1. RUTILE CRYSTAL STRUCTURE z x y

2. SEEING THE 1-D CHANELS IN RUTILE

3. NEW METASTABLE POLYMORPH OF TiO 2 BASED ON K 2 Ti 4 O 9 SLAB STRUCTURE - (010) PROJECTION SHOWN K + at y = 3/4 K + at y = 1/4 Different to rutile, anatase or brookite forms of TiO 2

4. Finding the number of crystallographically inequivalent oxygen sites in the K 2 Ti 4 O 9 slab and the number of each Oxygen count 1/3 + 3/4 Oxygen count 4 + 1/2 +2 +1/3 Oxygen count 1/3 + 3/4 1/3 1/4 1/2 1111 Topotactic loss of H 2 O from H 2 Ti 4 O 9 to give “Ti 4 O 8 ” (TiO 2 slabs) plus H 2 O, where two bridging oxygens in slab are protonated (TiOHTiOTiOH) [Ti(IV) 4 O 9 ] 2-

5. CHIMIE DOUCE: SOFT CHEMISTRY Figlarz synthesis of new WO 3 WO 3 (cubic form) + 2NaOH  Na 2 WO 4 + H 2 O Na 2 WO 4 + HCl (aq)  gel Gel (hydrothermal)  3WO 3.H 2 O 3WO 3.H 2 O (air, 420 o C)  WO 3 (hexagonal tunnel structural form of tungsten trioxide) More open tunnel form than cubic ReO 3 form of WO 3

6. Slightly tilted cubic polymorph of WO 3 with corner sharing Oh WO 6 building blocks, only protons and smaller alkali cations can be injected into cubic shaped voids in structure to form bronzes like Na x WO 3 and H x WO 3 1-D hexagonal tunnel polymorph of WO 3 with corner sharing Oh WO 6 building blocks, can inject larger alkali and alkaline earth cations into structure to form bronzes like Rb x WO 3 and Ba x WO 3

7. Hexagonal tunnels Injection of larger M + cations like K + and Ba 2+ than maximum of Li + and H + in c-WO 3 Apex sharing WO6 Oh building blocks Structure of h-WO 3 showing large 1-D tunnels

8. MOLTEN SALT ELECTROCHEMICAL REDUCTIONS OF OXYANIONS: GROWTH OF CRYSTALS Molten mixtures of precursors - product crystallizes from melt - inert crucibles and electrodes like Pt, graphite CATHODE Reduction of TM oxides to lower oxidation state materials CaTi(IV)O 3 (perovskite)/CaCl 2 (850 o C)  CaTi(III) 2 O 4 (spinel) Na 2 Mo(VI)O 4 /Mo(VI)O 3 (675 o C)  Mo(IV)O 2 (large crystals) Li 2 B 4 O 7 /LiF/Ta(V) 2 O 5 (950 o C)  Ta(II)B 2 Na 2 B 4 O 7 /NaF/V(V) 2 O 5 /Fe(III) 2 O 3 (850 o C)  Fe(II)V(III) 2 O 4 (spinel)

9. SYNTHETIC FORM: SHAPE IS EVERYTHING IN THE MATERIALS WORLD When thinking about a solid state synthesis of a particular composition it is also important to plan the form of the material that will ultimately be required for a specific application Shape is everything when it comes to designing structure-property-function-utility relations Form counts - polycrystalline, nanocrystalline, film, superlattice, wire, single crystal and so forth

10. BASICS LSSB: INJECTION-INTERCALATION CATHODES TiO 2, NbSe 3, WO 3, MoS 2, V 6 O 13, Li x CoO 2 Li + /e - charge equivalents of anode V oc,  E F (anode-cathode) Electrode-electrolyte interfacial kinetics Polymer segment dynamics Polymer T g controls crystalline vs glassy Li + /PEO cooperative motion effects Goal Li + RT conductivity Needs liquid (low MW PEO) plastisizers Electrode-electrolyte mechanical stability Electrode-electrolyte chemical stability Rocking chair architecture Secondary battery can be cycled Operational lifetime Safety, environmentally correct Li Li 3 N Li x C Li x CF LiAl LiSn Li x MnO 2 PEO Li + anode electrolyte cathode SPE

11. LiCoO 2 Li x C 6 Li ROCKING CHAIR LSSB

12. HOW TO SYNTHESIZE A BETTER LSSB? Improved Performance Cathode, Anode and Electrolyte

13. TEMPLATE SYNTHESIS OF NANOSCALE BATTERY CATHODE MATERIALS

14. A BETTER BATTERY CATHODE USING NANOSCALE MATERIALS - NANODIFFUSION LENGTHS FOR Li+ DIFFUSIVE INTERCALATION Template synthesis is a versatile nanomaterial fabrication method used to make monodisperse nanoparticles of a variety of materials including metals, semiconductors, carbons, and polymers. The template method has been used to prepare nanostructured lithium-ion battery electrodes in which nanofibers or nanotubes of the electrode material protrude from an underlying current- collector surface like the bristles of a brush. Nano-structured electrodes of this type composed of carbon, LiMn 2 O 4, V 2 O 5, Sn, TiO 2 and TiS 2 have been prepared.

15. A BETTER BATTERY CATHODE USING NANOSCALE MATERIALS - NANODIFFUSION LENGTHS FOR Li+ DIFFUSIVE INTERCALATION In all cases, the nanostructured electrode showed dramatically improved rate capabilities relative to thin-film control electrodes composed of the same material. The rate capabilities are improved because the distance that Li must diffuse in the solid state (the current- and power-limiting step in Li-ion battery electrodes) is significantly smaller in the nanostructured electrode. For example, in a nanofiber-based electrode, the distance that Li must diffuse is restricted to the radius of the fiber, which may be as small as 50 nm.

16. A BETTER BATTERY CATHODE USING NANOSCALE MATERIALS - NANODIFFUSION LENGTHS FOR Li+ DIFFUSIVE INTERCALATION Beating mechanical stability problem of repeated intercalation-deintercalation expansion-contraction cycles In addition to improved rate capabilities, the nanostructured electrodes do not suffer from poor cyclability observed for conventional electrodes. This is because the absolute volume changes in the nanofibers are small, and because of the brush-like configuration, there is room to accommodate the volume expansion around each nanofiber. Improved cycle life results show nanostructured electrode can be driven through 1400 charge/discharge cycles without loss of capacity.

17. nc-TiO 2 Nanocrystal-PEO electrolytes solid plasticisers for LSSB Ti(IV)-X - surface coordinated anion Li + cation Ti(IV)-O surface coordinated oxygen of PEO polymer chain PEO polymer chain coordinated to Li + cation and surface Ti(IV)

18. LiClO 4 -PEO-nc- TiO 2 LiClO 4 -PEO-nc-TiO 2 -high surface area nanocrystalline ceramic Br  nsted and Lewis acid-base sites - surface Ti(IV) coordination to O(CH 2 CH 2 )- Surface Ti(IV) binding to counteranion X - Polymer-particle crosslinking - no 60 o C glass transition nc-TiO 2 stabilizes glassy polymer state at RT Domains of local polymer disorder at PEO-nc-TiO 2 interface Optimal anchoring promotes local structural and dynamical modifications High RT Li+ conductivity Excellent mechanical stability, improved stress-strain curves Reduced reactivity with solid compared to liquid plasticizer Less cooperative PEO segmental motion with enhanced interfacial mobility of Li + Transport number t(Li + ), 0.3 pristine LiClO 4 -PEO, 0.6 in LiClO 4 -PEO-nc- TiO 2 nc-TiO 2

19. nc-CERAMIC OXIDES: SOLID PLASTICISERS IN POLYMER-ELECTROLYTE LITHIUM BATERIES LiClO 4 : PEO = 1 : 8, 10 wt% nc-TiO 2 or Al 2 O 3, anchoring PEO oxygens and counteranions to Br  nsted/Lewis acid surface sites, enhanced corrosion resistance of electrodes, better mechanical stability PEO, higher Li + conductivity & transport number, local disorder of polymer, loss of T g, stabilizes RT glassy state, discards need for PEO-Li + cooperative segmental motion

20. METHODS FOR SYNTHESIZING NANOCLUSTERS AND NANOCRYSTALS Vaporization of metals (thermal, laser ablation) in inert gas - condensation of mixture - Pt, Au Supersonic molecular beams - Knudsen cell vaporization with inert gas expansion - condensation into vacuum and mass selection and mass spectroscopy detection - Si, GaAs Plasma-arc vaporization - condensation - WC, SiC Aerosol spray pyrolysis of salt, sol-gel precursor solution - Y 3 Fe 5 O 12, Mn 0.8 Zn 0.2 FeO 4, PbZr 0.52 Ti 0.48 O 3, YBa 2 Cu 3 O 7, ZrO 2, TiO 2 Microemulsions, micelles, zeolites - precursors - confined nucleation and arrested nanocluster growth - capped CdSe, FePt, TiO 2, YBa 2 Cu 3 O 7

21. LENGTH SCALES IN CHEMISTRY, PHYSICS AND BIOLOGY Peter Day, Chemistry in Britain

22. Spatial and quantum confinement and dimensionality

23. WHEN IS SMALL GOOD?

24. Sub-dividing or perforating matter mono- or polydispersed particles, crystalline or amorphous, micro ( 1000 Å) length scale, organized or random arrangements, channels or pores, structure-composition-defects, surface area, sites, charge, hydrophobicity, functionality Property-function QSEs, of e, h, or h relative to materials size, dimensionality, interaction strength of components, interconnection and integration of parts, hierarchy and system architecture, function WHEN IS SMALL GOOD? Properties that are size and shape tunable mechanical, thermal, acoustical, dielectric, surface vs bulk, electrical, optical, electro-optical, magnetic, photonic, catalytic, photochemical, photophysical, electrochemical, separation, recognition, composite

25. CAPPED MONODISPERSED SEMICONDUCTOR NANOCLUSTERS nMe 2 Cd + n n Bu 3 PSe + m n Oct 3 PO  ( n Oct 3 PO) m (CdSe) n + n/2C 2 H 6 + n n Bu 3 P E g C = E g B + (h 2 /8R 2 )(1/m e * + 1/m h *) - 1.8e 2 /  R Coulomb interaction between e-h Quantum localization term

26. ARRESTED GROWTH OF MONODISPERSED NANOCLUSTERS CRYSTALS, FILMS ANDLITHOGRAPHIC PATTERNS nMe 2 Cd + n n Bu 3 PSe + m n Oct 3 PO  ( n Oct 3 PO) m (CdSe) n + n/2C 2 H 6 + n n Bu 3 P

27. MONODISPERSED CAPPED CLUSTER SINGLE CRYSTALS methanol 2-propanol toluene Rogach AFM 2002

28. THINK SMALL DO BIG THINGS!!! E g C = E g B + (h 2 /8R 2 )(1/m e * + 1/m h *) - 1.8e 2 /  R

29. SELF-ASSEMBLING AUROTHIOL CLUSTERS HAuCl 4 (aq) + Oct 4 NBr (Et 2 O)  Oct 4 NAuCl 4 (Et 2 O) nOct 4 NAuCl 4 (Et 2 O) + mRSH + 3nNaBH 4  Au n (SR) m

30. CAPPED METAL CLUSTER CRYSTAL CLUSTER SELF-ASSEMBLY DRIVEN BY HYDROPHOBIC INTERACTIONS BETWEEN ALKANE TAILS OF ALKANETHIOLATE CAPPING GROUPS ON GOLD NANOCRYSTALLITES

32. CAPPED FePt NANOCLUSTER SUPERLATTICE HIGH-DENSITY DATA STORAGE MATERIALS

33. ZEOLATE CAPPED SEMICONDUCTOR CLUSTERS

34. ZEOLATE LIGAND Crown ether - zeolate ligand analogy - metal coordination chemistry of zeolites

35. TOPOTACTIC MOCVD Intrazeolite reaction of acid zeolite Y (HY) with known amounts of Me 2 Cd or Me 4 Sn vapors Gives anchored MeCdY and Me 3 SnY, which react with H 2 S or H 2 Se to create encapsulated and zeolate capped nanoclusters Cd 4 S 4 Y and Sn 4 S 6 Y Defined by Reitveld PXRD structure refinement

36. MOCVD TOPOTAXY OF INTRAZEOLITE TIN SULFIDE, CADMIUM SELENIDE AND SILICON AND GERMANIUM NANOCLUSTERS

37. INTRAZEOLITE CVD OF SILICON NANOCLUSTERS

38. Si 2 H 6 + H 56 Y  (Si 2 H 5 ) 8 -Y (Si 2 H 5 ) 8 -Y  (Si 8 ) 8 -Y Superlattice of Si 8 clusters in ZY QUANTUM CONFINED SILICON - < 5 nm -MAKING SILICON GLOW THROUGH NANOCHEMISTRY

39. INTRAZEOLITE TUNGTEN OXIDE NANOCLUSTERS

40. NANOWIRES - FABRICATION OR SYNTHESIS Top down advanced nanolithography fabrication methods - expensive and time consuming Bottom up chemical synthesis methods - economical and fast Creation of 1D nanowires - used as functional components and interconnects in building nanodevices and nanocircuitry through self assembly strategies Most successful purely synthesis methods involve vapor-solid VS, vapor-liquid-solid VLS, solution-liquid solid SLS and solution-solid SS processes These chemical approaches have led to carbon nanotubes, metal and semiconductor nanowires and a range of inorganic materials Other approaches involve structure directing templates like channels in porous alumina, hexagonal lyotropic liquid crystals and block copolymers