Supplementary Information for
Limitation of Adsorptive penetration of Cesium into
Prussian Blue Crystallite
Hirotaka Fujita*, Risa Miyajima**, Akiyoshi Sakoda*
*Institute of Industrial Science, University of Tokyo, Japan
4-6-1 Komaba, Meguro-ku, Tokyo, 153-8505, Japan
e-mail: fujiozon@iis.u-tokyo.ac.jp
Tel/Fax: +81-3-5452-6348
**School of Science and Technology, Meiji University, Japan
1-1-1 Higashimita, Tama-Ku, Kawasaki-city, Kanagawa 214-8571, Japan
Section S1 Preparation of Prussian Blue crystallite
Section S2 Determination of average crystallite size by Williamson-Hall (W-H) method
Section S3 TEM and SEM observation
Section S1 Preparation of Prussian Blue crystallite
(1) Insoluble PB synthesized by an immediate precipitation reaction method (H3O+IPB-12)
The synthesis method is described in detail elsewhere (Fujita 2014). H3O+IPB-12 was prepared
under the conditions in which Fe(III)3+ was in excess of [Fe(II)(CN)6]4- (Louise 2013). Aqueous
solution (300cc) containing 1.72g of K4[Fe(II)(CN)6]·3H2O was added dropwise into 600cc of
aqueous solution containing 1.72g of Fe(III)Cl3 at ambient temperature. The precipitated IPB
was separated by centrifugal separation, followed by 5 rinses with 50cc of ion-exchanged water.
(2)Soluble PB synthesized by an immediate precipitation reaction method (K+SPB-14)
K+SPB-14 was prepared under conditions in which [Fe(II)(CN)6]4- was in excess of Fe(III)3+ in
contrast to H3O+IPB-12 (Louise 2013). Aqueous solution (600cc) containing 0.66g of Fe(III)Cl3
was added dropwise into 300cc of aqueous solution containing 4.5g of K4[Fe(II)(CN)6]·3H2O at
ambient temperature. PB dispersing in the synthesis solution was filtered using a membrane
filter with a 25-nm pore aperture, followed by 5 rinses with 50cc of ion-exchanged water.
(3) Soluble PBs prepared by oxidation of Berlin White (K+SPB-18 and K+SPB-45)
The synthesis procedure is described in detail elsewhere (Louise 2013). Aqueous solution (50cc)
containing 4.2g of K4[Fe(II)(CN)6]·3H2O at 50°C was mixed with 50cc of aqueous solution
containing 2.0g of Fe(II)Cl2 ·4H2O at 50°C under nitrogen atmosphere to generate Berlin White
(BW). As for the K+SPB-45, the solution was further maintained at 100°C in the water bath for
2hr with complete sealing to prevent the contact of oxygen with BW. Aging is a key process for
the increase of crystal size (Louise 2013). As for K+SPB-18, no aging process was performed.
Subsequently, 30 percent of H2O2 was added to the synthesis solution to oxidize BW into PB,
until there was no more explosive boiling by the addition of H2O2, which seems to be an index
of oxidation of BW. Then, PB was filtered using a membrane filter with a 25-nm pore aperture,
followed by 5 rinses with 50cc of ion-exchanged water.
(4) Soluble PB prepared by hydrothermal synthesis from K4[Fe(CN)6] solution (K+SPB-800)
The synthesis procedure is described elsewhere (Wu 2006). We used this method with some
modification of synthesis conditions, dissolving 0.6g of K4[Fe(II)(CN)6]·3H2O in 100cc of
distilled water. Subsequently, the solution was maintained at 60°C in the water bath. Then,
0.15cc of 10% NaClO and 1cc of 35‒37% HCl was added to this solution and kept at 60°C with
stirring at the rate of 130 rpm for 10 hr. The precipitate was filtered using membrane filter with
1-μm pore aperture, followed by 5 rinses with 50cc of ion-exchanged water. This synthesis
method is based on the release of Fe(II)2+ from [Fe(II)(CN)6]4- in the presence of high
concentration of H3O+, and the Fe(III)3+ generated by oxidation of the released Fe(II)2+ by ClOserves as a source material of PB (Wu 2006). Hence, it should be noted that dangerous cyanides
may be generated during the synthesis (Herrera 2008).
Section S2 Determination of average crystallite size by Williamson-Hall (W-H) method
Peak fitting by the nonlinear least-squares method was performed using the Lorentzian function
with consideration of the kα2 contribution, after background subtraction by the Sonneveld-Vier
method (Sonneveld 1975). The peak profile function considering kα2 contribution, I(2θ), can be
described in equations (S1)‒(S4)
𝐼(2𝜃) = 𝑖(2𝜃) + 0.5 ∙ 𝑖(2𝜃 + ⊿2𝜃𝑟 ) ∙∙∙∙∙ (𝑆1)
𝒊(𝟐𝜽) =
𝑨
𝟐𝜽 − 𝟐𝜽𝟎 𝟐
𝟏+(
)
𝜷𝒆𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕
⊿2𝜃𝑟 = 2𝑡𝑎𝑛𝜃 ∙
∙∙∙∙∙∙ (𝐒𝟐)
Δ𝜆
∙∙∙∙∙∙ (𝑆3)
𝜆𝐾𝛼1
Δ𝜆 = 𝜆𝐾𝛼2 − 𝜆𝐾𝛼1 ∙∙∙∙∙∙ (𝑆4)
where I(2θ) is the peak function including the contribution of both kα1 and kα2, A is the height
of the kα1 peak, θ0 is the angular position of the Kα1 peak, Δ2θr is the gap in angular position
between kα1 and kα2 peaks, βexperiment is the full width at half maximum (FWMH) of the kα1
peak and λkα1 and λkα2 are wavelengths. For the W-H method, instrumental broadening of the
peak, βinst, was determined using a large crystallite of KCl (Langford1996; Scardi 1994). If the
peak could be expressed by the Lorentzian function, the true peak broadening could be
calculated by equation (S5). The value of β was used for the W-H method (Georgea 2011).
𝛽 = 𝛽𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 − 𝛽𝑖𝑛𝑠𝑡 ∙∙∙∙∙∙ (𝑆5)
Fig.S1 (a) and (b) show an example of the peak fitting and the W-H plot, respectively. The
crystallite size was calculated by the W-H plot for samples except K+SPB-800. The crystallite
size is shown in Table S1.
(a) An example of peak fitting by the nonlinear least-squares method for K+SPB-800
(b) Williamson-Hall (W-H) plot
Fig. S1 Analysis results of XRD data
Table S1 Crystallite size of each PB sample
Section S3 TEM and SEM observation
Scanning electron spectroscopy (SEM) observation of PB samples was performed using
JSM-7500 (JEOL). Also, transmission Electron Microscopy (TEM) observation was performed
by the following procedure. The synthesized PB was dispersed in ethanol by sonication for 20
min. The dispersed solution was dropped onto the collodion membrane (COL-C-15 (Oken
Shoji)), and then the dried membrane was subject to TEM observation (JEM-2000EX (JEOL)).
The result is shown in Fig. S2.
H3O+IPB-12
K+SPB-14
K+SPB-18
K+SPB-45
NH4+/Na+SPB-65
K+SPB-800
Fig. S2 SEM and TEM images of PB samples
Reference
Fujita H., Sasano H., Miyajima R., Sakoda A.: Adsorption Equilibrium and Kinetics of Cesium onto
Insoluble Prussian Blue Synthesized by An Immediate Precipitation Reaction Between Fe3+ and
[Fe(CN)6]4-. Adsorption, 20, 905–915 (2014)
Georgea A., Sharmaa S. K., Chawlab S., Malika M.M., Qureshia M.S.: Detailed of X-ray
diffraction and photoluminescence studies of Ce doped ZnO nanocrystals., Journal
of Alloys and Compounds 509,5942–5946 (2011)
Herrera J. M., Bachschmidt A., Villain F., Bleuzen A., Marvaud V., Wernsdorfer W., Verdaguer M.:
Mixed valency and magnetism in cyanometallates and Prussian blue analogues. Phil. Trans. R.
Soc. A 366, 127–138 (2008)
Langford J.I., Daniel L.: Powder diffraction. Rep. Prog. Phys. 59,131-234(1996)
Louise S., Fernande G., Gary J. L., Pauline N. , Pierre B. , David S.: Relationship between the
Synthesis of Prussian Blue Pigments, Their Color, Physical Properties, and Their Behavior
in Paint Layers. J. Phys. Chem. C, 117 (19), 9693–9712(2013)
Scardi P., Lutterotti L., Maistrelli P.: Experimental determination of the instrumental
broadening in the Bragg–Brentano geometry, Powder Diffraction 9, 180-186 (1994)
Sonneveld E. J. and Visser J.W.: Automatic collection of powder data from photographs.
J. Appl. Crystallogr.. 8, 1-7(1975)
Wu X., Cao M., Hu C., He X.: Sonochemical Synthesis of Prussian Blue Nanocubes from a
Single-Source Precursor. Crystal Growth & Design, 6(1) , 26-28 (2006)