CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by...

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CHIMIE DOUCE: SOFT CHEMISTRY • Synthesis of new metastable phases • Materials not usually accessible by other methods • Synthesis strategy often involves precursor method • Often a close relation structurally between precursor phase and product • Topotactic transformations

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Transcript of CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by...

Page 1: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

CHIMIE DOUCE: SOFT CHEMISTRY

• Synthesis of new metastable phases

• Materials not usually accessible by other methods

• Synthesis strategy often involves precursor method

• Often a close relation structurally between precursor phase and product

• Topotactic transformations

Page 2: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

CHIMIE DOUCE: SOFT CHEMISTRY

• Tournaux synthesis of a new form of TiO2

• Beyond Rutile, Anatase, Brookite and Glassy form!!!

• KNO3 (ToC) K2O (source)

• K2O + 4TiO2 (rutile, 1000oC) K2Ti4O9

• K2Ti4O9 + HNO3 (RT) H2Ti4O9.H2O

• H2Ti4O9.H2O (500oC) 4TiO2 (new slab structure) + 2H2O

Page 3: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

KIRKENDALL EFFECT IN TOURNAUX SYNTHESIS

OF SLAB FORM OF TiO2

• 16K + - 4Ti4+ + 36TiO2 8K2Ti4O9

• 4Ti4+ - 16K+ + 9K2O K2Ti4O9

• Overall reaction stoichiometry

• 9K2O + 36TiO2 9K2Ti4O9

• RHS/LHS = 8/1 Kirkendall Ratio

Page 4: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

RUTILE CRYSTAL STRUCTURE

z

x

y

Page 5: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

SEEING THE 1-D CHANELS IN RUTILE

Page 6: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

NEW METASTABLE POLYMORPH OF TiO2 BASED ON K2Ti4O9 SLAB STRUCTURE - (010) PROJECTION SHOWN

K+ at y = 3/4

K+ at y = 1/4

Different to rutile, anatase or brookite forms of TiO2

1/2

1

1

1

1

1/2

1/3

1/3

1/3

1/2

1/2 x2

1/3 x2

1/3 x2

1/3 x2

Topotactic loss of H2O from H2Ti4O9 to give “Ti4O8” (TiO2 slabs) plus H2O, where two bridging oxygens in slab are protonated (TiOHTiOTiOH)

Page 7: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

CHIMIE DOUCE: SOFT CHEMISTRY

• Figlarz synthesis of new WO3

• WO3 (cubic form) + 2NaOH Na2WO4 + H2O

• Na2WO4 + HCl (aq) gel

• Gel (hydrothermal) 3WO3.H2O

• 3WO3.H2O (air, 420oC) WO3 (hexagonal tunnel structural form of tungsten trioxide)

• More open tunnel form than cubic ReO3 form of WO3

Page 8: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Slightly tilted cubic polymorph of WO3 with corner sharing Oh WO6 building blocks, only protons and smaller alkali cations can be injected into cubic shaped voids in structure to form bronzes like NaxWO3 and HxWO3

1-D hexagonal tunnel polymorph of WO3 with corner sharing Oh WO6 building blocks, can inject larger alkali and alkaline earth cations into structure to form bronzes like RbxWO3 and BaxWO3 as well as HxWO3 a 1D proton conductor having mobile protons diffusing from O site to site along channels

Page 9: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Hexagonal tunnels

Injection of larger M+ cations like K+ and Ba2+ than maximum of Li+ and H+ in c-WO3

Apex sharing WO6 Oh building blocks

Structure of h-WO3 showing large 1-D tunnels

Page 10: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Functional device, LED, laser, sensor, biolabel

High T solvent, ligand, protection, amphiphilic amines, carboxylic acids, phosphines, phosphine oxides, phosphonic acids

Inorganic precursor, oxides, sulphides, metals, nucleation of nanocluster seed

Growth and ligand capping of nanocluster core

Ligand capping arrested growth of nanocluster core

Page 11: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Arrested nucleation and growth synthetic method for making semiconductor nanoclusters in a high-boiling solvent. Adding a non-solvent causes the larger nanocrystals to precipitate first, allowing size-selective precipitation and nanocluster scaling laws to be defined

nMe2Cd + nnBu3PSe + mnOct3PO (nOct3PO)m(CdSe)n + n/2C2H6 + nnBu3P

Page 12: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

ARRESTED GROWTH OF MONODISPERSED NANOCLUSTERS

• Hydrophobic sheath of alkane chains of surfactant make the nanoclusters soluble in non-polar solvents - crucial for achieving purification and size selective crystallization of the nanoclusters.

• nMe2Cd + nnBu3PSe + mnOct3PO (nOct3PO)m(CdSe)n + n/2C2H6 + nnBu3P

• Tributylphosphine selenide in a syringe is rapidly injected into a 300C solution of dimethyl cadmium in trioctylphosphine oxide surfactant-ligand-solvent, known as TOPO.

Page 13: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

SIZE SELECTIVE CRYSTALLIZATION OF LIGAND CAPPED NANOCLUSTERS

Gradually add non-solvent acetone to a toluene solution of capped nanoclusters

Causes larger crystals to precipitate then smaller and smaller crystals as the non-solvent concentration increases.

Smaller ones more soluble because of easier solvation of less dense packed alkanethiolate chains.

Page 14: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

SIZE SELECTIVE CRYSTALLIZATION OF LIGAND CAPPED NANOCLUSTERS

When non-solvent added, nc-nc contacts become more favorable than nc-solvent interactions. Larger diameter capped nanoclusters interact via the chains of the alkanethiolate capping ligands more strongly than the smaller ones due to the smaller curvature of their surface and the resulting greater interaction area. As a result they are caused to flocculate that is aggregate and crystallize first.

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SIZE SELECTIVE CRYSTALLIZATION OF LIGAND CAPPED NANOCLUSTERS

Process repeated to obtain next lower size nanoclusters and procedure repeated to obtain monodispersed alkanethiolate capped gold nanoclusters.

Further narrowing of nanocluster size distribution achieved by gel electrophoresis – an electric field driven size exclusion separation stationary phase.

Page 16: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Additionof reagent

nucleation

aggregation

BASICS OF NANOCLUSTER NUCLEATION, GROWTH, CRYSTALLIZATION AND CAPPING STABILIZATION

capping and stabilization

nMe2Cd + nnBu3PSe + mnOct3PO (nOct3PO)m(CdSe)n + n/2C2H6 + nnBu3P

Gb > Gs

supersaturation

Page 17: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

CAPPED MONODISPERSED SEMICONDUCTOR NANOCLUSTERS

nMe2Cd + nnBu3PSe + mnOct3PO (nOct3PO)m(CdSe)n + n/2C2H6 + nnBu3P

EgC = Eg

B + (h2/8R2)(1/me* + 1/mh*) - 1.8e2/R

Coulomb interaction between e-h

Quantum localization term

Page 18: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.
Page 19: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.
Page 20: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

SIZE DEPENDENT OPTICAL ABSORPTION SPECTRA OF CAPPED CDSE NANOCLUSTERS, SYNTHESIS AND CHARACTERIZATION OF NEARLY MONODISPERSE CdE (E = S, Se, Te) SEMICONDUCTOR NANOCRYSTALLITES, MURRAY CB, NORRIS DJ, BAWENDI MG, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 115 (19): 8706-8715 SEP 22 1993)

Page 21: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

SIZE AND COMPOSITION DEPENDENCE OF THE OPTICAL EMISSION SPECTRA OF CAPPED InAs (RED), InP (GREEN) AND CdSe (BLUE), BRUCHEZ, M.JR; MORONNE, M.; GIN, P.; WEISS, S.; ALIVISATOS, A.P. SEMICONDUCTOR NANOCRYSTALS AS FLUORESCENT BIOLOGICAL LABELS, SCIENCE 1998, 281, 2013

Page 22: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Nanocluster Synthetic Control – size, shape, composition, surface chemical and physical properties, separation, amorphous, crystalline

Do it yourself quantum mechanics – synthetic design of optical, electrical, magnetic properties

PXRD, MALDI-MS, TEM CHARACTERIZATION OF CLUSTER CORE, CLUSTER SEPARATION LIGAND SHEATH,

Page 23: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

ARRESTED GROWTH OF MONODISPERSED

NANOCLUSTERS

CRYSTALS, FILMS AND LITHOGRAPHIC

PATTERNS

nMe2Cd + nnBu3PSe + mnOct3PO (nOct3PO)m(CdSe)n + n/2C2H6 + nnBu3P

Page 24: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

MONODISPERSED CAPPED CLUSTER SINGLE CRYSTALS

methanol

2-propanol

toluene

Rogach AFM 2002

Page 25: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

TRI-LAYER SOLVENT DIFFUSION CRYSTALLIZATION OF CAPPED NANOCLUSTER SINGLE CRYSTALS. MeOH TOP LAYER, TOLUENE BOTTOM LAYER, 2-PROPANOL MIDDLE BUFFER LAYER - OMITTING THE BUFFER LAYER CREATED ILL-DEFINED CRYSTALS, A NEW APPROACH TO CRYSTALLIZATION OF CdSe NANOPARTICLES INTO ORDERED THREE-DIMENSIONAL SUPERLATTICES, TALAPIN DV, SHEVCHENKO EV, KORNOWSKI A, GAPONIK N, HAASE M, ROGACH AL, WELLER H, ADVANCED MATERIALS, 13 (24): 1868, 2001

Page 26: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

GOLD ATOMIC DISCRETE STATES

GOLD CLUSTER DISCRETE MOLECULE STATES

GOLD QUANTUM DOT CARRIER SPATIAL AND QUANTUM CONFINEMENT

GOLD COLLOIDAL PARTICLE SURFACE PLASMON – 1850 MICHAEL FARADAY ROYAL INSTITUTION GB PIONEER OF NANO!!!

BULK GOLD PLASMON

Page 27: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

SELF-ASSEMBLING AUROTHIOL CLUSTERS

HAuCl4(aq) + Oct4NBr (Et2O) Oct4NAuCl4 (Et2O)

nOct4NAuCl4(Et2O) + mRSH (tol) + 3nNaBH4 Aun(SR)m (tol)

Diagnostic cluster size dependent optical plasmon resonance originating from dipole oscillations of conduction electrons spatially confined in nanocluster – wavelength plasmon depends on size, type of capping ligand and nature of the environment of nanocluster – also size dependent electrical conductivity – hopping from cluster to cluster - useful in nanoelectronic devices and nanooptical sensors – Faraday would be pleased!!!

Page 28: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Relationship between alkanethiolate polymer, nanocluster and self-assembled monolayer

Page 29: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

SIZE SELECTIVE CRYSTALLIZATION OF SELF-ASSEMBLING AUROTHIOL CLUSTERS Aun(SR)m

Gradually adding a non-solvent such as acetone to a toluene solution of capped gold nanoclusters first causes larger crystals to precipitate, then smaller and smaller crystals, as the non-solvent concentration increases. Smaller ones more soluble because of easier solvation of less dense packed alkanethiolate chains.

When non-solvent added, nc-nc contacts become more favorable than nc-solvent interactions. Larger diameter capped gold nanoclusters interact via the chains of the alkanethiolate capping ligands more strongly than the smaller ones due to the smaller curvature of their surface and the resulting greater interaction area. As a result they are caused to flocculate that is aggregate and crystallize first.

Process repeated to obtain next lower size nanoclusters and procedure repeated to obtain monodispersed alkanethiolate capped gold nanoclusters.

Page 30: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

CAPPED METAL CLUSTER CRYSTAL

CLUSTER SELF-ASSEMBLY DRIVEN BY HYDROPHOBIC INTERACTIONS BETWEEN ALKANE TAILS OF

ALKANETHIOLATE CAPPING GROUPS ON GOLD NANOCRYSTALLITES

U.Landman AM 1996

Page 31: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Plasmonics Basics – Size Effects

Page 32: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Plasmonics Basics – Size Effects

• What is the the surface plasmon resonance of gold nanostructures. On the top left corner is shown how the electron cloud of free-electrons in the gold respond to an oscillating electromagnetic field, depending on the shape and orientation of the particle. The formation of a dipole causes the emergence of a resonance at a specific wavelength, as shown on the right by the representative absorbance spectra. In the case of spherical particles the plasmon resonance occur at a single frequency, while for elongated nanocrystals you can have two resonance frequencies related with the two dipole oscillation modes (longitudinal or transverse).

• In the bottom part of the Figure is shown the origin of the absorbance features according to the Mie theory. The absorbance A is expressed as the product of two terms. The first term is scattering-related and has a 1/ dependence, while the second term is exclusively dependent on the dielectric constants of the metal and the surrounding medium. This last term represent the resonant plasmon mode which is shown as a peak centered at the surface plasmon resonance wavelength SPR. The product of the two terms is the spectrum observed experimentally.

Page 33: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

SURFACE PLASMON RESONANCE MIE THEORYMIE THEORY

• Extinction coefficient from Mie theory is the exact solution to Maxwell’s electromagnetic field equations for a plane wave interacting with a homogenous sphere of radius R with the same dielectric constant as bulk metal (scattering and absorption contributions).

• m is the dielectric constant of the surrounding medium – sensitive to environment

• 1 i is the complex dielectric constant of the particle

• Resonance peak occurs whenever the condition 1 = -2m is satisfied – sensitive to change in m of environment hence use as a surface plasmon sensor

• This is the SPR peak which accounts for the brilliant colors of various metal nanoparticles – form factors can be introduced to account for non-spherical shape – Gans modification of Mie theory.

Page 34: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Extinction spectra calculated using Mie theory for gold

nanospheres with diameters varying from 5 nm to 100 nm.

Page 35: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Detecting Biomolecules with Gold NanocrystalsSelf Assembly and Plasmon Coupling

Page 36: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Detecting Biomolecules with Gold NanocrystalsSelf Assembly and Plasmon Coupling

• The coupling of plasmons can be used for the detection of oligonucleotides in solution. Gold nanocrystals can be produced with thiol-functionalized oligonucleotides bound to their surface – a construct which we call the probe. The oligonucleotides on the nanocrystals are synthesized to be complementary to the ones one wants to detect. The ultraspecific binding of oligonucleotides for their complementary strand allows the particles to bind very efficiently to the analytes in solution. Such binding of two nanocrystals to the same analyte brings the nanocrystals very close together thus enabling the coupling of the plasmons.

• As shown in the diagram below, once the nanocrystals are close the dipole can extend over the ensemble of the two nanocrystals (as in resonance r2) while for single isolated particle the dipole is confined to the particle itself (resonance r1). The simultaneous presence of r1 and r2 resonances leads to an effective red shift of the absorbance peak of the nanocrystals thus changing their color, as shown in the photos thereby enabling detection of a specific oligonucleotide which shows complementary Watson-Crick base pairing.

Page 37: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Gold Nanocrystals to Gold Nanorods

• Gold nanocrystal ncAu seed mediated growth of gold nanorods nrAu

• ncAu seeds obtained by aqueous sodium borohydride reduction of HAuCl4 with sodium citrate surface stabilization

• nrAu obtained by surfactant (trimethylcetylammonium bromide CTAB) directed re-growth of ncAu seeds using ascorbic acid mild reducing agent of HAuCl4

Page 38: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Non-Spherical Shapes -Gans Modified Mie Theory

Page 39: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Au Nanorods – Shape Selective AdditivesAspect Ratio Tunes Longitudinal NOT Transverse SPR Modes

(a) L = 46 nm, w = 22 nm; (b) L = 61 nm, w = 22 nm; (c) L = 73 nm, w = 22 nm; (d) L = 75 nm, w = 22 nm; (e) L = 89 nm, w = 22 nm; (f) L = 108 nm, w = 22 nm. The right panel shows a representative TEM image of the sample corresponding to spectrum-f.

Calculated Gans Theory Gold Nanorod w = 20 nm

Page 40: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Gold NanorodsAspect Ratio Tunes Longitudinal NOT Transverse SPR Modes

NANOCHEMISTRY CURES CANCER

CANCER CELL TARGETED GOLD NANOROD ATTACHMENT

BURN AWAY THOSE NASTY CANCER CELLS BY NANORODS ABSORBING NIR PLASMON AND

TRANSFERING HEAT TO CANCER CELL – PHOTOTHERMAL CANCER THERAPY

Page 41: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Nano Medicine - Photothermal Cancer Therapy Using Gold Nanorods

Page 42: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

Nano MedicinePhotothermal Cancer Therapy Using Gold Nanorods

• In the top part of the Figure you can see how the plasmons relax back to the equilibrium state after being excited at their resonance. The relaxation occurs through emission of heat that can be used for killing cells to which they are selectively attached.

• In the middle part of the Figure is shown from the left the absorption/scattering spectrum of the biological tissues and water; the windows of low absorbance are indicated by the pink areas. In the next spectrum is shown how the different absorbances of the tissues at different wavelengths affect the intensity of light propagating in them; as it is shown in the graph the light with wavelength 1000 nm will propagate further than light 500 nm, which is instead strongly absorbed. On the right is a representative absorbance spectrum of gold nanorods highlighting how the second resonance peak can be made to fit in the biological window, thus increasing its potential for photothermal therapy.

• In the bottom part of the Figure are shown three different lines of cells (nonmalignant HaCat, malignant HSC and malignant HOC cells) after having exposed them to a strong NIR laser light (the circle highlights the area of exposure). The gold nanorods were made to bind selectively to the malignant cells thanks to an active targeting protocol. As you can see the nonmalignant cells were not harmed since they were not targeted by the nanorods. The malignant cells instead suffered strong damage because they were targeted by the nanorods and because the nanorods heated up upon irradiation with the laser.

Page 43: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.
Page 44: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

CAPPED FePt FERROMAGNETIC NANOCLUSTER SUPERLATTICE

HIGH-DENSITY DATA STORAGE MATERIALSHIGH-DENSITY DATA STORAGE MATERIALS

Page 45: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

NANOMAGNETIC SEPARATIONS OF

BIOLOGICAL MOLECULES

Page 46: CHIMIE DOUCE: SOFT CHEMISTRY Synthesis of new metastable phases Materials not usually accessible by other methods Synthesis strategy often involves precursor.

La Douce France

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S. Little, JERILI LITTLE in IRMA DOUCE

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