Supporting information

Probing the promotional roles of cerium in structure

and performance of Cu/SiO2 catalysts for ethanol

production

Peipei Aia, ‡, Minghui Tanc, ‡, Prasert Reubroycharoend, Yang Wang b, Xiaobo Feng b,

Guoguo Liub, Guohui Yangb, c, *, Noritatsu Tsubakib, *

a Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi

Province, Taiyuan University of Technology, Taiyuan, Shanxi 030024, PR China

b Department of Applied Chemistry, School of Engineering, University of Toyama,

Gofuku 3190, Toyama 930-8555, Japan

c State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese

Academy of Sciences, Taiyuan 030001, PR China

d Department of Chemical Technology, Faculty of Science, Chulalongkorn University,

Bangkok 10330, Thailand

* Corresponding Author: E-mail: yanggh@sxicc.ac.cn (Guohui Yang) tsubaki@eng.u-

toyama.ac.jp (Noritatsu Tsubaki)

‡ These authors contributed equally to this work.

Electronic Supplementary Material (ESI) for Catalysis Science & Technology.This journal is © The Royal Society of Chemistry 2018

S2

20 30 40 50 60 70 80 90

Inte

nsity

(a.u

.)

2 Theta (degree)

800

25

700600500400

350

300

250200

SiO2 copper phyllosilicate Cu

Figure S1 In situ XRD patterns after reduction at different temperatures for the calcined

2Ce-Cu/SiO2 catalyst.

S3

0.0 0.2 0.4 0.6 0.8 1.0

(j)

(i)

(h)

(g)

(f)

(e)

(d)

(c)

(b)Qua

ntity

ads

orbe

d (c

m3 /g

STP

)

Relative pressure (P/P0)

(a)

Figure S2 N2 physisorption isotherms of (a) SiO2, (b) 1Ce/SiO2, (c) Cu/SiO2, (d) 0.5Ce-

Cu/SiO2, (e) 1Ce-Cu/SiO2, (f) 1.5Ce-Cu/SiO2, (g) 2Ce-Cu/SiO2, (h) Cu/CeO2, (i)1Ce-

Cu/SiO2-i and (j) 1Ce-Cu/SiO2 catalysts.

S4

920 910 900 890 880 870

(b)

(c)In

tens

ity (a

.u.)

u'"u" u' u v'"

v" v' (d)v

(a)

Kinetic energy (eV)

Figure S3 Ce XPS of reduced (a) 0.5Ce-Cu/SiO2, (b) 1Ce-Cu/SiO2, (c) 1.5Ce-Cu/SiO2,

and (d) 2Ce-Cu/SiO2 catalysts.

S6

20 30 40 50 60 70 80

Inte

nsity

(a.u

.)

2Degree

Figure S4 XRD pattern of spent Cu/SiO2 catalyst after 100 h reaction.

S6

4 8 12 16 200

5

10

15

20

25

Perc

enta

ge (%

)

Particles size (nm)

Mean size = 11.6 nm

Figure S5 TEM image and particles size distribution of spent Cu/SiO2 catalyst.

S6

4 6 8 100

5

10

15

20

Perc

enta

ge (%

)

Particles size (nm)

Mean size = 6.54 nm

Figure S6 TEM image and particles size distribution of spent 1Ce-Cu/SiO2 catalyst.

S7

Table S1 Catalytic performance of 1Ce-Cu/SiO2 catalysts under different reaction

temperature

Sel. (%)Catalyst T Conv. (%)

Ethanol MG EG Others

1Ce-Cu/SiO2 300 100.0 88.6 0.8 0.8 9.8

1Ce-Cu/SiO2 280 100.0 91.8 0.5 0.7 7.0

1Ce-Cu/SiO2 260 99.8 73.2 1.0 9.8 16.0

1Ce-Cu/SiO2 240 99.8 31.3 0.5 55.7 12.5

1Ce-Cu/SiO2 220 99.5 8.6 0.6 85.4 5.4

1Ce-Cu/SiO2 200 99.5 2.2 0.1 95.7 2.0

1Ce-Cu/SiO2 180 87.9 0.6 22.9 71.7 4.8

Reaction conditions: P = 2.5 MPa, WHSV = 0.8 h-1, H2/DMO molar ratio = 200,

reaction time= 8 h. MG: methyl glycolate, EG: ethylene glycol, others mainly consist of

methyl methoxyacetate, methyl acetate, 1, 2-propanediol, 1, 2-butanediol and dimethyl

carbonate.