Supporting Information
Olefin hydrogenation catalysis of platinum nanocrystals with
different shapes
Ming Cao, Keiko Miyabayashi, Zhongrong Shen, Kohki Ebitani, Mikio Miyake*
School of Materials Science, Japan Advanced Institute of Science and Technology,
1-1, Asahidai, Nomi-shi, Ishikawa 923-1292, Japan.
E-mail: miyake@jaist.ac.jp
Calculation of Turnover frequency (TOF) values for Pt nanocrystals
To quantify TOF, the amounts of the surface atoms are calculated for the
different Pt nanocrystals used in the present study (Table S1). Pt cube is 6.7 nm,
composed entirely of (100) facet (calculated using cube model). Pt tetrahedron is 4.6
nm, composed entirely of (111) facet (calculated using the tetrahedron model). Pt
cuboctahedron (7.5nm) is formed with (100) and (111) facets, which is assumed to
follow a cuboctahedron structure model. The cylinder is used as model for Pt
nanowire (diameter 2nm, length 50nm), which is composed of entire (111) facet.
The assuming average Pt surface densities are of 1.31019 atomsm-2 and
1.51019 atomsm-2 for Pt(100) and Pt(111) facets, respectively (Anderson 1975).1
For each shape, formulae for the calculation of the total atoms, the number of surface
atoms could be obtained, which depended on the size of the Pt nanocrystals by TEM.
TOF 
Mol(substr ate)  conversion (GC)
The number of surface atoms (all Pt atoms)  Time
The number of surface atoms
The number of surface atoms
(all Pt atoms)

 Volume (all Pt atoms)
(one particle)
Volume (one particle)
1. Anderson JR (1975) Structure of Metallic Catalysts, Academic Press, London.
1
The number of surface atoms
(one particle)
Volume (all Pt atoms) 
 Surface Area (one particle)  surface density
Weight of catalyst  percent (% ICP) (mg)
Density of Pt (21.45  10 -18 mg/nm 3 )
Table S1 The surface area, volume and the number of surface atoms of a Pt
nanocrystal according to the ideal model
size (nm)*
Surface area
(one particle)
(nm2)
Volume
(one particle)
(nm3)
The number of surface
atoms (one particle)
(atoms)
Pt cube
a=6.7
269.3
300.8
3.51021
Pt tetrahedron
a=4.6
36.6
11.5
5.51020
Pt cuboctahedron
a=7.5
133.1
124.3
1.91021
Pt nanowire
a=2.0; L=50
314.2
157.1
4.71021
* a: length of edge for Pt cube and Pt tetrahedron, or diameter of Pt cuboctahedron and Pt
nanowire; L: length of cylinder for Pt nanowire.
2
Fig. S1 1HNMR of Pt nanowire with PAA.
3
Fig. S2 Shape distributions of Pt nanocrystals. (a) Pt cube (10.1 nm), (b) Pt cube (9.5
nm), (c) Pt cube (8.2 nm), (d) Pt cube (6.7 nm), (e) Pt tetrahedron (4.6 nm) and (f) Pt
cube (8.5 nm) after 3rd hydrogenation of cyclohexene.
Fig. S3 Size distributions of Pt nanocrystals. (a) Pt cube (10.10.7 nm), (b) Pt cube
(9.50.8 nm), (c) Pt cube (8.20.5 nm), (d) Pt cube (6.70.6 nm), (e) Pt tetrahedron
(4.61.2 nm), (f) Pt nanowire (2.0 nm), (g) Pt cuboctahedron (7.50.5 nm) and (h) Pt
cube (8.50.7 nm) after 3rd hydrogenation of cyclohexene.
4
Fig. S4 XPS spectra (Pt 4f) of (a) Pt cube (6.7 nm), (b) Pt tetrahedron (4.6 nm),
(c) Pt nanowire (2.0 nm) and (d) Pt cuboctahedron (7.5 nm).
Table S2 Binding energies of Pt 4f of Pt cube, Pt tetrahedron, Pt nanowire and Pt
cuboctahedron
Pt 4f5/2 (eV)
Pt 4f7/2 (eV)
Pt(x+)
Pt(0)
Pt(x+)
Pt(0)
Pt(x+)
content
Pt cube (6.7 nm)
75.5
74.3
72.2
71.0
12.8%
Pt tetrahedron (4.6 nm)
75.4
74.3
72.2
71.0
17.2%
Pt nanowire (2.0 nm)
75.5
74.4
72.2
71.1
19.4%
Pt cuboctahedron (7.5 nm)
75.5
74.4
72.3
71.1
16.8%
5