Final revised SI-1 - Royal Society of Chemistry · 2019-11-04 · Supporting Information Selective...

Supporting Information

Selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over

Rh-loaded carbon catalyst in aqueous media under mild conditions

Babasaheb M. Matsagar,*a† Chang-Yen Hsu,a† Season S. Chen,b Tansir Ahamad,c Saad M

Alshehri,c Daniel C.W. Tsang,*b and Kevin C.-W. Wu*a,c,d

a Department of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road,

Taipei 10617, Taiwan bDepartment of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung

Hom, Kowloon, Hong Kong, China. c Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh

11451, Saudi Arabia

d Center of Atomic Initiative for New Materials (AI-MAT), National Taiwan University, Taiwan e International Graduate Program of Molecular Science and Technology, National Taiwan University

(NTU-MST), Taiwan

† The first two authors contributed the paper equally

Email of corresponding authors matsagar03@ntu.edu.tw, dan.tsang@polyu.edu.hk,

kevinwu@ntu.edu.tw

Electronic Supplementary Material (ESI) for Sustainable Energy & Fuels.This journal is © The Royal Society of Chemistry 2019

Fig. S1 XRD of Rh/C catalyst

Fig. S2 TEM-EDS elemental mapping for Rh/C catalyst.

10 20 30 40 50 60 70 80

Inte

nsity

(a.u

.)

2 qo

22.8

43

26.3

(111)

(200)

(220)

200µm C Kα1

200µm Rh Lα1200µm O Kα1

sample

Fig. S3 (a) XPS of Rh 3d for Rh/C catalyst, (b) XPS of C 1s for Rh/C catalyst.

281283285287289291293295

Inte

nsity

(a.u

.)

BE (eV)

304306308310312314316

Inte

nsity

(a.u

.)

BE (eV)

C-C

C-O-C

O-C=O

Rh3d5/2(oxide)

Rh3d5/2(metal)Rh3d3/2

(oxide)

Rh3d3/2(metal)

(a)

(b)

Scheme 1 Synthesis of Ni/CB. For the synthesis of Ni/AC AC was used instead of CB.

Scheme 2 Synthesis of Ni/C derived from Ni-MOF.

0.5 g Ni(NO3)2·6H2O

solid

20 mL EtOH+10 mL H2O

1) 5 min stirring

1 h stirring (RT)

Reduction 450 ºC, 4 h

2) 1 g CB

Solvent separation

Ni/CB

2.52 g Trimesic acid 5..23 g Ni(NO3)2·6H2O

50 mL DMF

Ni-MOF (Ni-BTC)

Ni/C

50 mL DMF

30 min sonication

30 min sonication

2) 100 ºC, 24 h

Pyrolysis (N2 atm)450 ºC, 5 h

1) 200 mL DMF

Mixing

Fig. S4 XRD of Ni/CB catalyst after reduction at 450 ºC.

Fig. S5 XRD of Ni/C catalyst derived from Ni-MOF after reduction at 450 ºC.

10 20 30 40 50 60 70 80

Inte

nsity

(a.u

.)

2 qo

CB Ni (111)

Ni (200)

Ni (220)

10 20 30 40 50 60 70 80

Inte

nsity

(a.u

.)

2 θ�

Nickel carbide Ni (200) Ni (220)

Ni (111)

Carbon

Fig. S6 SEM of Ni/CB catalyst.

Fig. S7 SEM of Ni/C catalyst derived from Ni-MOF.

500 nm�500 nm�

200 nm� 200 nm�

(a)� (b)�

(c)� (d)�

200 nm� 200 nm�

(c)� (d)�

20 μm

Fig. S8 XRD of Active carbon and Rh/C catalyst.

Fig. S9 XRD of Rh/Al2O3 catalyst.

10 20 30 40 50 60 70 80 90

Inte

nsity

(a. u

.)

2qo

Active carbon

Rh/C

10 20 30 40 50 60 70 80 90

Inte

nsity

(a. u

.)

2 qo

Rh

(111

)

Rh

(200

) Rh

(220

)g-Al2O3g-Al2O3g-Al2O3

Rh

(311

)

Fig. S10 Effect of reaction time on the FOL hydrogenation under ambient H2 pressure.

Reaction condition: FOL 12 mg, Rh/C 5 mg, DMA 5 mL, H2 gas flow rate 30 mL min-1, 30 ºC.

Fig. S11 Effect of reaction time on the FAL hydrogenation under ambient H2 pressure.

Reaction condition: FAL 23 mg, Rh/C 10 mg, DMA 10 mL, H2 gas flow rate 30 mL min-1, 30

ºC.

0

20

40

60

80

100

5 8 12 16 20

Prod

uct Y

ield

(%)

Reaction Time (h)

2-MTHF THFA

0

20

40

60

80

12 16 20 24

Prod

uct Y

ield

(%)

Reaction Time (h)

2-MTHF THFA

Fig. S12 Effect of substrate concentration on the FOL hydrogenation under ambient H2

pressure. Reaction condition: Rh/C 5 mg, DMA 5 mL, H2 gas flow rate 30 mL min-1, 16 h.

Fig. S13 Effect of substrate concentration on the FAL hydrogenation. Reaction condition: Rh/C

25 mg, H2O 25 mL, H2 pressure 1 MPa, 30 ºC, 8 h.

0

20

40

60

80

100

12 64 124

THFA

Yie

ld (%

)

FOL (mg)

0

20

40

60

80

100

Prod

uct Y

ield

(%)

FAL (g)

FOL THFA

Fig. S14 (a) The rate constant for FAL hydrogenation into FOL, (b) Arrhenius plot for FAL

hydrogenation into FOL. Reaction condition: FAL 60 mg, Rh/C 25 mg, water 25 mL, H2 gas

flow rate 30 mL min-1.

0

1

2

3

4

5

0 10 20 30 40 50

-ln(1

-X)

Time (min)

30 degree

45 degree

60 degree

Linear (30degree)Linear (45degree)

-3

-2.7

-2.4

-2.1

0.0029 0.003 0.0031 0.0032 0.0033 0.0034

lnK

1/T (K-1)

(a)

(b)

Fig. S15 Proposed mechanism for the hydrogenation of FAL into THFA over Rh/C catalyst.

Rh

+H2

-H2

OO

Rh Rh Rh Rh

OO

Rh Rh Rh

H H

Rh

OO

Rh Rh Rh

H H

Rh

OHO

Rh Rh Rh

Rh Rh Rh Rh

-H2+H2

H H H H

OHO

Rh Rh Rh Rh

H H H H

OHO

Rh Rh Rh Rh

OHO