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
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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
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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
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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.
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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
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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
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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
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Actinides Nanoparticles
Aceta d’uranium (VI) réduit par « rouille verte » Fe(II)/Fe(III) sous N2 / H2
Environ. Sci. Technol. 2003, 37, 721-727
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Actinides Nanoparticles by Au nano template
Journal of Colloid and Interface Science 254, 108–112 (2002)
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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
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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
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