FCC Inverse Spinel Crystalline System

Fe(III) Tetrahedral
Fe(II, III) Octahedral
 +

+ +
-
-
-

+ - Magnetite
- +

- -
-

+ +

+
 TETRAMETHYL AMMONIUM CATION

HYDROXYL ANION
1

Hydrolysi
Si OR + HOH s Si OH + ROH
Reesterification

Alkoxysilane Silanol Alcohol

2
Water
a Condensation
Si OH + Si OH Si O Si + HOH
Hydrolysis

Silanol Silanol Siloxane Water

2 Alcohol
b Condensation
Si OH + Si OR Si O Si + ROH
Alcoholysis

Silanol Alkoxysilane Siloxane Alcohol

 MeO
MeO OH
+H2O Si
MeO -MeOH +H2O
MeO
MeO OMe OH
Si
MeO MeO Si OH
“TMOS” O
MeO MeO O OMe O Si
Si Si O
O
Si
OMe MeO OMe OH
O OH +H2O
MeO Si OH
-MeOH
Si
MeO O Si Magnetite@Silica
Si O O OMe
O O Si
O Si OH
MeO Si O
O O O
MeO
MeO
SiO2
Igepal CA-520

Igepal CO-520
 Inverse Microemulsion
Inverse Micelle

Aqueous
phase

Hydrophobic Organic phase

Surfactant

Hydrophilic
Cyclohexane + Magnetite suspension + Tetramethylorthosilicate 24 hours stirring
Igepal CO-520 Ammonium Hydroxide (TMOS) Solvent washing
Decantation

Inverse Micelle Formation Silanol Hydrolysis Microemulsion breaking Magnetite@Silica

Condensation Nanoparticles
 OCH3 OH
Hydrolysis
H Si OCH + 3H2O H Si OH + CH3OH
S 3 S
OCH3 OH

H H
O S S
H H O
OH O H
H Si OH + H O
S OH O H
H O
O O H OH OH
H HO Si O Si
O O
Self Condensation Si O Si O Si
-H2O
HS HS

OH O
H H O
H Si OH O H
S O
+ H
O H
O
O
H O OH
H Si OH HO Si OH Si
O O H
S OH H O O
Si O Si O Si
2 Steps Synthesis Water Bath Sonication
2 Steps Synthesis Probe Sonication
Dialysis Sample
Dialysis Sample
1 Steps Synthesis
 ~ 44
nm
Igepal CA-520

~ 10
nm

~ 59
nm
Igepal CO-520
 ~7
nm
~1
5n
Igepal CO-520

~2
9n
m
d= 0.40 nm

Igepal
CO-520
Igepal CO-520 Silica Phase
Igepal CO-520 Magnetite@Silica
 (220)

(311)

(400) Igepal CO-520 Magnetite@Silica

(511)

(440)
Igepal CO-520 Magnetite@Silica
Igepal CO-520 Magnetite@Silica

1 step Synthesis magnetite

d=
0.3
8 nm
Igepal CO-520 Magnetite@Silica

1 step Synthesis magnetite

 (220)

(331)

(400)
Igepal CO-520 Magnetite@Silica

1 step Synthesis magnetite

(422)

(511)
(440)
 ~ 1.70 nm

Igepal CO-520 Magnetite@Silica

2 Steps Syntehsi magnetite Dialyzed

Igepal CO-520
Magnetite@Thiols
functionalized Silica

2 step Synthesis
magnetite

511
422

331

220
Igepal CO-520
Magnetite@Thiols
functionalized Silica

2 step Synthesis
magnetite
Igepal CO-520
Magnetite@Thiols
functionalized Silica

2 step Synthesis
magnetite
Igepal CO-520
Magnetite@Thiols
functionalized Silica

2 step Synthesis
magnetite
Igepal CO-520
Magnetite@Thiols
functionalized Silica

2 step Synthesis
magnetite
C

Igepal CO-520
Magnetite@Thiols
functionalized Silica
Cu
O
Cr
2 step Synthesis
Fe magnetite
Si

Fe
Cu
Al S Cr Au
 811

2837 2495

1067
964
563 Igepal CO-520
954 Magnetite@Thiols
799 functionalized Silica
1059
552

954
3270 1482 2 step Synthesis
563 magnetite

IR spectra
1067 810

954
3260
1479
2 step Synthesis
magnetite Oleic Acid
pre-coating
 (422) (331)
(220)
(400)
(511)

(440)

2 step Synthesis magnetite Oleic Acid pre-coating

 d = 0.48 nm
10.25 nm
4.10 nm

8.80 nm
3.40 nm
9.50 nm

Monocrystallline
Magnetite core

Magnetite@Silica
2 step Synthesis magnetite oleic acid
 2.30 nm

13.60 nm

1.90 nm

9.90 nm
2.30 9.81 nm
nm

Magnetite@Silica
2 step Synthesis magnetite oleic acid
 Magnetite@Silica

Magnetite-Oleic Acid

Silica Nanoparticles

Oleic Acid

2 step Synthesis magnetite-oleic acid IR spectra

Magnetite@Thiols functionalized Silica Sample 2

Magnetite@Thiols functionalized Silica Sample 1

Magnetite@Silica

Magnetite-Oleic Acid

Silica Nanoparticles

Oleic Acid
A-1 A-2

Magnetite@TMAOH
2 step Synthesis magnetite

B-1 B-2
Magnetite@TMAOH
1 step Synthesis magnetite
 Magnetite@Silica

C-1 C-2 C-3

D-1 D-2 D-3

Magnetite@Thiols functionalized Silica

Multicore Nanocomposites Mono-core Nanocomposites
Thiols functionalized silica film

1427
2930 2549 d (CH2)
u as(CH2) u (SH)
3413 786
u s(OH) 2853 u (Si-O)
u s(CH2)
920
u (Si-O-Si)

Glass Substrate

790
u (Si-O)

993
u (Si-O-Si)