Title: Electronics and adsorption properties of model catalytic systems contains cerium Author: Miloš Cabala Department: Department of Surface and Plasma Science, Supervisor: RNDr. Kateřina Veltruská, Department of Surface and Plasma Science, Abstract: The doctoral thesis contains the study of model catalyst systems based on cerium and ceria. The thesis deals with model systems of CeAg, CeO2/Cu(111), Ni- CeO2/Cu(111) a Ni-Sn-CeO2/Cu(111). We have studied these systems using photoelectron spectroscopy, ion scattering spectroscopy and low energy electron diffraction. Model systems were prepared under strictly defined conditions. The strong bimetallic interaction was observed on the CeAg layers. Molecular adsorption of carbon monoxide on CeAg was demonstrated. We also observed intensive reaction of these layers with oxygen. By measurements in different directions of surface Brillouin zone, we managed to reconstruct the band structure of the prepared CeO2/Cu(111) layer. We have shown that the Cu substrate interacts weakly with deposited CeO2 layer. This interaction results in a charge transfer from Cu into CeO2. Overall, in the valence spectrum we have identified three main electron bands corresponding to O 2p state bound in CeO2. It has been proven that the deposition of Ni on CeO2 layers leads to partial...

This work comprises studies addressing fundamental questions of the diamond surface physics for different doping concentrations of nitrogen and boron, and how doping is reflected in the core shell analysis, valance band structure and work function values. A second aspect of the work is the controllable creation of nitrogen-vacancy (NVs) centers accompanied by comprehensive surface spectroscopy studies (XPS,UPS and MIES). Additionally, in order to increase and stabilize NV negative (NV-), which are required for quantum computing system, studies on diverse oxygen termination procedures has been executed. The efficiency of oxygen termination procedures compared and is confirmed by spectroscopy and wet contact angle (WCA) measurements. Furthermore, an alternative method of hydrogen termination of the diamond surface is proposed and compared to the traditional hydrogen plasma termination. As related side aspect, the deposition of C60 molecules on the diamond surface is performed and investigated by means of UPS and MIES spectroscopy. A distinctive experimental capability of studies is the implementation of the Metastable Impact Electron Spectroscopy (MIES) spectroscopy. This unique surface spectroscopy technique and individual instrumentation design for probing the electronic structure of the outermost surface layer, including measurement examples is introduced in this work.

Doctoral thesis is dealing with the methods for analysis of surfaces by photoelectrons being emitted by X-ray radiation. The methods are: X-ray Photoelectron Spectroscopy - XPS, Angle-resolved XPS - ARXPS and X-ray Photoelectron Diffraction - XPD. The work is especially focused on a method of ARXPS, which is used for the depth compositional analysis of sample surfaces. To obtain an information about the depth composition from the measured ARXPS spectra, a calculation software in the Matlab environment has been developed. The software has been tested both for simulated and real sample data. For an experimental implementation of these methods, a complete manipulation system has been developed. It ensures the transport of samples inside a vacuum apparatus and the experiment itself. The system is controlled mainly by a software and enables to run the experiments automatically.

With the rapid increase in miniaturization of mechanical components, the need for a hard, protective coatings is of great importance. In this study we investigate some of the mechanical, chemical and physical properties of the SiCN thin films. Thin films of amorphous silicon carbide nitride (a-SiCxNy) were deposited in a RF magnetron sputtering system using a powder pressed SiC target. Films with various compositions were deposited on to silicon substrate by changing the N2/Ar gas ratios during sputtering. Nano-indentation studies were performed to investigate the mechanical properties such as hardness and reduced modulus of the SiCN films. Surface morphology of the films was characterized by using atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) data indicated that the chemical status is highly sensitive to the nitrogen ratios during sputtering. Further, the films were annealed in dry oxygen ambient in the temperature range of 400 – 900°C and characterized using XPS to investigate the chemical composition and oxidation kinetics at each annealing temperature. The surface roughness of these films was studied as a function of annealing temperature and film composition with the help of a "Veeco" optical profilometer. Nano-indentation studies indicated that the hardness and the reduced modulus of the film are sensitive to the N2/Ar ratio of gas flow during sputtering. AFM studies revealed that the films become smoother as the N2/Ar ratio is increased. XPS data indicated the existence of C-N phases in the as-deposited films. The study of oxidation kinetics of RF sputter deposited SiCN thin films, using XPS, suggest that N2 co-sputtering helps to suppress the formation of a surface oxide, by allowing un-bonded Si to bond with N and C inside the vacuum chamber as opposed to bonding with O in atmosphere.

Heavy metals, oxyanions (NO3-, PO4-), pharmaceuticals, and dyes in aquatic environments are inevitable economic and health concerns. Ingestion of these contaminants, even in trace amounts, causes long and short-term serious threats to human health. Conventional pollutant mitigation strategies can be costly or ineffective. Due to high efficiency, simplicity, low price, adsorbent reuse, and pollutant (e.g., phosphates) recovery, adsorption has been widely used for wastewater purification. Many efficient, environmentally compatible, and cost-effective sorbents have been successfully applied in environmental remediation. Chapter I is about characterization of graphene-coated pinewood biochar hybrids and evaluation of their copper removal performances. Here, we synthesized three types of pinewood biochar-graphene composites consisting of three different graphene precursors and compared their aqueous Cu2+ removal performances against raw pinewood biochar. To the best of our knowledge, no previous work has characterized the copper decontamination by graphene-biochar hybrids. Chapter II is about thermally- and chemically-treated lignite adsorbents for phosphate remediation. We engineered a cost efficient lignite system with co-precipitated Ca2+/Mg2+ followed by pyrolysis at 600 ⁰C to remediate aqueous phosphates. Micro-sized surface deposited oxide/hydroxide/carbonate particles promoted phosphate uptake of Ca2+/Mg2+-modified-lignite by 31 and 72 times, compared to thermally treated lignite (w/o a chemical treatment) and the raw lignite, respectively. The exhausted adsorbent can act as a slow-release fertilizer, which is comparable with commercial phosphate fertilizers. Chapter III is about synthesis of activated lignite [A-L], Ca2+-modified lignite [Ca-L], and Fe3O4 nanoparticle-loaded activated lignite (Fe3O4-A-L) for phosphate remediation. Even though A-L has a very high surface area (2854 m2/g), it did not achieve much phosphate sorption. Ca-L phosphate uptake was highest due to the high concentrations of surface deposited CaCO3, CaO, and Ca(OH)2. A pH-independent (from pH 5 to 9) phosphate removal was reported by highly basic Ca-L. However, the Ca2+ leaching was highest at pH 5. Precipitation of Ca2+ phosphates/hydrophosphates is the major phosphate removal mechanism of Ca-L. Fe3O4 and Fe2O3 sites of Fe3O4-A-L enhanced phosphate adsorption capacity, 8-fold versus A-L (67.6 mg/g vs 8.0 mg/g at 25 ºC). Fe3O4-A-L remediated phosphates via inner-sphere surface complexation and precipitation.

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This work represents an interdisciplinary effort to investigate microbiological and chemical manganese (Mn) cycling in drinking water systems using concepts and tools from civil and environmental engineering, microbiology, chemistry, surface science, geology, and applied physics. Microorganisms were isolated from four geographically diverse drinking water systems using selective Mn-oxidizing and -reducing culture media. 16S rRNA gene sequencing revealed that most are bacteria of the Bacillus spp. (i.e., Bacillus pumilus and Bacillus cereus). These bacteria are capable of performing Mn-oxidation and -reduction under controlled laboratory conditions. Pseudo-first order rate constants obtained for microbiological Mn-oxidation and -reduction (aerobic and anaerobic) of these isolates ranged from 0.02 - 0.66 days⁻¹. It is likely that spores formed by Bacillus spp. protect them from chlorine and other disinfectants applied in drinking water systems, explaining their ubiquitous presence. A new method was developed using X-ray photoelectron spectroscopy (XPS) to identify Mn(II), Mn(III), and Mn(IV) on the surfaces of pure oxide standards and filtration media samples from drinking water treatment plants. A necessary step for the comprehensive analysis of Mn-cycling in drinking water systems is to characterize the chemical properties of filtration media surfaces. Analyses of filtration media samples show that, while Mn(IV) was predominant in most samples, a mixture of Mn(III) and Mn(IV) was also identified in some of the filtration media samples studied. The use of both the XPS Mn 3s multiplet splitting and the position and shape of the Mn 3p photo-line provide added confidence for the determination of the oxidation state of Mn in complex heterogeneous environmental samples. XPS was applied to investigate Mn(II) removal by MnOx(s)-coated media under experimental conditions that closely resemble situations encountered in drinking water treatment plants in the absence and presence of chlorine. Macroscopic and spectroscopic results suggest that Mn(II) removal in the absence of chlorine was mainly due to adsorption, while in the presence of chlorine was due to oxidation. Mn(IV) was predominant in all the XPS analyses while Mn(II) was detected only in samples operated without chlorine. Future research should apply XPS under different experimental conditions to understand the specific mechanisms affecting Mn(II) removal by MnOx(s)-coated media. / Ph. D.

The self-assembly blends of cellulose propionate (CP) and fluorine (F)-containing cellulose derivatives was examined on a model system of solvent cast films. The F-containing derivatives were either high molecular weight statistical cellulose esters with a number of F-containing substituent evenly distributed along the backbone (F-esters), or F-terminated CP-segments with exactly one F-containing endgroup. The F-esters were synthesized in a homogeneous phase and identified by 19F-NMR. Thermal analysis showed improved thermal stability of the F-esters when compared to F-free derivatives. 1-monohydroxy functionalized CP-segments were synthesized by HBr depolymerization using either a commercially available CP with residual OH-groups or a perpropionylated CP (CTP). The hydrolysis using the commercial CP yielded only segments of a minimum DP of 50 and the Mark-Houwink constant declined from 1 to 0.6. The results indicate that in the presence of free hydroxyls branches are formed by transglycosidation. The hydrolysis from perpropionylated CP resulted in segments with a minimum DP of 7, which is in accordance to previous studies. F-terminated CP segments were synthesized by coupling of the appropriate F-containing alcohol to the CP segment via toluene diisocyanate. Solutions containing F-terminated CP-segments showed typical critical micelle behavior. The critical micelle concentration depended on the molecular weight of the CP segment and the type of F-containing endgroup. The micelles are thought to consist of a core of the F-endgroups and a corona made-up of CP. Films containing the oligomers cast from micellar solution revealed a linear decrease in wetting force according to the blend composition of the oligomer, i.e. behavior according to the rule of mixing. This indicated the absence of surface segregation of the F-endgroup and it is explained with the fact that the micellar structure is retained in the solid state, suppressing surface segregation. The solid state micelles were visualized as dome-like protrusions by height image atomic force microscopy. In systems blended with CP the distance between the protrusions was found to increase with increasing CP content which was explained by a dilution process. Films containing F-esters were characterized by wetting force measurements and x-ray photoelectron spectroscopy (XPS). The wetting force decreased dramatically at low blend content of the F-ester and at the same time an F surface-concentration higher then expected from the blend composition was found by XPS. This indicated self-assembly by surface segregation of the F-containing species during film formation. The extent of surface segregation was found to depend on the type of the F-ester group as well as on the blend concentration of the F-ester. Dynamic wetting force measurements revealed hysteresis in films containing either F-esters or F-terminated CP segments. The hysteresis was found to be both kinetic (water sorption and reorganization) and thermodynamic (surface roughness and surface coverage with F-moieties) in nature. Consecutive force loops revealed an increase in the wetting force (advancing and receding) with increasing loop number, indicating the increased hydrophobicity of the surface. The force increase was determined to be due to water sorption as well as due to surface reorganization. An increase in the size of the F-groups signified a decrease in reorganization rate due to a decreased mobility of the group. The process of reorganization was fully reversible, a behavior which is congruent with the definition of smart behavior. / Ph. D.

Chapter 1 Dynamic Processes Occurring at the Cr^III_aq – Manganite (γ-MnOOH) Interface: Simultaneous Adsorption, Microprecipitation, Oxidation/Reduction and Dissolution The complex interaction between Cr^III_aq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10⁻⁴ to 10⁻² M CrOH²⁺_aq. Solution compositional changes during batch reactions were characterized by ICP and UVvis. The manganites were characterized before and after reaction with XPS, SEM, high-resolution FESEM, and EDS analysis. Fluid-cell AFM was used to follow these metal-mineral interactions in situ. The reactions are characterized by 1) sorption of Cr^III and the surface-catalyzed microprecipitation of Cr^III-hydroxy hydrate on manganite surfaces, 2) the acidic dissolution of the manganite, and 3) the simultaneous reductive dissolution of manganite coupled with the oxidation of Cr^III_aq to highly toxic Cr^VI_aq. Cr^III-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to faster acid-promoted and Mn-reduction- promoted dissolution. Due to direct redox coupling with Mn reduction, Cr oxidation was most rapid in the lower pH range. Neither Mn^II nor Cr^VI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, Cr^III_aq was effectively removed from solution to form Cr^III-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and Cr^VI_aq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals, and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites. Chapter 2 Comparison of the Reactivity of Various Mn-Oxides with Cr^III_aq: Microscopic and Spectroscopic Observations of Dissolution, Cr-sorption and Cr and Mn Redox Interactions The interaction between Cr^III_aq and seven different Mn-oxides (6 monomineralic, 1 synthetic) have been observed in pH ~4.4 HNO₃ and pH ~4.4 ~10⁴ M Cr^III_aq solutions. For each mineral-solution interaction, the aqueous chemical concentrations (e.g. [Mn]_aq, [Cr]_aq, [Cr^VI_aq]) were measured with time. Reacted samples were examined by XPS to determine if, and to what extent, the surface chemical states of Cr, Mn and O had changed. Microscopic observations of the reacted surfaces were obtained using AFM and high-resolution, low-voltage FESEM. The solubility of the Mn-oxides in the acidic, non-Cr bearing solutions varied inversely with the average Mn valence, but did not show systematic behavior with respect to the mineral structure type (e.g. tunnel, layer, framework). This trend was interpreted as resulting from the relative ability of an adsorbed proton to polarize surface Mn-O bonds, with the polarizability being in the order Mn²⁺-O > Mn³⁺-O > Mn⁴⁺-O. For samples reacted with Cr^III_aq, the rate and extent of reductive dissolution was always greater than for acidic dissolution during the initial time period. The measured ratios of the [Mn]_aq : [Cr^VI]_aq were approximately in agreement with the values expected from the proposed stoichiometric reactions. Cr-uptake was observed to occur in undersaturated solutions as a result of adsorption, absorption and surface catalyzed precipitation. The chromium as detected by XPS was predominately Cr^III, however pyrolusite contained both Cr^III and Cr^VI. Previous studies have implicated a chromium surface precipitate to be responsible for the cessation of the Cr^III_aq oxidation reaction. Our surface sensitive FESEM and AFM observations tend to suggest that Cr-uptake is by isolated site binding, very small (<30 nm) surface clusters or monolayer scale films. Cr-uptake was followed by slow Cr-release on several of the solids (particularly the layered solids) after a substantial portion of the total aqueous Cr had been converted to Cr^VI_aq. The oxidizing ability of the different Mn-oxides for Cr^III_aq is evaluated with regards to the energy level of the redox couple (i.e. the redox potential) as compared with the Fermi energy level of the Mn-oxide. Although these energies were calculated rather than directly measured, the results indicate that electrons originating from adsorbed Cr^III ions may be transferred into the conduction band or more likely, into available surface states. The presence of an initial limited quantity of electron accepting surface states likely explains the observation of a rapid initial Cr^III-oxidation followed by much slower oxidation. The Mn-oxides that exhibited the greatest and longest lasting Cr^III-oxidizing power were the Mn-oxides containing Mn⁺, and in particular those containing Mn³⁺ and Mn⁺. It is believed that the combined presence of a reducible Mn ion (e.g. Mn³⁺) and a highly soluble Mn⁺ ion facilitates a sustained Cr^III-oxidation reaction because fresh surface is exposed during the reaction. / Ph. D.

Commercial aluminum (Al) alloys are often precipitation strengthened to improve strength and wear resistance. However, localized corrosion due to the galvanic coupling between the precipitates and Al matrix often leads to degraded performance when these alloys are exposed to corrosive environment. In this work, Al-based solid solution was synthesized to simultaneously improve the strength and corrosion resistance of Al alloys, which ultimately led to high tribocorrosion resistance. Specifically, the effects of testing condition (e.g. sliding frequency) and alloying effects (e.g. Mn and Mo) on the corrosion and tribocorrosion behavior of Al-based binary and ternary solid solutions were studied. To understand the effects of wear condition on the depassivation-repassivation kinetics during tribocorrosion, in the first study, the tribocorrosion behaviors of Al-20 at.%Mn alloys were investigated in simulated seawater by changing the sliding frequency from 0.05 to 1 Hz in reciprocal motion. The results show that the depassivation rate of passive film increased with increasing sliding frequency. Mechanical wear also increased with increasing sliding frequency, which was mainly related to the increase of coefficient of friction and real contact area. Chemical wear tended to increase with scratching frequency, most likely due to faster repassivation kinetics at lower frequency. The surface layer was analyzed by cross-sectional transmission electron microscopy, indicating the passive film was primarily consisted of aluminum oxide where manganese was selectively dissolved. Despite extensive past research, the fundamental understanding of the alloying effects on the atomistic structure, composition, and chemical state of the passive layer of Al alloys and their formation mechanism is still not well understood. In the second study, the effects of Mn on the aqueous corrosion of Al-Mn alloys were investigated. It was confirmed that Mn alloying could enhance the corrosion resistance of Al without participating in the surface oxidation. Atom probe tomography analysis confirmed the absence of Mn in the anodized and corroded surface of Al-Mn alloys. The selective dissolution of Mn in these alloys was believed to increase the free volume at the metal/oxide interface to facilitate the formation of a denser, thinner oxide layer with closer to stoichiometry composition, leading to its enhanced corrosion resistance than pure Al. Lastly, to better understand the corrosion and tribocorrosion resistance of Al-based lightweight concentrated alloys and the effects of alloying concentrations on the structure and property of the passive layer, the third study investigated the effects of a passive element (Mo) and non-passive element (Mn) on the corrosion and tribocorrosion behavior of Al-Mn-Mo alloys. Specifically, Al80Mn8Mo12 exhibited higher corrosion resistance than Al80Mn20 due to the formation of a more compact and less defective passive film, as explained by the roles Mo played in both the substrate and the passive film. It was found that the pitting potential and corrosion current density of Al-Mn-Mo increased with Mo%. The effect of Mo alloying concentration on the tribocorrosion behavior of Al-Mn-Mo alloys was investigated as well. Adding Mo to Al-Mn alloys led to a lower wear and tribocorroison resistance of Al-Mn-Mo alloys. In addition, decreasing Mn and Mo concentrations resulted in a reduction of the tribocorrosion resistance in the ternary alloy, which was mainly dominated by the mechanical response under the selected testing conditions. / Doctor of Philosophy / Various critical current and future applications in the fields of aerospace, transportation, energy, and biomedical industries require not only a strong and tough metal, but one that is robust and reliable when interacting with some very corrosive environment. Such corrosive environment is testing the limits of most engineering metals and challenging the current understanding of the underlying degradation mechanism. For example, strength and wear resistance in most precipitation-hardened Al (aluminum) alloys is often achieved at the expense of sacrificed corrosion resistance, mainly due to micro-galvanic coupling between the soft matrix and hard precipitates. In addition, the performance of Al alloys deteriorates dramatically when there is combined wear and corrosion, i.e. tribocorrosion attack at the surface, due to the depassivation on the wear track as a result of mechanical removal of the passive film. Recent study shows that alloying Al with appropriate transition metals in supersaturated solid solution simultaneously improves the corrosion and wear resistance of Al. In this thesis, Al-Mn and Al-Mn-Mo solid solutions was synthesized and studied to understand the effects of testing condition (e.g. sliding frequency) and alloy composition (e.g. Mn and Mo concentration) on the corrosion and tribocorrosion behavior. First, the depassivation mechanism during tribocorrosion of Al-Mn alloys was investigated by performing tribocorrosion test using different sliding frequency from 0.05 to 1 Hz in 0.6 M NaCl aqueous solution. Results showed that both chemical and mechanical wear increased with increasing frequency. The mechanical wear increased with scratching frequency due to faster depassivation rate and increased real contact area, while chemical wear increased with frequency due to higher repassivation kinetics. Secondly, the effects of Mn on the aqueous corrosion and passivation of Al-Mn solid solution alloys were investigated by electrochemical experiments and advanced surface characterization. It was found that Mn addition enhanced the corrosion resistance of Al without participating in the surface oxidation. A denser, thinner oxide layer was formed on Al-Mn due to the increased free volume at the metal/oxide interface as a result of Mn dissolution. Lastly, the effects of alloying concentration on the aqueous corrosion and tribocorrosion of Al-Mn-Mo alloys were studied experimentally. The pitting potential and corrosion current density of Al-Mn-Mo were found to increase with Mo%. The passive film thickness depended on the total alloy concentration, while its compactness and defect density on the individual ones. The tribocorrosion resistance of Al-Mn-Mo alloys decreased with increasing Mn and Mo concentrations. In summary, the results from this thesis develop mechanistic understanding of the corrosion and tribocorrosion mechanisms of Al-based solid solution alloys, which sheds light on a new alloy design strategy for making lightweight, strong, and corrosion-resistant metals.