Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information (ESI) Novel Nickel-Palladium Catalysts Encased in a Platinum Nanocage Balachandran Jeyadevan* a, Jhon L. Cuya a, Yoshinori Inoue a, Kozo Shinoda b, Takashi Ito c, Derrick Mott d, Koichi Higashimine d, Shinya Maenosono d, Takatoshi Matsumoto b and Hiroshi Miyamura a a Department of Material Science, The University of Shiga Prefecture, 2500 Hassaka Cho, Hikone 522-8533, Shiga, Japan. Email; jeyadevan.b@mat.usp.ac.jp;fax;+81 749 28 8486;Tel:+81 749 28 8352. b Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai, Japan. E-mail: shinoda@tagen.tohoku.ac.jp; Fax:+81 22 217 5624; Tel: +81 22 217 5624. c Institute Frontier Research Institute for Interdisciplinary Sciences, Tohoku University, Sendai, Japan. E-mail: ito@cir.tohoku.ac.jp; Fax:+81 22 217 5624; Tel: +81 22 217 5624 d School of Material Science, Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa Prefecture, 923-1211, Japan. E-mail: shinya@jaist.ac.jp; Fax:; Tel: +81 761 51 1611
A. Electronic State of the Metals in Ni-Pd-Pt NPs Photoelectrons were excited by monochromated Al Kα radiation. Detection was performed with a delay-line detector and a concentric hemispherical analyzer. The X-ray tube was operated at 150 W. The pass energy of the concentric hemispherical analyzer was 20 for narrow-scan spectra. The analyzed area on the specimen surface was 300 700 mm 2 and was located in the center of the irradiated region. For the sample preparation, the precipitated NPs were deposited on carbon tape and dried in air. The instrument was operated at a vacuum level of 1 10 8 torr. Pd3d and Pt4f areas show that Pd and Pt are present in the zero valent metallic state in the Ni- Pt/Pd alloy NPs.The Pd3d and Pt4f XPS analytical results are shown below for Ni-Pd-Pt NPs: 4000 Intensity (Counts/s) 3500 2500 2000 1500 345 Pd3d 3/2 Pt4f 340.3 5/2 74.0 Pd3d 5/2 Pt4f 335.0 7/2 70.7 Pt4d 3/2 Ni3p 331.0 66.1 340 335 330 Binding Energy () 325 Intensity (Counts/s) 2500 2000 1500 1000 500 Pt4f 7/2 Pt4f 5/2 70.7 74.0 Ni3p 66.1 0 75 70 65 Binding Energy () 60 Fig. S1. XPS spectra taken for Ni-Pd-Pt NPs in the Pd3d and Pt4f areas. Pd3d and Pt4f areas show that Pd and Pt are present in the zero valent metallic state in the Ni-Pd-Pt alloy NPs.
B. Elemental Distribution in Ni-Pt NPs. (a) (b) (c) (d) Fig. S2. EDS Mapping results of Ni-Pt NPS. (a) STEM-HAADF image and (b-d) EDS elemental mapping images of the Ni-Pt NPs. (b) overview of the mapping results, (c) Ni K edge, and (d) Pt M edge.
C. Identification of Oleylamine Adsorbed on the Surface of Ni-Pd-Pt Particles (A) a. Oleylamine (B) a. Oleylamine Transmittance (a.u.) b. 1 st cycle c. 2 nd cycle d. 3 rd cycle Transmittance (a.u.) b. 2 nd cycle c. After etching with HNO 3 3100 2900 2800 2700 2600 3100 2900 2800 2700 2600 Wavenumber (cm -1 ) Wavenumber (cm -1 ) Fig. S3. FTIR spectra of Ni-Pd-Pt samples. The figures (A) and (B) shows the results of FTIR analysis used to examine the presence/absence of oleylamine. The results in Fig. (A) are that of samples washed with the mixture of toluene and methanol for different number of times. On the other hand, the results for the samples etched with nitric acid after washing with the mixture of toluene and methanol is shown in Fig. (B). For convenience, the analysis was made in the range from 2600 to 3100 cm -1. The symmetric and asymmetric vibration of alkyl chain at 2850 and 2918 cm -1, the stretching vibration mode of CH 3 at 2952 cm -1 and the corresponding peak C-H stretching mode of C H adjacent to the C=C bond at 3005 cm -1 are observed in 70 % pure oleylamine (curve (a) in figures (A) and (B)). The spectra show progressive reduction in the intensities of the peaks corresponding to oleylamine with the increase in the number of washing cycles. On the other hand, the removal of oleylamine was confirmed when the sample was etched with nitric acid (curve (c) in Fig. (B)).
D. Estimation of Oleylamine Adsorbed on the Surface of Ni-Pd-Pt Particles 0 (b) NPs etched with HNO 3 Weight (%) -5-10 (a) Ni-Pt-Pd NPs 4.5 % 7.9 % -15 0 100 200 300 400 500 Temperature ( o C) Fig. S4 Thermogravimetric analysis of (a) as-synthesized and (b) acid etched Ni-Pd-Pt particles in N 2 gas atmosphere. The weight loss corresponding to the region below 200 o C, could be ascribed to the desorption of solvents such as toluene and methanol used to wash the particles. At temperatures above 200 o C, a weight loss of 5.8 % and 2.3 %, which could be ascribed mainly to oleylamine were observed for samples washed with (a) mixture of toluene and methanol and (b) nitric acid, respectively. If we assume that the 20 nm cubic Ni-Pd-Pt particles are covered with monolayer of oleylamine, the weight fraction will be around 7.5 % (assuming the cross-section of oleylamine molecule to be 20 Å 2 ). Thus the surfactant coverage in particles used for the measurement of catalytic activity is estimated to be less than 30 %.