ᐇ㦂ሗ࿌᭩ᵝᘧ䠄୍⯡฼⏝ㄢ㢟䞉ᡂᯝබ㛤฼⏝䠅㻌䠄 䈜ᮏሗ࿌᭩䛿ⱥㄒ䛷グ㏙䛧䛶䛟䛰䛥䛔䚹䛯䛰䛧䚸⏘ᴗ฼⏝ㄢ㢟䛸䛧䛶᥇ᢥ䛥䜜䛶䛔䜛᪉䛿᪥ᮏㄒ䛷グ㏙䛧䛶䛔䛯䛰䛔䛶䜒⤖ᵓ䛷䛩䚹 䠅
承認日Date of Approval 2017/9/16

Experimental Report

承認者Approver Jun-ichi Suzuki
ᥦฟ᪥ Date of Report 2017/08/19

ㄢ㢟␒ྕ㻌 Project No.㻌⿦⨨㈐௵⪅ Name of responsible person㻌

2017A0007

Hiroki Iwaseᐇ㦂ㄢ㢟ྡ㻌 Title of experiment㻌⿦⨨ྡ Name of Instrument/䠄BL No.䠅㻌

Structural Analysis of Silver Nanoparticles in Emulsions

BL15

Composed of Ionic Liquid/Water/Surfactant Systems.

ᐇ᪋᪥ Date of Experiment㻌ᐇ㦂㈐௵⪅ྡ㻌 Name of principal investigator㻌

2017/06/19䡚2017/06/21㻌

Masafumi Haradaᡤᒓ㻌 Affiliation㻌
Nara Women’s Universityヨᩱ䚸ᐇ㦂᪉ἲ䚸฼⏝䛾⤖ᯝᚓ䜙䜜䛯୺䛺䝕䞊䝍䚸⪃ᐹ䚸⤖ㄽ➼䜢䚸グ㏙䛧䛶ୗ䛥䛔䚹䠄㐺ᐅ䚸ᅗ⾲ῧ௜䛾䛣䛸䠅㻌
Please report your samples, experimental method and results, discussion and conclusions. Please add figures andtables for better explanation.
㻝㻚 ヨᩱ Name of sample(s) and chemical formula, or compositions including physical form.
1. D2O(100μL)/[OMIm][PF6](2mL)/Tween20(80μL)
2. D2O solution of AgNO3(100μL)/[OMIm][PF6](2mL)/Tween20(80μL)/Benzoin(10mg) before photoirradiation.
3. D2O solution of AgNO3(100μL)/[OMIm][PF6](2mL)/Tween20(80μL)/Benzoin(10mg) after photoirradiation.
[OMIm][PF6]: 1-octyl-3-methylimidazolium hexafluorophosphate, Tween20: C12H23F6N2P,Benzoin: C14H12O2㻞㻚 ᐇ㦂᪉ἲཬ䜃⤖ᯝ㻌 䠄ᐇ㦂䛜䛖䜎䛟䛔䛛䛺䛛䛳䛯ሙྜ䚸䛭䛾⌮⏤䜢グ㏙䛧䛶䛟䛰䛥䛔䚹䠅
Experimental method and results.

If you failed to conduct experiment as planned, please describe reasons.

Experimental
Preparation of the Ag particles in D2O-in-[OMIm][PF6] microemulsions.
㻌 Colloidal dispersions of Ag particles were synthesized by the photoreduction of AgNO3 in the presence ofTween20 in D2O-in-[OMIm][PF6] microemulsions. The concentration of Ag+ ion in the D2O-in-[OMIm][PF6]microemulsions were 60.3mM. The weight fraction of Tween20 (WTween20(wt%)), the [OMIm][PF6]-to-Tween20
molar ratio (R) and the weight fraction of D2O (WD2O(wt%)) was adjusted to 3.3 (%), 102, and 4.1 (%),
respectively. Here the value of WTween20 and WD2O is a fraction of surfactant and D2O, respectively, relative to thesum of weight of [OMIm][PF6], Tween20, D2O and benzoin. Briefly, 80μL of Tween20 was added to 2 mL of[OMIm][PF6] followed by the addition of 10 mg benzoin powder and the mixture was then stirred vigorously.
Prior to the UV-light irradiation of a 500W super-high-pressure mercury lamp, 100μL of D2O solution of AgNO3(1.32 M) was added to the mixed solution with the simultaneous ultrasonication. Subsequently, the obtained
Ag+-containing D2O-in-[OMIm][PF6] microemulsions were poured into a quartz cell and irradiation by UV-light
was started with continuous stirring using a magnetic stirrer.
1㻞㻚㻌 ᐇ㦂᪉ἲཬ䜃⤖ᯝ䠄䛴䛵䛝䠅㻌 Experimental method and results (continued)
SANS experiments of the Ag particles in D2O-in-[OMIm][PF6] microemulsions.
SANS experiments were performed using a time-of-flight diffractometer, on the BL15 (TAIKAN) at J-PARC,
Japan, in the q range of 0.07-14 nm-1 at room temperature with neutron wavelengths between 0.1 and 0.7 nm. Alldata were normalized to an absolute intensity by the coherent scattering of a glassy carbon as a reference sample
after the necessary data corrections such as air scattering, empty-cell scattering, and the transmission factor. Asample changer was mounted on the goniometer. The solution samples were placed into a quartz cell. Thethickness of the cell was 1.0 mm for all the samples. For the contrast variation (CV) SANS measurements, thescattering length density (SLD) of Ag atom is 3.47 (10-6/Å2). Here the SLDs of H2O and D2O are -0.561(10-6/Å2) and 6.402 (10-6/Å2), respectively. Hence, since the SLD of the Ag particles is matched to that of themixture for H2O/D2O=42/58, we can estimate the average size of the water droplets that consisted of aggregatesof ionic precursors of AgNO3 before photoreduction and Ag particles after photoreduction.
Results and discussion
Figure 1 shows SANS patterns (log I(q) vs. log q) of the colloidal dispersions of Ag particles in
D2O-in-[OMIm][PF6] microemulsions during photoreduction in the presence of Tween20. A comparison with theD2O-in-[OMIm][PF6] microemulsions without ionic precursors of AgNO3 is also performed. The scattering
patterns do not change at larger q range (q ≥ 1.5 nm-1), and the broad scattering peaks (centered around 3.0 nm-1)of each sample do not shift at all. This might suggest that the production of Ag particles does not so much affectthe morphology of high degree of self-organization in [OMIm][PF6]. However, the peak intensity of
Ag+-containing D2O-in-[OMIm][PF6] microemulsions decreases in intermediate q range of 0.4 – 1.5 nm-1 whencompared to pure D2O-in-[OMIm][PF6] microemulsions, although no peak shift is observed in this range. It
reveals that D2O droplets are formed in [OMIm][PF6], and Ag+ ions are dissolved in the D2O droplets.
Furthermore, the peak intensity of D2O-in-[OMIm][PF6] microemulsions containing Ag particles after
photoreduction decreases much more in this q range. The decrease in the intensity can be attributed to thedecrease in the total contrast factor resulting in reduction in scattering intensity of the samples containing Ag+ions and Ag particles. On the other hand, there is no100

significant difference in intensity at low q region (q ≤64-10.2 nm ). This strongly indicates that fractal10in the microemulsions is generated. To estimate the64I(q)structure of aggregates consisting of many droplets
fractal structure, CV SANS measurements should be

Tween20/AgNO3/D2O/[OMIM][PF6]2

before reduction
after 1h reduction
Tween20/D2O/[OMIM][PF6][Ag+]=60.3 mM

21done in future work after the incoherent scattering

64

subtraction of [OMIm][PF6].

20.1

References

6 80.1[1] M. Harada et al., J. Colloid Interface Sci., 339(2009) 373-381.
[2] M. Harada et al., J. Colloid Interface Sci., 406(2013) 94-104.

246 812-1q (nm )

4

6 8

102

Fig. 1. SANS profiles of the Ag colloidal solutions
prepared in Tween20/D2O/[OMIm][PF6] before andafter the photoirradiation.

2