of nanorods with a large density of point defects in the ≈500 nm range near the zinc substrate, and low defect density in the regions further away from the interface. The growth, which proceeds over several hours, can be interrupted at any time. Large salt concentrations in the corrosive medium increase the growth rate, but also the amount of point defects. The resulting rods show strongly position-dependent luminescence and Raman spectra. Different luminescence can thus be selectively excited, based on the position of excitation.

Cyclodextrin inhibits zinc corrosion by destabilizing point defect formation in the oxide layer

Corrosion inhibitors are added in low concentrations to corrosive solutions for reducing the corrosion rate of a metallic material. Their mechanism of action is typically the blocking of free metal surface by adsorption, thus slowing down dissolution. This work uses electrochemical impedance spectroscopy to show the cyclic oligosaccharide β-cyclodextrin (β-CD) to inhibit corrosion of zinc in 0.1M chloride with an inhibition efficiency of up to 85%. Only a monomolecular adsorption layer of β-CD is present on the surface of the oxide covered metal, with Raman spectra of the interface proving the adsorption of the intact β-CD. Angular dependent X-ray photoelectron spectroscopy (ADXPS) and ultraviolet photoelectron spectroscopy (UPS) were used to extract a band-like diagram of the β-CD/ZnO interface, showing a large energy level shift at the interface, closely resembling the energy level alignment in an n–p junction. The energy level shift is too large to permit further electron transfer through the layer, inhibiting corrosion. Adsorption hence changes the defect density in the protecting ZnO layer. This mechanism of corrosion inhibition shows that affecting the defect chemistry of passivating films by molecular inhibitors maybe a viable strategy to control corrosion of metals.