Synthesis of cupper hexacyanoferrates nanoparticles
“click” on silica and their application in removal of
radioactive cesium.
Guilhem Arrachart, , Carole Delchet, Raphaël Turgis , Cyrielle Rey, Yves Barré, Yannick
Guari, Joulia Larionova, Stéphane Pellet-Rostaing, and Agnès Grandjean
Supplementary Materials
S1 Experimental details on the characterization methods used.
S2 Description of the synthesis of CuFC@glass nanocomposites
Figure S1: schematic view of the complex Diazole-Cupper
Figure S2: IR spectra of nano-composite.
Figure S3: XRD powder pattern of nanocomposite CuFC@glass compared to
bulk CuFC
Table S1: Amount of organic grafting and elemental composition.
Table S2: Amount of nanoparticles and elemental composition
S3 Experimental details for the sorption tests.
Table S3: Cu released and Cs sorption capacity at saturation in pure water
(initial Cs concentration of 1mmol/L).
Table S4: distribution factor in, sea water (initial Cs concentration of
0.1mmol/L) and radioactive sea water (initial Cs concentration 6 10-8mmol/L)
of nanocomposite and of pure CuFC.
- S1 -
S1.Experimental details on the characterization methods
used.
Thermal analysis was performed with a Setaram Instrument under air flow with a heating rate
of 5°C/min
FT-IR in the solid state were measured using ATR crystal or as KBr pellets on a Perkin Elmer
100 spectrometer with 4cm-1 resolution.
1
H, 13C and 29Si solution NMR spectra were obtained on Bruker 400 ultrashield VS
pectrometer with deuterated chloroform as solvent and internal standard. Chemical shift are
reported in part per million (ppm).
The 29Si and 13C CP MAS NMR spectra were recorded with a Bruker 400 ultrashield VS
spectrometer with a MAS spinning rate of 12 kHz (typical contact time: 2–3 ms, typical
recycle delay: 5 s).
Chemical shifts were referenced to TMS and Bruker MAS probes (4 mm rotors) were used.
Carbon analysis was performed with a LECO CS-230. Combustion of 10mg of solid under
oxygen in an induction oven created carbon dioxide gases which are analysed by infrared
solid detector.
Powder X Ray diffraction pattern were measured on a bruker D8 advanced Diffractometer in
Bragg-Brentano geometry with Ni-Filtered Cu-Ka radiation.
Transmission Electron Microscopy (TEM) measurements were carried out at 200kV with a
JEOL 200CX microscope.
Cesium species concentrations in solution for sorption experiment in inactive solution were
measured using ionic chromatography (from Dionex). Solutions were injected in a column as
mobile phase at 30°C. Cs species are retained on the stationary phase and are then eluted after
30min and analysed by conductivity.
S2 Description of the synthesis of CuFC@Glass
Samples support were commercially glass Vycor pearls with size between 200 to 400µm;
pore size of 28nm and specific surface by BET method of 180m2/g.
3-Chlorotriethoxypropylsilane; sodium azide; ascorbic acid; cupper sulphate; propargyl
alcohol and Copper (II) tetrafluoroborate were purchased from Aldrich and used as received;
Anhydrous solvent were purchased from Acros Organics.
K3Fe(CN)6 and TBAClO4 were purchased from Acros Organics.
(TBA)3(Fe(CN)6) was obtained by reaction of K3Fe(CN)6 and TBAClO4 in methanol as
described in the literature1.
The synthesis of the molecular precursor and materials was carried out under a nitrogen
atmosphere, using vacuum line and Schlenk techniques.
Synthesis of the molecular precursor:
3-azidopropyltriethoxysilane was prepared according to literature2.
To a solution of 3-chloropropyltriethoxysilane (10 mL, 42 mmol) in dry DMF (100 mL) was
added sodium azide (10 g – 154 mmol). The heterogeneous mixture was then heated at 90°C
- S2 -
under inert atmosphere for 4 hours. The solvent was removed by distillation under reduced
pressure and the residue washed with pentane. The mixture was then filtered through cellite
under argon and the solvent was distilled off under vaccum. 3-azidopropyltriethoxysilane was
obtained as a colorless oil (6.2g - 60%)
1
H NMR (CDCl3): δ (ppm) = 3.75 (q, 6 H; CH3CH2O), 3.20 (t, 2H; CH2N3), 1.64 (m, 2H;
SiCH2CH2), 1.16 (t, 9H, CH3CH2O), 0.61 (m, 2H; SiCH2). 13C NMR (CDCl3) δ (ppm) =
58.37 (CH3CH2O), 53.75 (CH2N3), 22.62 (SiCH2CH2), 18.15 (CH3CH2O), 7.56 (SiCH2). 29Si
NMR (CDCl3) δ (ppm) = -46.3.
IR (ATR crystal): cm-1) : 2095 (-N3 as)
Grafting
Step one: synthesis of glass-N3
The synthesis of Glass-Azido composite was prepared by polymerisation of the 3azidopropyltriethoxysilane with glass pearls according to the literature,3 from 1.02g of -3azidopropyltriethoxysilane and 3.8g of porous glass in 100mL of dry toluene, at reflux
(115°C) under Ar atmosphere for 24 hours in a schlenk flask. Once cooled, the solid product
was filtered and washed with ether.
13
C CP MAS solid state NMR δ (ppm): 53.32 (CH2N3), 22.25 (SiCH2CH2), 8.65 (SiCH2)
29
Si CP MAS NMR δ (ppm): -110.74 (q4), -102.14 (q3)
IR (KBr): cm-1) : 2110 (-N3 as)
Step two: synthesis of glass-diazole
The third step consists in clicking the azide silica and propargyl alcohol in presence of cupper
sulphate as catalyst and ascorbic acid.
Cupper should form, in our material, a dimeric complex with two triazol or bidente complex
with the triazol and hydroxyle group as shown on the figure S1
- S3 -
O
O
Si
O
N
O
Si
O
N
N
OH
N
O
N
N
OH
Cu2+
Cu
O
O
Si
O
N
N
O
OH
Si
N
O
N
O
O
N
C u2+
O
2+
Si
N
O
N
OH
N
N
OH
Figure S1:
Possible complex between Cupper and triazol group.
1g of Glass-N3 was introduced in absolute ethanol with 0.17g of propargylic alcohol.
0.57g of cupper sulphate and 1g of ascorbic acid were diluted in ultrapure water and then this
aqueous solution was mixing with the previous ethanolic solution (ratio EtOH/H2O 1:1)
during 24 hours. The solid product was then filtered and washed with ethanol and acetone.
13
C CP MAS solid state NMR δ (ppm): 146.69 (CHCN3), XXX (CHCN3)
29
Si CP MAS NMR δ (ppm): -111.36 (q4)
Step three:
The growth of Cu2+/[Fe(CN)6]3- nanoparticles inside the grafted glass support was done
according to the literrature4. The solid product obtained at the end of the third step was
consecutively treated 5 times first with a methanolic solution of Cu(TBF4)2 and a second with
a methanolic solution of [N(C4H9)4]3[Fe(CN)6]. At each step of the treatment the obtained
powder was thoroughly washed with methanol. At the end of the 5th growth step, the solid
product was dried in air over night.
IR (KBr): cm-1): 2100 and 2180 (-CN )
Intensity (a.u.)
Intensity (a.u.)
CuFC
Glass
Glass-N3
Glass-click
2250
2200
2150
2100
-1
cm
2050
2000
CuFC@Gl
2300
2200
2100
-1
cm
Figure S2:
IR spectra of (a) Pristine Glass pearl; Glass-N3 (grafting step one); Glass-Click (grafting
step two) and (b) of the CuFC@glass composite compared to the bulk CuFC.
- S4 -
2000
19
Intensity (a.u.)
CuFC
CuFC@Glass
10
20
30
40
2
50
60
Figure S3
XRD Powder pattern of nanocomposite CuFC@glass compared to bulk CuFC.
Table S1: Elemental analysis of Glass-N3 (step 1).
Sample
Glass-N3
Glass-Diazole
Loading (mmol/g)
0.23
0.17
Table S2: Elemental analysis of Nanocomposite CuFC@Glass (step 3).
Sample
CuFC@Glass
Cu/Si
0.025
Fe/Si
0.015
Cu/Fe
1.7
Wt% CuFC
8
Loading (mmol/g)
0.12
3. Experimental details for the sorption tests
Three kinds of experiments were conducted: in pure water, in saline water (sea water); and in
saline water with radioactive Cs.
The saline solution has the composition of sea water to simulated the effluents from
Fukushima site and then contains (Na (9.6g/L); Mg (1.28g/L); Ca (0.4g/L); K (0.5g/L) and Sr
(0.008 mg/L)) as chloride.
Sorption in pure water and saline water:
- S5 -
In a typical experiment, 10 mg of pearls of nanocomposite was shaken in a 20mL of 1mmol/L
of CsNO3 solution deionised water or 1mmol/L of CsCl solution saline water for 24 hours,
where equilibrium is reached according to the literature5. The liquid phase was filtered
through a 0.2µm cellulose acetate membrane. The remaining Cs concentration of the liquid
phase was then analysed by ionic chromatography.
Sorption in radioactive saline water:
One litter of radioactive solution is realized from sea water and 137Cs radioactive source.
From this 137Cs enriched sea water at 29kBq/L (corresponding to 6 10-8 mmol/L), 50mg of
powder pearls of nanocomposite was shaken with 100mL of this solution for 24 hours. After
that, the solution was filtered and analysed by gamma spectrometry.
The distribution coefficient Kd (mL/g) was calculated using equation (S1), where Ci is the
initial concentration of the metal ion in solution, Cf the residual metal ion concentration and
V/M the solution volume to solid-mass ratio (V=volume of solution treated and m=mass of
nanocomposite used).
Kd 
(Ci  Cf )  V 
 
Cf
m
(S1)
The cation uptake capacity Q (mmol/g) of the samples was calculated using eqn (S2):
Q  Ci  C f
V
m
(S2)
Table S3: Cu released and Cs sorption capacity at saturation in pure water (initial Cs
concentration of 1mmol/L).
Sorbent
CuFC
CuFC@Glass
QCu meq. per gram of
composite
-0.19
-0.044
QCs meq. per gram of
composite
0.71
0.61
QCs meq. per gram of
CuFC particles
0.71
7.6
Table S4: distribution factor in, sea water (initial Cs concentration of 0.1mmol/L) and
radioactive sea water (initial Cs concentration 6 10-8mmol/L) of nanocomposite and of pure
CuFC.
Sorbent
CuFC
CuFC@Glass
Kd, mL.g-1 (sea water,
Cs: 0.1 mmol/L)
>104 *
104
Kd, mL.g-1 (radioactive sea water,
Cs: 6. 10-8mmol.L-1)
n.m
104
* The Cs equilibrium concentration in sea water here was out of detection limit (lower than
0.5 ppm).
- S6 -
1.
2.
3.
4.
5.
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- S7 -