C8888 Nanochemistry

Faculty of Science
Spring 2023
Extent and Intensity
1/0. 1 credit(s) (plus extra credits for completion). Recommended Type of Completion: zk (examination). Other types of completion: k (colloquium).
Teacher(s)
prof. RNDr. Jiří Pinkas, Ph.D. (lecturer)
Guaranteed by
prof. RNDr. Jiří Pinkas, Ph.D.
Department of Chemistry – Chemistry Section – Faculty of Science
Contact Person: prof. RNDr. Jiří Pinkas, Ph.D.
Supplier department: Department of Chemistry – Chemistry Section – Faculty of Science
Timetable
Mon 15:00–16:50 B11/305
Prerequisites
C7780 Inorganic Materials Chemistry
Thorough knowledge of principles and facts covered by the courses of Inorganic, Organic, Physical, and Materials Chemistry is required.
Course Enrolment Limitations
The course is also offered to the students of the fields other than those the course is directly associated with.
fields of study / plans the course is directly associated with
Course objectives
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.
Learning outcomes
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

Syllabus
  • Chapter 1. Introduction to Nanochemistry.
  • Size, shape, surface, self-assembly, defects in nanoobjects. Surface-to-bulk ration effects, quantum confinement effects, definition of nanoregime.
  • Chapter 2. Instrumental techniques in Nanochemistry I.
  • Microscopy Techniques (optical, SEM, TEM, AFM, STM) Diffraction Techniques (XRD, SAXS, SAED, neutron) Spectroscopic Techniques (IR, Raman, UV-vis, XPS, EDAX, EXAFS, NMR, MS, SIMS, RBS).
  • Chapter 3. Instrumental techniques in Nanochemistry II.
  • Magnetic Techniques (Moessbauer, magnetometry, SQUID) Separation Techniques (GC, GPC) Thermal Techniques (TG, DSC, DTA, EGA) Adsorption Techniques (BET, BHJ) Electrical Techniques (conductivity, Seebeck-Hall, zeta potential)
  • Chapter 4. Silica 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 7. Gold and metals II.
  • Size: Electrical conduction, dipole moment, plasmon, surface plasmon resonance, Mie theory, plasmon resonance frequency. Photothermal treatment, hyperthermia. Shape: Diffusion, galvanic replacement, synthesis of hollow nanoparticles. Self-assembly: Plasmon resonance shift, plasmon coupling, oligonucleotide detection. Defects: Fcc structure, cube, cubeoctahedron, octahedron, tetrahedron, surface energy, surface-to-volume ratio, twinning, unidirectional growth, synthesis of nanorods.
  • Chapter 8. CdSe and semiconductors I.
  • Structure: Crystal structures based on filling interstices in closed packed anion arrays: sfalerite, wurzite, rock salt. Synthetic methods for 13-15 and 12-16 semiconductors. Surface: Anionic, cationic, nonpolar crystal facets, ligand affinity, self assembled monolayers of ligands. Core-shell structures, epitaxy (layer-by-layer synthesis), heterogeneous nucleation.
  • Chapter 9. CdSe and semiconductors II.
  • Size: Band theory, valence and conduction bands, bandgap, exciton, Bohr radius, quantum confinement effects, blinking, multiple-exciton generation. Shape: Shape control, spherical and elongated particles, La Mer model, solubility product, supersaturation, burst nucleation, growth, hot injection method, focusing, defocusing. Face-selective ligand affinities, directed growth of nanorods, oriented attachment, growth of nanowires. Self-assembly: Layer-by-layer deposition, coulombic attraction, ionic strength. Defects: Band gap and wave function engineering, composition, impurity doping, selective dopant adsorption, distribution of dopants, band offset, lattice strain.
  • Chapter 10. Iron oxides and other metal oxides I.
  • Structure: Crystal structures of iron oxides and hydroxides, polymorphism. Synthetic methods for metal oxide nanoparticles, sol-gel preparation, solution thermolysis, laser-induced homogeneous pyrolysis, sonochemical synthesis, inverse micelle synthesis, microemulsion. Surface: Monolayers of functional ligands, binding group, bridging group, head group.
  • Chapter 11. Iron oxides and other metal oxides II.
  • Size: Magnetic properties, spin, saturation and remanent magnatization, coercive field, hysteresis, Weiss domains, ferro-, ferri-, antiferromagnetism, superparamagnetism. Magnetic ferrofluids. Shape: Kirkendall effect, hollow nanoparticles. MRI contrast agents, magnetohyperthermia. Self-assembly: Colloidal stabilization, evaporation induced self-assembly (EISA), superlattices. Metal-oxide core-shell nanoparticles.
  • 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.
Literature
  • OZIN, Geoffrey A., André C. ARSENAULT and Ludovico CADEMARTIRI. Nanochemistry : a chemical approach to nanomaterials. 2nd ed. Cambridge: RSC Publishing, 2009, liii, 820. ISBN 9781847558954. info
  • CADEMARTIRI, Ludovico and 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
Teaching methods
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.
Assessment methods
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%.
Language of instruction
English
Further Comments
Study Materials
The course is taught annually.
The course is also listed under the following terms spring 2018, Spring 2019, Spring 2020, Spring 2021, Spring 2022, Spring 2024, Spring 2025.
  • Enrolment Statistics (Spring 2023, recent)
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