Room-temperature synthesis of mesoporous CuO nanostructure and its catalytic activity for cyclohexene oxidation

Xinxin Sang, Jianling Zhang*, Tianbin Wu, Bingxing Zhang, Xue Ma, Li Peng, Buxing

Han, Xinchen Kang, Chengcheng Liu, Guanying Yang

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid

and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of

Sciences.

4000 3500 3000 1500 1000 500

Wavenumber / cm-1

commercial CuO CuO in this work

Inte

nsity

Fig. S1 FT-IR spectrum of (a) CuO synthesized in TEA and (b) commercial CuO. CuO

obtained in this work presents the same FT-IR spectrum as commercial CuO. The

bands in the infrared spectrum at below 700 cm-1 are due to Cu-O vibrations.

The peak at 3500 cm-1 indicates that there are still traces of hydroxyl groups

due to the surface adsorption. No peaks of TAE were observed.

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015

1200 800 400

Inte

nsity

Binding energy (eV)

a

960 950 940 930

953.5

Inte

nsity

Binding energy (eV)

933.6Cu2pShake-upsatellites

b

534 531 528

c

Inte

nsity

Binding energy (eV)

529.7

531.2

Fig. S2 XPS study of CuO synthesized in TEA: (a) A wide-range of XPS spectra (b) Cu2p

spectra (c) O1s spectra. The survey spectra (Fig. S2a) indicates that there is no

amine left on the surface of CuO nanocrystals because the characteristic N1s

peaks do not appeare in the range of 394-410 eV. In Fig. S2b, the peaks located

at 933.6 eV and 953.5 eV can be assigned to Cu2p3/2 and Cu2p1/2 of CuO,

respectively. The Cu2p spectrum contains a characteristic (for the Cu2+ state)

“shake-up” satellite. In Fig. S2c, the peak at 529.7 eV corresponds to O2− in CuO.

The O1s spectrum contains a small shoulder on the side with binding energy 531.2

eV, which can be attributed to the weakly charged oxygen species from air. The Cu2p

and O1s spectra presented in Fig. S2 are typical for CuO samples and agree well with

the literature data.1

Trimethylamine

(222

)(3

11)

(113

)(3

10)

(113

)(2

02)

(020

)(202

)(1

12)

(111

)(0

02)

Inte

nsity

2-Theta / o

(110

)

20 30 40 50 60 70 80

JCPDS:48-1548

Inte

nsity

Tripropylamine

10 20 30 40 50 60 70 80

JCPDS:48-1548

JCPDS:13-0420

2-Theta / o

Inte

nsity

Tributylamine

10 20 30 40 50 60 70 80

JCPDS:48-1548

JCPDS:13-0420

2-Theta / o

2-Theta / o

JCPDF 13-0420

Inte

nsity

Diethylamine

JCPDF 48-1548

10 20 30 40 50 60 70 80

Inte

nsity

2-Theta / o

Ethylamine

JCPDF 13-0420

10 20 30 40 50 60 70 80

Fig. S3 XRD patterns of the samples synthesized in different amine solution.

Fig. S4 TEM images of the samples synthesized in TMA (a, b), TPA (c, d), TBA (e, f)

solution.

Fig. S5 TEM images of the samples synthesized in DEA (a, b) and EA (c, d).

20 30 40 50 60 70 80

c

b

2-Theta / o

Inte

nsity

a

Fig. S6 XRD patterns of the CuO synthesized from Cu(NO3)2 (a), CuSO4 (b) and CuCl2

(c) in TEA aqueous solution.

Fig. S7 TEM image of commercial CuO.

0.0 0.2 0.4 0.6 0.8 1.00

2

4

6

Relative Pressure (P/Po)

Vol

ume a

dsor

bed /

cm3 g-1

Fig. S8 N2 adsorption-desorption isotherm of commercial CuO.

Fig. S9 TEM image of the CuO reused four times.

References

1. H. Cao, H. F. Jiang, X. S. Zhou, C. R. Qi, Y. G. Lin, J. Y. Wu and Q. M. Liang, Green

Chem., 2012, 14, 2710.