Academic year 2019/2020
- Course ID
- Prof. Silvia Bordiga (Lecturer)
Prof. Lorenzo Maschio (Lecturer)
Dott. Elena Clara Groppo (Lecturer)
- Degree course
- Master's Degree in Materials Science
- 1st year
- Course disciplinary sector (SSD)
- CHIM/02 - chimica fisica
- Class Lecture
- Type of examination
- Written and oral
- Solid basis in physics and chemistry, atomic structure, chemical bond, termodinamicand thermochemistry,
crystallography, knowledge ofspectroscopies
Sommario del corso
The goal in the first part of the course is to give general tools for multielectronic wave function building. In the second part the main goal is to supply theoretical tools and experimental methods for understanding the phenomena occurring at the surfaces of the materials, from adsorption to reactivity.
Understanding of the leading factors of the inter-electronic interaction, and knowledge of the most diffuse theoretical techniques for their study.
Ability to foresee, understand and study by the suitable experimental techniques the liquid-liquid, solid-solid and in particular solid-gas interface phenomena. It is expected that the student will learn the basic principles at the basis of catalysis: types of activation of simple molecules by homogeneous systems and by surfaces, and why; which are the factors affecting the reactivity at the surfaces of different kind of materials.
– Materials quantum chemistry.
– The multielectronic problem. Mono and multi-electronic functions; detor and antisymmetry.
– Terms in the hamiltonian. Mono and multi particle angular momentum operators.
– The Hartree-Fock method and equation. Matrix elements among detors: the Slater rules. The configuration Interaction, The Brillouin theorem. The Moeller Plesset perturbative scheme and the Coupled Cluster method. The Density Functional Theory.
– Finite Groups and selection rules for the matrix elements of the hamiltonian. Projector Operator; Band theory; reciprocal space and first Brillouin zone. Bloch functions and Bloch theorem.
– The Fermi level and Fermi surface. The multi-electronic problem for crystalline systems.
1) Interface phenomena.
viscosity, surface and interfacial tension, capillarity. Solid-gas interface
The adsorption phenomenon: elementary thermodynamic aspects of the adsorption process and their experimental evaluation.
Physisorption: BET model, surface area, surface porosity and their determination.
Chemisorption: main isotherm models for its description and information that could arise from. Molecular and dissociative chemisorption on metals, oxides, reducible oxides, and on metal-oxide nanocomposites: electronic effects, cumulative and depletive chemisorption.
Nanoparticles: structure, thermodynamic, surface tension
Thermodynamic consideration at the metal-oxide interface (adhesion, mutual wettability, oxide reducibility), electronic effects at the metal-semiconductor interface.
Experimental methods for the characterization of metal-oxide systems able to catalyze reactions between gases: evaluation of the support role and of the metal particle size role.
2) Reactivity at the surfaces of materials
Reactivity at single-sites
a) Homogeneous complexes as “perfect” single-sites
- The Wilkinson catalyst for hydrogenation reactions; the activation of the hydrogen molecule by a single-metal site
- Metallocene complexes for olefin polymerization; activation of ethylene molecule
b) Heterogeneous single-sites
- protonic zeolites: the oligomerization of molecules with double and triple bonds
- TS-1: selective oxidation reactions; the role of titanium in the activation of the oxidant (H2O2);
- the Phillips catalyst Cr/SiO2 for ethylene polymerization.
Reactivity at metal surfaces
a) Reactivity of extended metal surfaces (single crystals)
b) From single crystals to nanoparticles
c) Hydrogenation of hydrocarbons and how to induce selectivity.
Reactivity at metal-oxides
a) Bulk and surface properties of metal oxides
b) Reactivity of metal-oxides having insulating behavior
- Silica and silica-based materials
- magnesium oxide
c) Reactivity of metal-oxides having semi-conducting behavior
- zinc oxide
- titanium dioxide
Reactivity of metal chlorides
Ziegler-Natta catalysts for olefin polymerization as an example of complex systems.
Lessons: 56 hours;
Laboratory: 16 hours
Total: 72 hours.
The attendance at the lessons is not compulsory. The attendance at the laboratory is compulsory and cannot be less than 70% of the total.
Learning assessment methods
The exam is separated in two parts.
The first part of the exam (Prof. Maschio) is written.
The second part (Profs. Bordiga and Groppo) is oral. The student should be able to elaborate the results of the experiments performed in the lab in the form of graphs and to comment them. Starting from this preliminary discussion, additional questions will be done, in order to verify the knowledge of the topics developed during lessons.
The mark will result as the average of the two parts, expressed in thirties.
Italian students may sustain the exam in italian.
Suggested readings and bibliography
Slides and notes given by the professors