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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 [email protected], [email protected],
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