This course covers advanced principles of Nanochemistry with the emphasis on five typical nanomaterials: silica, gold, CdSe, iron oxides, and carbon. The lectures focus on the physico-chemical methods for the characterization of structure, morphology and properties of nanomaterials, on the relation between structure and properties of nanomaterials, and on the synthetic methods including self-assembly. Students will learn: • the principles of structural chemistry and selected structural types of compounds, they will be able to apply them to other structural problems; • mechanical, thermal, optical, electric, and magnetic properties of nanomaterials in correlation to their structure and judge new materials properties; • to employ a variety of physico-chemical methods for the characterization of structure, morphology and properties of nanomaterials; • to understand principles of advanced and new synthetic techniques for variety of nanomaterials; • to apply these synthetic methods to the fabrication new compounds and new morphologies;
Chapter 1. Introduction to Nanochemistry.
Size, shape, surface, self-assembly, defects in nanoobjects. Surface-to-bulk ratio effects, quantum confinement effects, definition of nanoregime.
Chapter 2. Instrumental techniques in Nanochemistry I.
Structure: SiO4 structural units, silicates, tridymite, cristobalite, quartz, stishovite. Glassy and crystalline state, thermodynamic and kinetic stability, metastability.
Surface: Silanols, surface chemical composition and reactivity, IR spectroscopy of surface species. Surface functionalization, anchoring of functional groups and catalytic centers. Hydrophilic and hydrophobic surfaces. HF etching of SiO2.
Size: Sol-gel preparation of silica, hydrolysis/condensation, alkoxides, TEOS. Acidic and basic catalysis. Colloides, nucleation, growth, polydispersity control. Surface charge, salt effect. Stoiber silica. Core/shell nanoparticles. Porosity, calcination, sintering.
Chapter 5. Silica II.
Shape: Templating. AAO pore arrays, infiltration, silica nanowires and nanotubes. Micelles, surfactants, CMC, mesoporous silica MCM, surface area, pore size and volume, nitrogen isotherm and BET, X-ray diffraction. Polystyrene spheres as template. Nanocomposites of silica matrix with metal oxide nanoparticles. Silica films by CVD. Silica fibers.
Self-assembly: Evaporation induced self-assembly, photonic crystals, opals and inverse opals, optical properties, stopgap, slow photons.
Defects: Intrinsic and extrinsic defects, 0, 1, 2, and 3 dimensional defects. Refraction and refractive index control in opals.
Chapter 6. Gold and metals I.
Structure: Crystal structures of metals: unit cell, close packing, ccp, hcp, bcc, crystallographic planes, Miller indices. Synthetic methods for metal nanoparticles. Vapor condensation routes. Reduction routes. Sonochemical routes. Ligand capping.
Surface: Self assembled monolayers (SAM) of thiols on Au, synthesis, structure, van der Waals forces. Modification of SAMs.
Chapter 12. Carbon, diamonds, fullerenes, nanotubes, graphene I.
Structure: Crystal structures of diamond. Synthetic methods for diamond, CVD, high-pressure route, hydrothermal, plasma method. Synthesis of carbon nanotubes, single-, double-, and multiwalled carbon nanotubes. Electrical properties.
Surface: Modification and functionalization of fullerene and nanotube surfaces. Halogenation, nitrene reactions, Bingels cyclopropanation reaction, oxidative cutting, wall- and end-functionalization, surfactants, solubility of CNT.
Chapter 13. Carbon, diamonds, fullerenes, nanotubes, graphene II.
Size: Nanodiamond density and mechanical properties, grain boundaries.
Shape: Synthesis of fullerenes, endohedral, exohedral, heterofullerens, open fullerenes, fullerides, carbynes, large fullerens, carbon onions.
Self-assembly: CNT bundling, mats. Graphene, graphite-peeling technique, graphite oxide exfoliation/reduction, SiC vacuum pyrolysis. Electrical properties, carrier mobility, single molecule detection. Graphene layers by spin and dip coating.
OZIN, Geoffrey A., André C. ARSENAULT a Ludovico CADEMARTIRI. Nanochemistry : a chemical approach to nanomaterials. 2nd ed. Cambridge: RSC Publishing, 2009. liii, 820. ISBN 9781847558954. info
CADEMARTIRI, Ludovico a Geoffrey A. OZIN. Concepts of nanochemistry. Edited by Jean-Marie Lehn. Weinheim: Wiley-VCH, 2009. xix, 261. ISBN 9783527325979. info
Nanoscale materials in chemistry. Edited by Kenneth J. Klabunde - Ryan Richards. 2nd ed. Hoboken, N.J.: Wiley, 2009. xiii, 777. ISBN 9780470222706. info
The course is taught in English. It consists of 13 lectures of 50 minutes each. Course materials, such as lecture slides, supplementary articles, tables, are available to students in the Information System of Masaryk University. Additional relevant lectures by visiting professors under INNOLEC program are part of the course in particular cases.
There are 3 graded homeworks during the semester. At the end of the course every student will give a short presentation on a selected topic concerning materials chemistry. Written final exam worth 100 pts, minimum 50 pts to pass. Weights: final test 75%, homeworks 15%, presentation 10%.
Předmět je vyučován každoročně.
Výuka probíhá každý týden.