Recent applications of nanostructured materials - from solar cells and batteries to biological markers

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1 Recent applications of nanostructured materials - from solar cells and batteries to biological markers Prof. Jan Augustyński o Origins of nanotechnology - limits of miniaturization. o Nanoparticle size dependent activity of heterogeneous catalysts. o Photovoltaic solar cells an overview. o Third generation cells; the nanostructured dye-sensitized solar cell. o Photocatalysis on semiconductor nanoparticles. o Photoelectrochemical water splitting. o Nanostructured electrodes for lithium batteries. o Nanoparticle-based biological markers.

2 R. P. Feynman, Eng.Sci. (1960) 23, 22 There is plenty of room at the bottom Scanning tunelling microscope (STM) IBM Zurich Research Laboratory H. Rohrer, G. Binnig Nobel Prize for Physics in 1986 Atomic force microscope (AFM) IBM Almaden Research Center and Stanford University 1986 Dynamic investigations of the catalytic surface reactions G. Ertl Fritz Haber Institute Berlin Nobel Prize for Chemistry in 2007 G. Somorjai University of Berkeley and LBNL

3 Nanocatalysis - catalytic properties of Au nanoparticles The dissociative chemisorption energies for oxygen on transition metal surfaces with respect to a molecule in vacuum calculated by density functional theory (DFT). All results are for adsorption at either a body-centered cubic (210) surface (for Fe, Mo, W) or a face-centered cubic (211) surface (other metals).

4 Reported catalytic activities (in mmol/gau s, left axis) for CO oxidation at 273 K as a function of Au particle size (d, in nanometers) for different support material. The supports are indicated by the symbol shape: open symbols correspond to reducible supports, closed symbols to irreducible supports.

5 Calculated reaction energies for CO oxidation on an Au 10 cluster (shown in insert). The lower layer of the cluster is kept fixed in the direction perpendicular to the support. Two reaction routes are shown: one dissociates O 2 before reaction with CO to form CO 2, and the other reacts molecular O 2 directly with CO.

6 The correlation between the binding energies for O 2, O, and CO on Au and the coordination number of the Au atoms in different surfaces and clusters. The binding energies are calculated using DFT and the experimental values are from elsewhere.

7 Calculated fractions of Au atoms at corners (red), edges (blue), and crystal faces (green) in uniform nanoparticles consisting of the top half of a truncated octahedron as a function of Au particle diameter. The insert shows a truncated octahedron and the position of representative corner, edge, and surface atoms.

8 Activity at 273 K as a function of Au particle diameter for two series of Au/TiO 2 catalysts containing 4.5 wt.% and 7.2 wt.% Au, respectively. The particle size has been varied by heat treatment at various temperatures between 423 K and 773 K. The rate is expressed per total amount of Au.

9 A liquid-phase air-oxidation process has been developed by Nippon Shokubai in Japan for the one-step direct production of methyl glycolate from ethylene glycol and methanol using a Au catalyst: HOCH 2 CH 2 OH + MeOH + O 2 -> HOCH 2 COOMe + 2H 2 O (1) Methyl glycolate is used as a solvent for semiconductor manufacturing processes, as a building block for cosmetics, and as a cleaner for boilers and metals.

10 The oxidation of glucose to gluconic acid can be maintained at high activity and selectivity using a stirred tank reactor for up to 110 days with a nanoparticulate Au on alumina catalyst prepared by deposition precipitation with urea. 3.8 tonnes of gluconic acid can be obtained per gram of Au in 70 days.

11 Comparison of CO tolerance results (1000 ppm CO, 0.5 A cm -2, 1.5 times stoichiometric hydrogen flow rate, SV over 3 wt. % Au/TiO 2 catalyst = ml gcat -1 h -1, Au-based catalyst chamber at 25 C, fuel cell at 80 C, 30 psi.)

12 TEM photographs of Au/Al2O3 prepared via HDP with NH2 (CO) NH2

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