Synthesis and Characterization of Double Metal Hexacyanoferrates

Manganese Hexacyanoferrate (MnHCF) and nickel doped manganese hexacyanoferrate were synthesized by simple co-precipitation method. The water content and chemical formula was obtained by TGA and MP-AES measurements, functional groups by FT-IR analysis, the crystal structure by PXRD and a local geometry by XAS. Elemental species of cycled samples were further investigated by TXM and 2D XRF. Electrochemical tests were performed in the glass cell. With addition of nickel, vacancies and water content increased in the sample. Crystal structure changed from monoclinic to cubic. Ni disturbed the local structure of Mn, site, however, almost no change was observed in Fe site. After charge/discharge cycling of MnHCF intercalation was already found in the peripheries of charged species after 20 cycle in 2D XRF analysis and randomly distributed intercalated regions after 50 cycles in TXM analysis. Cyclic voltammetry showed that peak-to-peak separation is increasing in case of the addition of Ni to MnHCF.

Synthesis and surface characterization of metal (Mn, Ti) hexacyanoferrate electrodes

Due to the limited resources of lithium, new chemistries based on the abundant and cheap sodium and even zinc have been proposed for the battery market. Prussian Blue Analogues (PBAs) are a class of compounds which have been explored for many different applications because of their intriguing electrochemical and magnetic properties. Manganese and titanium hexacyanoferrate (MnHCF and TiHCF) belong to the class of PBAs. In this work, MnHCF and TiHCF electrodes were synthetized, cycled with cyclic voltammetry (CV) in different setups and subsequently, the surfaces were characterized with X-ray Photoelectron Spectroscopy (XPS). The setups chosen for CVs were coin cell with zinc aqueous solution for the MnHCF series, three-electrode cell and symmetric coin cell with sodium aqueous solution for the TiHCF series. The electrodes were treated with different number of cycles to evaluate the chemical changes and alterations in oxidation states during cycling.

Synthesis, characterization and catalytic performances of ruthenium-based catalysts for the acceptorless dehydrogenative coupling of butanol

A growing interest towards new sources of energy has led in recent years to the development of a new generation of catalysts for alcohol dehydrogenative coupling (ADC). This green, atom-efficient reaction is capable of turning alcohol derivatives into higher value and chemically more attractive ester molecules, and it finds interesting applications in the transformation of the large variety of products deriving from biomass. In the present work, a new series of ruthenium-PNP pincer complexes are investigated for the transformation of 1-butanol, one of the most challenging substrates for this type of reactions, into butyl butyrate, a short-chain symmetrical ester widely used in flavor industries. Since the reaction kinetics depends on hydrogen diffusion, the study aimed at identifying proper reactor type and right catalyst concentration to avoid mass transfer interferences and to get dependable data. A comparison between catalytic activities and productivities has been made to establish the role of the different ligands bonded both to the PNP binder and to the ruthenium metal center, and hence to find the best catalyst for this type of reaction.

Study of Co-based hydrotalcite-derived mixed metal oxides partially modified with silver as potential catalysts for N2O decomposition

Co-Al-Ox mixed metal oxides partially modified with Cu or Mg, as well as Ag were successfully prepared, characterized and evaluated as potential catalysts for the N2O decomposition. The materials were characterized by the following techniques: X-Ray Diffraction, Thermogravimetric Analysis (TGA), N2 Physisorption, Hydrogen Temperature-Programmed Reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS). Ag-modified HT-derived mixed oxides showed enhanced activity compared to the undoped materials, the optimum composition was found for (1 wt.% Ag)CHT-Co3Al. The catalyst characterization studies suggested that the improved catalytic activity of Ag-promoted catalysts were mainly because of the altered redox properties of the materials.

Synthesis, Characterization, and Applications of a Novel Cu(II)-MOF Based on a Propargylcarbamate-Functionalized Isophthalate Ligand

This work describes the synthesis of a propargylcarbamate-functionalized isophthalate ligand and its use in the solvothermal preparation of a new copper(II)-based metal organic framework named [Cu(1,3-YBDC)]ˑxH2O (also abbreviated as Cu-MOF. The characterization of this compound was performed using several complementary techniques such as infrared (ATR-FTIR) and Raman spectroscopy, X-ray powder diffraction spectroscopy (PXRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS) as well as thermal and surface area measurements. Synchrotron X-ray diffraction analysis revealed that this MOF contains a complex network of 5-substituted isophthalate anions bound to Cu(II) centers, arranged in pairs within paddlewheel (or “Chinese lantern”) structure with a short Cu…Cu distance of 2.633 Å. Quite unexpectedly, the apical atom in the paddlewheel structure belongs to the carbamate carbonyl oxygen atom. Such extra coordination by the propargylcarbamate groups drastically reduces the MOF porosity, a feature that was also confirmed by BET measurements. Indeed, its surface area was determined to be low (14.5 ± 0.8 m2/g) as its total pore volume (46 mm3/g). Successively the Cu-MOF was treated with HAuCl4 with the aim of studying the ability of the propargylcarbamate functionality to capture the Au(III) ion and reduce it to Au(0) to give gold nanoparticles (AuNPs). The overall amount of gold retained by the Cu-MOF/Au was determined by AAS while the amount of gold and its oxidation state on the surface of the MOF was studied by XPS. A glassy carbon (GC) electrode was drop-casted with a Cu-MOF suspension to electrochemically characterize the material through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The performance of the modified electrodes towards nitrite oxidation was tested by CV and chronoamperometry.

Catalytic reduction of organic pollutants using supported metal nanoparticles

Metal nanoparticle catalysts have in the last decades been extensively researched for their enhanced performance compared to their bulk counterpart. Properties of nanoparticles can be controlled by modifying their size and shape as well as adding a support and stabilizing agent. In this study, preformed colloidal gold nanoparticles supported on activated carbon were tested on the reduction of 4-nitrophenol by NaBH4, a model reaction for evaluating catalytic activity of metal nanoparticles and one with high significance in the remediation of industrial wastewaters. Methods of wastewater remediation are reviewed, with case studies from literature on two major reactions, ozonation and reduction, displaying the synergistic effects observed with bimetallic and trimetallic catalysts, as well as the effects of differences in metal and support. Several methods of preparation of nanoparticles are discussed, in particular, the sol immobilization technique, which was used to prepare the supported nanoparticles in this study. Different characterization techniques used in this study to evaluate the materials and spectroscopic techniques to analyze catalytic activities of the catalyst are reviewed: ultraviolet-visible (UV-Vis) spectroscopy, dynamic light scattering (DLS) analysis, X-ray diffraction (XRD) analysis and transmission electron microscopy (TEM) imaging. Optimization of catalytic parameters was carried out through modifications in the reaction setup. The effects of the molar ratio of reactants, stirring, type and amount of stabilizing agent are explored. Another important factor of an effective catalyst is its reusability and long-term stability, which was examined with suggestions for further studies. Lastly, a biochar support was newly tested for its potential as a replacement for activated carbon.

Synthesis and Characterization of Iron carbide carbonyl clusters

This study is focused on the synthesis, characterization and reactivity of new low nuclearity iron carbide carbonyl clusters. In particular, the oxidation of the highly reduced monocarbide tetraanionic cluster [Fe6C(CO)15]4- was studied in details using different oxidants ([Cp2Fe][PF6], HBF4·Et2O, MeI and EtI), different stoichiometries and experimental conditions. Different products were obtained depending on the reaction conditions, among which previously reported [Fe6C(CO)16]2- and [Fe5C(CO)14]2-, and new [Fe6C(CO)14(CO)13]4- and [Fe5C(CO)13(COMe)]3- were isolated and fully characterized. In the second part of this study, the reactions of [Fe6C(CO)15]4- with organic or inorganic molecules containing sulphur (S8, S2Cl2 and PhSH) were investigated aiming at introducing S-atoms within the structure of iron carbide carbonyl clusters. In particular, the reaction of [Fe6C(CO)15]4- with PhSH afforded the new [Fe6C(CO)14(SPh)]3- cluster. Conversely, using S8 and S2Cl2, oxidation of [Fe6C(CO)15]4- occurred following a path similar to that observed with other oxidizing agents. All these species have been analyzed by Single Crystal X-ray diffraction (SC-XRD) and IR spectroscopy.

Design, fabrication and mechanical characterization of a structural node made using Wire and Arc Additive Manufacturing (WAAM) technology

Additive Manufacturing (AM), also known as “3D printing”, is a recent production technique that allows the creation of three-dimensional elements by depositing multiple layers of material. This technology is widely used in various industrial sectors, such as automotive, aerospace and aviation. With AM, it is possible to produce particularly complex elements for which traditional techniques cannot be used. These technologies are not yet widespread in the civil engineering sector, which is slowly changing thanks to the advantages of AM, such as the possibility of realizing elements without geometric restrictions, with less material usage and a higher efficiency, in particular employing Wire-and-Arc Additive Manufacturing (WAAM) technology. Buildings that benefit most from AM are all those structures designed using form-finding and free-form techniques. These include gridshells, where joints are the most critical and difficult elements to design, as the overall behaviour of the structure depends on them. It must also be considered that, during the design, the engineer must try to minimize the structure's own weight. Self-weight reductions can be achieved by Topological Optimization (TO) of the joint itself, which generates complex geometries that could not be made using traditional techniques. To sum up, weight reductions through TO combined with AM allow for several potential benefits, including economic ones. In this thesis, the roof of the British Museum is considered as a case study, analysing the gridshell structure of which a joint will be chosen to be designed and manufactured, using TO and WAAM techniques. Then, the designed joint will be studied in order to understand its structural behaviour in terms of stiffness and strength. Finally, a printing test will be performed to assess the production feasibility using WAAM technology. The computational design and fabrication stages were carried out at Technische Universität Braunschweig in Germany.