1

Physical measurements and Actinide Electronic Struct ure

2

Ln

Am CmNp BkU Cf EsPu

Orbitals 5f -> activdelocalised

High number oxidation sates (III, IV, V, VI, VII)

Light Actinides

Important Differences : Light Actinides / Lanthanides

Light Actinides / Heavy Actinides

Few Differences : Heavy Actinides / Lanthanides

Specificity: chemistry and physics of 5f electrons and o rbitals

Heavy Actinides

Orbitals 5f -> inactivLocalised

Few oxidation sates (II,III, IV)

Orbitals 4f -> inactivFew oxidation sates (II,III, IV)

Lanthanides

Th IVPa IV VU III, IV, V, VINp III, IV, V, VI, VIIPu III, IV, V, VI, VII, (VIII)Am III, IV, V, VI, (VII)Cm III, IVBk, Cf… III

III, IV Pseudo sperical AnLn (n= 8,9)

V, VI Bipyramide O=An=O +/2+ Actinyle

VII … misc, tri oxo

3

Interdisciplinary-multilevel studies

Stage 1

Study of this Am specificity

Analytical approach:

Concentration effects, electrochemistry

Molecular level approach

Structure determination, spectroscopic studies, theoretical studies

CEA Marcoule, IPN Orsay

Stage 2

Focus on Am compounds

Microscopic level

Electronic organisation at the Am core

CEA Marcoule, IPN Orsay, ITU

Stage 3

Extension to Uranyl / Neptunyl

Microscopic level; Aqueous non-aqueous

High oxidation state stabisilation

Spatial and Electronic organisation at the Actinide core for 5f0, 5f1, 5f2

CEA Marcoule, ITU, CEA Saclay, IPN Orsay

4

Stage 1: Am specificity

Mechanism

Spéciation Am

Ln(III)Am(III)Cm(III)

Solution ou solide

Amsolution

LnCm εεεε Amsolide

SolutionOH-

Fe(III)(CN)6

Amsolide

5

Stage 1: Main Results

0,00

0,01

0,10

1,00

10,00

100,00

0 10 20 30 40 50 60 70

temps (mn)

% de de dissolutionAnalytical approach:

- 3 « électrons » are exchanged, no free Fe(III)(CN) 63-

- Thermodynamics do not agree with free AmO 22+

- AmO 2+ excluded by equilibrium potential

X-ray absoprtion studies on solid compound⇒ identified compound

Hydroxyde Na2AmO2(OH)3 3H2O⇒ Geometrical structure partially determined⇒ Comparison with other AmO2

+ compoundAm(TEMA) and K3AmO2(CO3)2

2.551.93K3AmO 2(CO3)2

2.491,95Na2AmO 2(OH)3

dAm-OH ÅdAm=O ÅRaman spectroscopy studies in solution

⇒ speciation of the Am compound in solutionelectro-deficient « type Am(VI) »

Existence of Am-Ferricyanure complex

750 12501000850

800

Wavenumber ( cm -1 )

O=Am=O

O=AmVI=O 800 cm-1

O=AmV=O 750 cm-1

Amv

O

O

NHO

HO

OH

C FeIII

CN

CN

CN

NC

CN

2-

AmVI

O

O

NHO

HO

OH

C FeII

CN

CN

CN

NC

CN

2-

e-

e-

6

Concentration effects

⇒ we need 3 Fe(III) for maximum dissolution⇒ Influence of NaOH….

UV-visible spectroscopy

⇒ In solution no Fe(III) remains in solution⇒ Am cannot be determined in solution⇒ Dissolution of solid shows AmO2

+

Electrochemistry

⇒ Fe(III) can oxidize Am(III) to Am(V) but not to Am(VI)⇒ Equilibrium potential do not agree with the expected Fe(II) AmO2

+

⇒ Voltametry shows the couples FeIII(CN)63-/FeII(CN)6

4- and AmO2

2+/AmO2+

Results:

⇒ 3 « électrons » are exchanged, no free Fe(III)(CN) 63- in solution

⇒ thermodynamics do not agree with free AmO 22+

⇒ AmO 2+ excluded by equilibrium potential

-0,6 -0,4 -0,2 0,0 0,2 0,4 0,6 0,8 1,0

-1,0x10-4

0,0

1,0x10-4

2,0x10-4

3,0x10-4

4,0x10-4

5,0x10-4

Inte

nsité

(A

)

potentiel (V/ENH

)

Eéq

AmVIO2(OH)

4

2- / AmVO2(OH)

4

3-

Fe(CN)6

3- / Fe(CN)6

4-

-0,020

0,000

0,020

0,040

0,060

450 500 550 600 650 700 750 800 850 900

AmV

Longueurs d'ondes (nm)

AmO2+

Stage 1: Main Results

7

X-ray absoprtion studies on solid compound

⇒ identified compoundHydroxyde Na2AmO2(OH)3 3H2O

⇒ Geometrical structure partially determined

⇒ Comparison with other AmO2+ compound

Am(TEMA) and K3AmO2(CO3)2

1,4

1,0

18,6418,6218,6018,5818,5618,5418,5218,50

0,8

1,2

K3AmVO2(CO3)2

Précipité R

Am(III)[TEMA]TEMA: N,N,N’,N’ TétraéthylmalonamideTEMA: N,N,N’,N’ Tétraéthylmalonamide

} Composés de référenceComposés de référence

R (Å)

F(R)

1ère distance Am-O

2ème distance Am-O

0 2 4 6 8

Am(TEMA)2 18517,2 eVNa2AmO2(OH)3 3H2O 18518,6 eVK3AmO2(CO3)2 18520,0 eV

2.551.93K3AmO2(CO3)2

2.491,95Na2AmO2(OH)3 3H2O

dAm-OH ÅdAm=O Å

Stage 1: Main Results solid

8

750 12501000850

800

Wavenumber ( cm -1 )

O=Am=OO=AmVI=O 800 cm-1

O=AmV=O 750 cm-1

Amv

O

O

NHO

HO

OH

C FeIII

CN

CN

CN

NC

CN

2-

AmVI

O

O

NHO

HO

OH

C FeII

CN

CN

CN

NC

CN

2-

e-

e-

Raman spectroscopy studies

⇒ speciation of the Am compound in solutionelectro-deficient « type Am(VI) »

Existence of Am-Ferricyanure complex

⇒ Electronic studies for several solid compounds with changing electron density at the Am core.

⇒ XPS 4f Binding energy of Am⇒ Mössbauer 237Np decayed from 241Am ?

790 cm-1

Stage 1: Main Results liquid

9

Mössbauer spectroscopy 237Np

Adapted for electronic analysis for Am Molecular compounds ?

What can we do with the results ?

Compounds:

AmFe(CN)6 Am(III)

Na3AmO2(OH)4 Am(V)

K3AmO2(CO3)2 Am(V)

Photoelectron spectroscopy (XPS)

Surface layer analysis (surface-bulk) adapted for molecular species ?Relative electron density at metal core binding energy shift.

Compounds:

Am(OH)3 Am(III)AmF 3 Am(III)AmFe(CN)6 Am(III)AmO2 Am(IV)Na3AmO2(OH)4 Am(V)K3AmO2(CO3)2 Am(V)

Collaboration with JRC-ITU

Stage 2: Electronic Structure Studies

10

241Am

237Np 237Np

α

γI*=-5/2

I=5/2 E=0

E*=59,53keV

T1/2=458 years

T1/2=2.106 years

τ=90ns

Source Absorbant

∆<r2>

∆ρ∆ρ∆ρ∆ρe(0)

241Am

237Np*

237Np 237Np

Source Sample

Sample Source

Am chemistry Np chemistry

α decay

γ release

Valence electron

rearrangement

Time

Stage 2: Mössbauer source experiments

11

Na3AmO2(OH)4(H2O)x

99.20

99.40

99.60

99.80

100.00

-150 -100 -50 0 50 100 150

T = 4.2 K

Tra

nsm

issi

on (

%)

Speed (mm/s)

-39.4

16.2

44.2

3+ 4+ 5+ 6+ 7+

99.40

99.50

99.60

99.70

99.80

99.90

100.00

100.10

-150 -100 -50 0 50 100 150

T = 4.2 K

Tra

nsm

issi

on (

%)

Speed (mm/s)

14.5

40.6

3+ 4+ 5+ 6+ 7+

-5.5

K3AmO2(CO3)2

98.80

99.00

99.20

99.40

99.60

99.80

100.00

-150 -100 -50 0 50 100 150

T = 4.2 K

Tra

nsm

issi

on (

%)

Vitesse (mm/s)

-39.1

70.7

3+ 4+ 5+ 6+ 7+

-0.7AmFe(CN)6

Stage 2: Mössbauer results

12

237Np Mössbauer spectroscopy using source experiments c an be suitable investigating the electronic properties of 241Am in limited cases:

“AmO2” compounds, rearrangement have started“Am” compound no rearrangements

=> More compounds need to be analysed: Role of Oxyg en

Mössbauer conclusions

13

hv e- hv e-

BE=hν-KE-∆Echarge

Charging Effects:

“Surface effects”

Decomposition (H2O)

Oxidation

dstab

dsmeasech EEE tantan

arg −=∆

charging

no charging

545 540 535 530 525

532.5

535.8 O1sAmO2

Inte

nsity

(ar

b. u

nits

)

Binding Energy (eV)

eVE 3.3≈∆

Binding Energy: Real Oxydation stateCharging effect

Surface technique: Chemical composition Surface vs BulkVery low pressure 10-5 bar

14

-200 0 200 400 600 800 1000 1200 1400

overview

Na1sOKLL

FKLL

Am4d

F1s

O1s

C1s

Am5d

Am4f

AmO2

Na3AmO2(OH)4

AmF3

Am(OH)3

Inte

nsity

(arb

. uni

ts)

Kinetic Energy (eV)-200 0 200 400 600 800 1000 1200 1400

N1s

K2pK2s

overview

Fe2p

Am4d

OKLL

CsA

Cs3dO1s

Am4f

W4f

Cs4d

C1sAm5d

Cs4Am(SiW11O39)2 x H2O

Inte

nsity

(arb

itrar

yun

its)

Kinetic Energy (eV)

AmFeCN)6

K3AmO2(CO3)2

AmF3 is ‘oxygen’ freeNo water in AmFe(CN) 6

Most case => Agreement with postulated compositionSlight variation for hydratation.Core molecular architecture agree. For Cs 4Am(SiW 11O39)2 not enough Am

15

449.2

K3AmO2(CO3)2

V

447.2

AmFe(CN)

6

III

451.5449.8449.6449.1449.5

448.2447.1BE (eV)4f5/2

AmF3AmO2Na3AmO2(OH)

4

Am(OH)3Am2O3Am metCompound

IIIIVVIIIIIIIIIFormal OxState

Am(III)

Am(V)

Am(VI)

Am(IV)

HighMore covalent

LowIonic

Electron density at metal core

-Oxo pi donor effect on binding energy for Am(V)- Ferricyanide is an overall electron density donor ligand (potentially stabilizing AmO 2

2+ in basic media)- AmF3 is probably strongly ionic, electron density for Am (III) is very weak.- Need to be confirmed by Au deposition on samples f or a more precise charge effect measurement- Am(IV) and molecular Am(VI) measurements need to b e done (unstable compounds)- What's going on with Am(VII) and Am(II) ?

“Revising” the Formal Oxidation State concept in som e case

Stage 2: XPS results, 4f 5/2

16

- XPS and Mössbauer spectroscopy can be used for elect ronic investigations on molecular species

- Extend to other techniques- XPS/UPS 4F and 5F, ligand XPS (1sO)…- XAS Low Energy levels (L and M levels)- Magnetic measurements (SQUID)- EPR ?

- Extend the measurements to other actinides elements

- Strong collaboration needed with the theoretical ap proach

- perspectives- Experimental structural (spatial and electronic) st udies on Actinyl (5f 0, 5f1, 5f2) on U and Np compounds, clearing the 5f contributio n on high oxidation state stabilisation- Theoretical qualitative valence shell description in the studied series

Stage 2: Conclusions

17

Molecular orCoordinationcompounds

Modelling

XPS, Mössbauer

Magnetism

XANES

ElectronicStructure

characterisation

Stage 3: Stabilisation of high oxidation states

Raman, IR

U et Np

An 5f-6d 4 π

O 2p 2 σ

donation σσσσ : Charge lowering at Am core

donation ππππ : Influence on the ‘yle’ substructure

An

O

S S

L L

An

L

O

Equatorial bonding features

18

[UO2(O=PPh3)4][CF3SO3]2 (UO2Cl2(THF)2)2

Np(VI) 5f1

NpO2CO3, xH2ONpO2(OH)2, xH2O

Np(V) 5f2

KNpO2CO3, H2O (NpO2)2C2O4, 6 H2ONpO2OH, H2O

UO2(CF3SO3)2

Stage 3: Actinyls systems

19

382,9 eV

393,8 eV

386,7 eV

397,6 eV

[UO2(OPPh3)4][OTf] 2 UO2(CF3SO3)2

XPSU 4f5/2-7/2

Charge U + < ++

ννννRaman 993cm -1 897cm -1

5f0

UH3PPO

H3PPO OPPH3

OPPH3

O

O

Stage 3: Uranyle XPS vs Raman : Contradiction ?

Great difference for same oxidation State = 4eV.

Charge at U : UOPPh 3 < UTf

Contradiction Raman/XPS

Axial – Equatorial discoupling

U (VI-) reduced U (VI+) oxidized

O=Am(V)=O 750 cm-1 O=Am(VI)=O 800 cm-1

20

Stage 3: Modelling

UO2(OH)2(H2O)3 UO2CO3(H2O)3 UO2X2(H2O)3 X=F, Cl, Br

Gaussian –Relativistic pseudopotentials small core - base : 6-31+G* s – DFT B3LYP

1,80

UO2Br 2(H2O)3

1,811,821,811,80d(U-O) Å

UO2CO3(H2O)3UO2(OH)2(H2O)3UO2F2(H2O)3UO2Cl2(H2O)3

-0,61

2,17

UO2CO3(H2O)3

O

U

Mulliken Charge

-0,58

1,84

UO2Br 2(H2O)3

-0,58

2,01

UO2Cl2(H2O)3

-0,61

2,23

UO2F2(H2O)3

-0,65

2,23

UO2(OH)2(H2O)3

Weak equatorial effect on actinyl

Charge difference important Cl- / Br - and F- / OH- / CO32-

Cl-, Br -

Molecular orbitals centered on uranylLess disturbance of the uranyle orbitals

F-, OH-, CO3

2-Uranyl-equ ligand mixing more importantππππ equatorial interaction

21

Mössbauer Np(VI)

XPS Np(V)

Magnetism (Squid) Np(V) et Np(VI)

Modelling

Stage 3: Neptunyle

22

• Large Quadrupolar interaction

• Hyperfine magnetic structure -> slow paramagnetic re laxation• Model problem : approximation not valid for coordi nation compounds

NpO2(OH)2.xH2O NpO2CO3.xH2O

Etape 3: Mössbauer Np(VI)

Studies onHBf et e²qQ

23

Oxidation state (VI) du Np

Comparaison des degrés d’oxydation « réels »

NpO2(OH)2.xH2ONpO2CO3.xH2O

Isometric displacement δ (mm.s-1)

δ (NpO2CO3.xH2O) = - 44 mm.s-1

δ (NpO2(OH)2.xH2O) = - 41 mm.s-1 / NpAl2

Charge at Np core

lowered for OH ligand

π equatorial donation

Etape 3: Mössbauer Np(VI)

24

Etape 3: 4f XPS Np(V)

400402404406408410412414416418420

Energie de liaison (eV)

inte

nsité

(u.

a.)

KNpO2CO3.H2O

NpO2OH.H2O

(NpO2)2C2O4.6H2O

Np4f5/2Np4f7/2

Charge at Np + ++ +++

(NpO2)2(C2O4).6H2O NpO2OH.H2O KNpO 2CO3.H2O

Covalency + 0 -

25

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

0 10 20 30 40 50T (K)

0

10

20

30

40

50

60

Squid 2K à 300K

2 types of behaviour

ParamagneticFerromagnetic <12K

Interaction between neptunyl groups« Cation-cation »

(NpO2)2C2O4, 6 H2O

0

50

100

150

200

250

300

350

400

0 50 100 150 200 250 300

T (K)

0

0,05

0,1

0,15

0,2

0,25

0,3

χ (em

u.m

ol-1

Np)

1/χ(m

ol.emu

-1N

p)

KNpO2CO3, H2O

χ (em

u.m

ol-1

Np)

1/χ(m

ol.emu

-1N

p)

Stage 3: Magnetism Np

26

KNpO2(CO3)2.66

NpO2(OH)2.59

(NpO2)2(C2O4)2.65

NpO2(OH)21.91

NpO2(CO3)2.29

Np(VI) Np(V)

3,58Np5+

3,62Np4+

2,68Np3+

RSthéorique� Magnetic moment close to Np3+

� variation of μeff as a function of ligand

� μeff Np(VI) < μeff Np(V)

μeff low Charge high ?

μeff (μB)

Moments effectifs (μB)

Stage 3: Magnetism Np

27

KNp(V)O2CO3, H2O Np(V)O2OH, H2O

Np(V)O2CO3, xH2O Np(VI)O2(OH)2, xH2O

XPS

μeff +-

+ -

Charge at Np

Mössbauer

μeff

+ -

+-

contradiction

Effective magnetic momentNature of the Orbitals (5f electron)Crystal field and spin orbit not cleared

Etape 3: Summary

28

Mössbauer → Problème de modèle pour traiter les spectres Np

Relaxation paramagnétique lente

Spectre complexe

SQUID → Prise en compte des effets du cristal et du spin orbite

HM = HO + Hes + HSO + HCC

Effets non pris en compte

→ peuvent être responsables de l’évolution de μeff

XPS → Charge réelle sur le Np

→ Séparation effets axiaux et équatoriaux :

développement de la chimie non aqueuse du Np

Stage 3: Conclusions expérimentales

29

Adding f electron increase An=O bond lenght

Equatorial ligands have weak effect on the yle structure

Cl-, Br- F-, OH-, CO32-

Lowering charge at AnPeu de perturbation

du système orbitalaire

π interaction in equatorial planeInteractions multiples

Etape 3: Modelling

NpO2X2(H2O)3n+

X = F, Cl, Brn = -1; 0; +1

NpO2(OH)2(H2O)3n+

n = -1; 0; +1NpO2CO3(H2O)3

n+

n = -1; 0; +1

30

Conclusion

[UO2(OPPh3)4][OTf]2 : stabilisation U(VI) by axial system

Uranium (VI) :

Axial and equatorial effects can be unsettled Equatorial ππππ effects can be observedF effects modulated Am(III)/Np(V)

UO2(CF3SO3)2 : Important equatorial interaction

Neptunium (V, VI) :

F and OH compounds stabilised by π equatorial donation (6d behaviour)

Carbonate : Bonding system is different, « more » ionic (5f)

Oxalate : cation-cation system

Am (III)

Am-F is rather Ionic

1

Cours de Chimie Séparative n° 9:

1) De la molécule à la nanoparticule

2) Mesure physique et charge sur les actinidesEtude d’un cas

- Les nanoparticules, généralité, pourquoi

- Synthèses (voies moléculaires)

- Les actinides

2

Recherche ISI nanoparticle*

1

10

100

1000

10000

100000

1945 à1959

1960 à1969

1970 à1979

1980 à1989

1990 à1999

2000 à2010

Les nanoparticules

100 à 1000 atomes1 à 100 nm

Plus de surface que de bulk

Recherche ISI actinide* et uran* Recherche ISI colloid*

1

10

100

1000

10000

100000

1945 à1959

1960 à1969

1970 à1979

1980 à1989

1990 à1999

2000 à2010

0

20

40

60

80

100

120

140

1990 1992 1994 1996 1998 2000 2002 2004 2006 2008

Nanoparticle*, nanosize et nanocluster

Colloid*

3

Pourquoi ce développement des études sur le nanoparticules ?

Comportement particulier

- Chimique : réactivité, vecteur (bio),

- Physico-chimique : dépend de la forme

- Physique : magnétique, électronique

- organiques (nanotube de C…)

- avec des métaux

- métallique M0 et les MXn (type oxyde p.e.)

- autres…

4

Nanoparticules Généralités

Probleme de stabilité des NP (eau)

Tension de surface

Forces dispersion vs attraction

Acc. Chem. Res. 1999, 32, 397-406

5

Chimique : catalyse

Hydrogenation des olefines par Ni NPEchange H-D par Pd NPsur C nanotube

Tetrahedron 65 (2009) 10637–10643

Alkylation par TiN NP

Chem. Eur. J. 2009, 15, 11999 – 12004 Catalysis Today 139 (2008) 154–160

6

Chimique : Vecteur (bio),

T2-weighted images of tumor-implanted mouse at 4.7 T and T2 color maps (tumor site in red circle) at different temporal points after the PEG-PAsp-coated-FeOOH nanoparticles injection.

Nanoparticule de FeO(OH)

poly(ethylene glycol)-poly(α,β-aspartic acid) block copolymer (PEG-PAsp)

M. Kumagai et al.,Colloids and Surfaces B: Biointerfaces 56 (2007) 174–181

Manuel Arruebo et al., Journal of Nanomaterials; Volume 2009, Article ID 439389, 24 pages

7

Physico-chimique : dépend de la forme

Morphologie

f(Au) Au/Ag

RapportL x l

TailleAg

Transmission

Epaisseur SiO215 nm d’Au constant

Reflection

Luis M. Liz-Marzán; Materials Today, February 2004, 31 Langmuir, Vol. 22, No. 1, 2006 35

8

Physique

2 nmAM = 9,1 106 erg/cm3

2 nmAM = 1,6 107 erg/cm3

Aniso Magnétique (AM):Aimantation d’une substance s’oriente préférentiellement selon certaines de ses directions

Effet de super-structure

Magnéto-resistivité / transmissionSpintronic et stockage de l’information

R.P. Tan et al.- Journal of Magnetism and Magnetic Materials 320 (2008) L55–L59- PRL 99, 176805 (2007)

J. Am. Chem. Soc., Vol. 122, No. 35, 2000

1

Synthèse de NP

Plusieurs voies de synthèses de NP (avec des M) existent:

- Moléculaires

- Métallique M0

- MXn, Oxydes

- Physiques (ablation laser, décharge électriques…)

- Bioassité réduction enzymatiques par des microorganismes (algues bleus…)

- …

2

Synthèse de NP metal

Coagulation of Colloidal GoldB. V. ENÜSTÜN and J. TURKEVICH

JACS, 5, 21, p3317 (1963)

Gold NP in 2 phase systemM. Brust et al., Chem. Comm., 1994, 801

HAuCl4 dans l’eau / Tetraoctylammonium Br dans ToluèneRajouter NaBH4 comme réducteurRécupère dans le toluène les NPTetraoctylammonium Br: transfert de phase et stabilisateur

Aggrégation 1 à 2 semaines. Pour éviter l’aggrégationutiliser des thiols ui se lient de façon covalmente à Au.

HAuCl4 dans l’eau / citrate de Na

C.J. Murphy et al. J. Phys. Chem. B 2001, 105, 4065M.A. El-Sayed et al. Chem. Mater. 2003, 15, 1957

Contrôle de la morphologieHAuCl4 + surfactant + Acide Ascorbique

3

Synthèse de NP metal: Polyol

Polyvinylpyrrolidone NO

RuCl3 nH2O

polyol comme solvant et réducteur

Conditions T taille (nm)1 Ethylene glycol 160 7.4 2 Ethylene glycol 180 6.23 Ethylene glycol Reflux, 198 5.44 Diethylene glycol Reflux 245 2.95 Triethylene glycol Reflux 285 1.86b Ethylene glycol µwave 1.4

J. Mater. Chem., 2001, 11, 3387–3391

4

Synthèse de NP metal: Polyol mécanisme

J. Phys. Chem. C, Vol. 113, No. 13, 2009

1

Synthèse de NP metal: Polyol

NiPt et Ag

PtPM PVP 8000, 10 000, 40 000 et 1 300 000

Langmuir 2002, 18, 5959-5962

J. Am. Ceram. Soc., 89 [5] 1510–1517 (2006)

2

Synthèse de NP metal: organometallique

polyvinylpyrrolidone, PVP;nitrocellulose, NC; cellulose acetate, AC

Ru/PVP

Dassenoy F et al. (1998) New J. Chem. 703-711

Gomez Set al. (2001) Chem. Commun., 1474-1475

B. Chaudret, Oil & Gas Science and Technology – Rev. IFP, Vol. 62 (2007), No. 6, p799

3

Synthèse de NP metal: organometallique / Liquide ionique

Ru dans BMI PF6

Scheeren C.W.et al; (2003) Inorg. Chem. 42, 4738-4742.Silveira E.T., et al., (2004) Chem. Eur. J. 10, 3734-3740.

4

Synthèse de NP metal: organometallique / surfactant

décomposition d’organometallique en présence de surfactant

Hexadecylamine / stearic acid

mélange 2/1 acide oleique et oleylamineCo(C8H13)(C8H12)

Fe[N(SiMe3)2)]2 Mélange acide / amine à longue chaine

Co(C8H13)(C8H12)

Dumestre F.,et al., (2003) Angew. Chem. Int. Edit. 42, 5213-5216

5

Synthèse de NP metal: sonochimie

Ultrasonic irradiation of 0.2 mL of Fe(CO)5 in 20 mL of octanol with 1 g of polyvinylpyrrolidone (PVP, average molecular weight of 40 000 ) at 20 °C under a rigorously oxygen free argon atmosphere produced a black colloidal solution.

Suslick et al.,J. Am. Chem. Soc. 1996, 118, 11960-11961

6

La(+III)/La(0); ‐2,379Sm(+III)/Sm(0);  ‐2,379

Y(+III)/Y(0); ‐2,372Pr(+III)/Pr(0); ‐2,353Ce(+III)/Ce(0); ‐2,336Er(+III)/Er(0); ‐2,331Ho(+III)/Ho(0); ‐2,33

Nd(+III)/Nd(0);  ‐2,323Tm(+III)/Tm(0);  ‐2,319

Pm(+III)/Pm(0); ‐2,3Dy(+III)/Dy(0); ‐2,295Lu(+III)/Lu(0); ‐2,28Tb(+III)/Tb(0); ‐2,28

Gd(+III)/Gd(0); ‐2,279Ac(+III)/Ac(0); ‐2,2Yb(+III)/Yb(0); ‐2,19Sc(+III)/Sc(0); ‐2,077

Am(+III)/Am(0); ‐2,048Cm(+III)/Cm(0);  ‐2,04Pu(+III)/Pu(0); ‐2,031Eu(+III)/Eu(0); ‐1,991

Am(+II)/Am(0); ‐1,9Th(+IV)/Th(0); ‐1,899Np(+III)/Np(0);  ‐1,856

U(+III)/U(0); ‐1,798Al(+III)/Al(0); ‐1,662

Ti(+II)/Ti(0); ‐1,63Hf(+IV)/Hf(0); ‐1,55Pa(+IV)/Pa(0); ‐1,49Zr(+IV)/Zr(0); ‐1,45

Ti(+III)/Ti(0); ‐1,37Mn(+II)/Mn(0); ‐1,185

V(+II)/V(0); ‐1,175Nb(+III)/Nb(0);  ‐1,099

Cr(+II)/Cr(0); ‐0,913Zn(+II)/Zn(0); ‐0,762Cr(+III)/Cr(0); ‐0,744

Ta(+III)/Ta(0);  ‐0,6Ga(+III)/Ga(0);  ‐0,549

Fe(+II)/Fe(0); ‐0,447Cd(+II)/Cd(0); ‐0,403

In(+I)/In(0); ‐0,338Tl(+I)/Tl(0); ‐0,336Co(+II)/Co(0); ‐0,28Ni(+II)/Ni(0); ‐0,257Mo(+III)/Mo(0); ‐0,2

Ga(+I)/Ga(0); ‐0,2In(+III)/In(0); ‐0,14

Sn(+II)/Sn(0); ‐0,138Pb(+II)/Pb(0); ‐0,126Fe(+III)/Fe(0); ‐0,037

W(+III)/W(0); 0,1Ge(+IV)/Ge(0); 0,124

Ge(+II)/Ge(0); 0,24Re(+III)/Re(0); 0,3Bi(+III)/Bi(0); 0,308Cu(+II)/Cu(0); 0,342Tc(+II)/Tc(0); 0,4Ru(+II)/Ru(0); 0,445Bi(+I)/Bi(0); 0,5Cu(+I)/Cu(0); 0,521Rh(+I)/Rh(0); 0,6

Tl(+III)/Tl(0); 0,741Rh(+III)/Rh(0); 0,758Ag(+I)/Ag(0); 0,8Hg(+II)/Hg(0); 0,851Pd(+II)/Pd(0); 0,951

Ir(+III)/Ir(0); 1,156Pt(+II)/Pt(0); 1,18

Au(+III)/Au(0); 1,498Au(+I)/Au(0); 1,692

‐3,5 ‐3 ‐2,5 ‐2 ‐1,5 ‐1 ‐0,5 0 0,5 1 1,5 2 2,5

E°(V)

H2O/H2

‐O,8277

O2/H2O1,229

Na+/Na‐2,71

K+/K‐2,931

Li+/Li‐3,04

Potentiel Redox Mn+/M0

1

Synthèse de NP oxydes

Hydrolyse d’alcoxysilaneStöber, JCIS, vol 26, 1968, p62

15ml of deionized water + 7,8ml TEOS + 15ml NH3(25%). The mixture is added to 162ml EtOH and stirred at room temperature during 3 hours.

2

Synthèse de NP oxydes condensation non-hydrolytique

Alkoxide routeMCln + M(OR)n 2 MOn/2 + n RCl

Alcohol routeMCln + n/2 ROH MOn/2 + n/2 HCl + n/2 RCl

EtherMCln + n/2 ROR MOn/2 + n RCl

M = Al, Fe, Ti, Nb, V, W, Zn, Zr, Y…; R = Me, Et, iPr, tBu...

A. Vioux et al.; J. Mater. Chem. 1992; ibid. 1996

M-O-M + R2OM-O-R + R-O-M

M-O-M + R'CO2RM-O-R + R'-CO2-M

M-O-R + Cl-M M-O-M + RCl

3

Synthèse de NP oxydes condensation non-hydrolytique

4

Synthèse de NP oxydes condensation non-hydrolytique

5

Synthèse de NP nanocrystals

Ti(OR)4

[Ti4O2](OR)10(O2CR’)2

[Ti6O4](OR)12(O2CR’)4

[Ti6O4](OR)8(O2CR’)8

[Ti9O8](OR)4(O2CR’)16 [Ti6O6](OR)6(O2CR’)6

[Ti4O4](OR)4(O2CR’)4 [Ti3O](OR)8(O2CR’)2

R,R’=iPr,Me

R,R’=iPr,CMeCH2

R,R’= Et,Co3C(CO)9iPr,HiPr,MeiPr,Np

Et,CH2=CHnBu,MeiPr,Me

R,R’=

Et,MeEt,PhOC6H4iPr,MeiPr,PhOC6H4

R,R’=

iPr,Co3C(CO)9iPr,MeiPr,Np

R,R’=

Np,MeR,R’=

Summer School 2008 J Bartlett

6

Actinides Nanocrystals - nanoclusters

Actinyl Peroxide Nanospheres

U28 : [K16(H2O)2(UO2)(O2)2(H2O)2{(UO2)(O2)1.5}28]14-

Np24 : [Li6(H2O)8NpO2(H2O)4{(NpO2)(O2)(OH)}24]20-

Angew. Chem. Int. Ed. 2005, 44, 2135 –2139 J. AM. CHEM. SOC. 2009, 131, 16648–16649

7

Actinides Nanocrystals - nanoclusters

[Pu38O56Cl54(H2O)8]14-

Synthesis 242Pu that had been treated with various alkali dyroxides and hydrogen peroxide was acidified with concentrated nitric acid and loaded onto an anion-exchange resin. During loading and the initial wash of the column with 7.5m HNO3, a large fraction of the plutonium broke through the column, thus indicating the presence of colloidal plutonium. This colloidal fraction was heated several times to near dryness and reconstituted in HCl. Aqueous 2m LiCl was added to an aliquot ofthis solution; upon evaporation of the solution at room temperature, red crystals of the reported compound formed afterapproximately one month.

Angew. Chem. Int. Ed. 2008, 47, 298 –302

8

Actinides Nanoparticles

Aceta d’uranium (VI) réduit par « rouille verte » Fe(II)/Fe(III) sous N2 / H2

Environ. Sci. Technol. 2003, 37, 721-727

9

Actinides Nanoparticles by Au nano template

Journal of Colloid and Interface Science 254, 108–112 (2002)

10

Actinides Nanoparticles

organisationPS-b-P2VPBloc co-polymers

C6H5CH3

UO2(OAc)2.2H2OMetallation

Assembling Atomic Plasma Conversion

O (UO3) or H (UO2)

D. Hudry, Th. Gouder; in the Frame of the Collaboration Agreement ICSM/LCPA - ITU

11

100 nm

TEM: after deposition HR-SEM: after atomic treatment

~ 200°C, 40 min; Oxygen-> UO3, Hydrogen -> UO2

PS1654P2VP400 ≈ 15 nm PS529P2VP476 ≈ 25 nm PS115P2VP405≈ 42 nm

D. Hudry, Th. Gouder; in the Frame of the Collaboration Agreement ICSM/LCPA - ITU