1  

Supporting Information for

Aerobic Oxidation of Primary Aliphatic Alcohols over

Bismuth Oxide Supported Platinum Catalysts in Water

Tianliang Lu, a,b Zhongtian Du, a Junxia Liu, a,b Hong Ma a and Jie Xu*a

a Dalian National Laboratory for Clean Energy, State Key Laboratory of Catalysis,

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P.

R. China

b University of the Chinese Academy of Sciences, Beijing 100039, P. R. China

Phone &Fax: (+86)-411-8437-9245

*Corresponding author: E-mail: xujie@dicp.ac.cn

Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2013

 

 

2  

Additional Results

20 30 40 50 60

Pt/Bi2O

3-300

Pt/Bi2O

3-200

Pt/Bi2O

3-urIn

tens

ity

2Theta / o

Bi2O

3-ur

 

Fig. S1 XRD patterns of Bi2O3-ur, Pt/Bi2O3-ur, Pt/Bi2O3-200 and Pt/Bi2O3-300.

1000 800 600 400 200 0

Bi 4s Bi 4p O 1sBi 4d

Pt

4fBi

5d

Pt/Bi2O

3-200

Inte

nsit

y / C

PS

Binding Energy / eV

Bi2O

3-ur

Bi2O

3-200

Pt/Bi2O

3-ur Bi 4f

 

Fig. S2 X-ray photoelectron survey spectrum of Bi2O3-ur, Bi2O3-200, Pt/Bi2O3-ur and

Pt/Bi2O3-200.

Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2013

 

 

3  

80 75 70 65

Pt 4f7/2

69.9 eV

Inte

nsit

y / C

PS

Binding Energy / eV

Pt 4f5/2

73.2 eV

3.3 eV

Pt0

 Fig. S3 XPS spectra of Pt 4f in Pt/Bi2O3-150.

170 165 160 155

(1)Bi4f

5/2 162.4 eV

Bi4f7/2

157.0 eV5.4 eV

a Bi4f5/2

160.6 eV

b Bi4f7/2

155.2 eV5.4 eV

a b

Binding Energy / eV

(2)

Inte

nsit

y / C

PS

a b5.4 eV

5.4 eV

Bi4f7/2

157.3 eVBi4f

5/2 162.7 eV

a Bi4f5/2

160.4 eV

b Bi4f7/2

155.0 eV

 Fig. S4 XPS spectra of Bi 4f in (1) Pt/Bi2O3-200 and (2) Pt/Bi2O3-200 (after reaction).

Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2013

 

FFig. S6 TEM images and p

Fig. S5 TEM

photographs o

P

 

 

4 

M image of Pt/

of (a) Bi2O3-u

Pt/Bi2O3-200

/γ-Al2O3-200

ur, (b) Bi2O3-2

0.

0.

200, (c) Pt/Bii2O3-ur and (d)

Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2013

 

 

5  

0

20

40

60

80

100 n-butanal n-butyric acid

Sel

ecti

vity

/ %

Reaction temperature / oC

RT 50 70 90

0

20

40

60

80

100

conversion

Con

vers

ion

/ %

Fig. S7 Effect of reaction temperature on the oxidation of n-butanol. Reaction conditions: 2.5

mmol n-butanol, 2 mL H2O, 0.20 g Pt/Bi2O3-200, 0.2 MPa O2, 5 h.

0.1 0.20

20

40

60

80

100

Con

vers

ion

or s

elec

tivi

ty /

%

O2 Pressure / MPa

conversion n-butanal n-butyric acid

Fig. S8 Effect of O2 pressure on the oxidation of n-butanol. Reaction conditions: 2.5 mmol

n-butanol, 2 mL H2O, 0.20 g Pt/Bi2O3, 90 oC, 5 h.

Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2013

 

Fig.

Reac

Sche

as so

2

4

6

8

10

Con

vers

ion

/ %

S9 Time co

ction conditio

F

O

eme S1: Prop

olvent.

0

0

20

40

60

80

00

ourse of n-b

ons: 2.5 mmo

Fig. S10 Prop

OHPt/Bi2O3

O2

posed reactio

2

Pt/Bi

butanol oxida

ol n-butanol, 2

posed sketch

n pathway fo

 

 

6 

4

Reaction tim

i2O

3-200

ation over Pt

2 mL H2O, 0.

for the prepa

OH2O

or Pt/Bi2O3 ca

6

me / h

Pt/gama-A

t/Bi2O3-200

.20 g catalyst

aration of Pt/B

OH

OH

atalyzed oxid

8

Al2O

3-200

and Pt/γ-Al2

t, 90 oC, 0.1 M

Bi2O3 catalyst

H O2

Pt/Bi2O3

dation of n-bu

10

 

2O3-200 cata

MPa O2.

 

t.

O

OH

utanol using w

lysts.

O

water

Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2013