conversion of furfural into cyclopentanone over ni-cu ... · 1 supporting information for...
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1
Supporting Information for
Conversion of furfural into cyclopentanone over Ni-Cu bimetallic catalysts Yanliang Yang,ab Zhongtian Du, a Yizheng Huang,a Fang Lu,a Feng Wang,a Jin Gaoa and Jie
Xu*a aDalian National Laboratory for Clean Energy, State Key Laboratory of Catalysis,
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023,
China bUniversity of Chinese Academy of Sciences, Beijing 100039, China
E-mail: [email protected]
Contents: 1. Characterization of Catalysts (pp.2-5)
2. Isolation of Key Intermediates (p.6)
3. Optimization of Reaction Conditions (pp.7 and 8)
4. Control Experiments (pp.9 and 10)
5. Preparation of Cycloalkanes (pp.11-13)
6. NMR, MS and GC Traces (pp.14-31)
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1. Characterization of Catalysts
N2 physical adsorption/desorption measurement was carried out at liquid nitrogen
temperature on an Autosorb-1 Quantachrome instrument. Samples were pre-degassed at
300 °C for about 10 h to remove water and other physically adsorbed species. The BET
surface area (SBET) was calculated using the Brunauer-Emmett-Teller equation (relative
pressure between 0.05 and 0.25). The pore size and pore volume were calculated from the
desorption branches of the nitrogen isotherms employing the Barrett-Joyner-Halenda
(BJH) model.
Temperature programmed reduction (TPR) profiles were obtained on a
Micromeritics AutoChem II 2920 Instrument with a thermal conductivity detector (TCD).
Typically, 50 mg sample of the calcinated catalyst was degassed at 200 oC in an
atmosphere of Ar for 2 h. After the sample was cooled to a temperature of 50 oC under Ar
flow, the in-line gas was switched to 10% H2/Ar, and the sample was heated to 800 oC at
a rate of 10 oC min-1. The H2 consumption was monitored by a TCD detector.
The X-ray powder diffraction (XRD) patterns were obtained using Rigaku D/Max
2500/PC powder diffractometer with Cu Kα radiation (λ = 0.15418 nm) at 40 kV and 200
mA in a scanning rate of 5o/min.
The microstructure of the materials was examined by transmission electron
microscopy (TEM) on a JEOLJEM-2000EX electron microscopy.
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1 2 3
Inte
nsi
ty(a
.u)
2 theta/degree
Fig S1. Small angle XRD pattern of as-synthesized SBA-15.
0.0 0.2 0.4 0.6 0.8 1.00
200
400
600
800
1000 Adsorption Desorption
Vo
lum
e ad
so
rbe
d (
cm
3 /g)
Relative pressure (P/P0)
40 80 120 160 200
0
2
4
6
8
Dv(
log
d) (c
c/g)
Pore diameter (Angstrom)
Fig S2. N2 adsorption/desorption isotherms of as-synthesized SBA-15.
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100 200 300 400 500 600 700 800
Temperature / oC
H2
con
su
mp
tio
n (
a.u
.)
Ni
NiCu-10
NiCu-30
Cu
NiCu-80
NiCu-50
Fig. S3 TPR profiles of the monometallic Ni/SBA-15, Cu/SBA-15 and bimetallic
NiCu/SBA-15 catalysts.
20 30 40 50 60 70 80
Inte
ns
ity
(a.
u)
Cu/SBA-15
2 Theta/degree
Ni/SBA15
NiCu-80/SBA-15
NiCu-50/SBA-15
NiCu-30/SBA-15
NiCu-10/SBA-15
Before reduction
20 30 40 50 60 70 80
Inte
nsi
ty (
a.u
)
2 Theta/degree
Cu/SBA-15
Ni/SBA-15
NiCu-80/SBA-15
NiCu-50/SBA-15
NiCu-30/SBA-15
NiCu-10/SBA-15
After reduction
Fig S4. Wide angle XRD patterns before and after reduction.
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Fig S5. TEM images of as-synthesized SBA-15.
Fig S6. TEM images of NiCu-50/SBA-15.
Table S1 Physic properties of as-synthesized catalysts.
Sample DPore (nm) VPore (cm3g-1) SBET (m2g-1)
SBA-15 6.5 1.37 952
Ni/SBA-15 5.7 1.25 816
NiCu-10/SBA-15 5.6 1.25 672
NiCu-30/SBA-15 5.6 1.08 641
NiCu-50/SBA-15 5.6 1.09 691
NiCu-80/SBA-15 4.3 1.14 727
Cu/SBA-15 5.6 1.26 883
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2. Isolation of Key Intermediates
2.1 Isolation of 4-Hydroxy-2-cyclopentenone
4-hydroxy-2-cyclopentenone was synthesized in water without any catalyst.
Typically, a solution of furfuryl alcohol (15.0 g, 0.15 mol) in water (300 mL) was
loaded into a 600 mL Parr stainless steel autoclave. After sealed and purged with H2 for 4
times to exclude air, the autoclave was heated to 160 oC and then purged with 2 MPa of
H2. After the reaction was completed (8 h), the solvent was removed under reduced
pressure and red dark oil was obtained. The crude product was purified by silica gel
chromatography using 3:1 n-hexane/ethyl acetate and then 1:1 n-hexane/ethyl acetate to
afford the product, red yellow oil (Yield 52%, 7.78 g). 1H NMR (400 MHz; CDCl3;Me4Si)
δ = 7.58 (dd, J = 5.6Hz, 2.3Hz, 1H, CH), 6.25 (dd, J = 5.6Hz, 0.8Hz, 1H, CH), 5.08 (t, J
= 5.6Hz, 1H, CH), 2.80 (dd, J = 18.5Hz, 6.1Hz, 1H, CH2), 2.30 (dd, J = 18.5Hz, 2.1Hz,
1H, CH2), 2.11 (d, J = 6.5Hz, 1H, OH); 13C NMR (100 MHz; CDCl3; Me4Si) δ = 207.6
(C), 164.1(CH), 134.9(CH), 70.3(CH), 44.3(CH2). m/z 98 (M+, 100%), 97 (41),70 (75),
55 (54), 44 (40), 43 (45), 42 (95).
The corresponding 1H NMR, 13C NMR and MS are shown in Fig S10 and S13.
2.2 Isolation of 2-Cyclopentenone
10.0 g aqueous solution of 4-hydroxy-2-cyclopentenone (10.2 mmol) and NiCu-50/SBA-
15 (0.20 g) were loaded into a 60 mL stainless steel autoclave. After sealed and purged
with H2 for 4 times to exclude air, the autoclave was purged with 0.1 MPa of H2 and then
heated to 160 oC. 4 h later, the reactor was cooled and the mixture was centrifuged.
Product was extracted by dichloromethane and purified by silica gel chromatography
using 3:1 n-hexane/ether, 2:1 n-hexane/ether and then 1:1 n-hexane/ether to afford the
product, colorless oil. 1H NMR (400 MHz; CDCl3; Me4Si) δ = 7.74 (dt, J = 5.6 Hz, 2.7
Hz, 1H, CH), 6.22 (dt, J = 4.8 Hz, 2.1 Hz, 1H, CH), 2.71 (dq, J = 6.7 Hz, 2.2 Hz, 2H,
CH2), 2.40-2.33 (m, 2H, CH2). 13C NMR (100 MHz; CDCl3; Me4Si) δ = 210.7 (C), 164.9
(CH), 134.7 (CH), 34.2 (CH2), 29.1 (CH2). m/z 82 (M+, 100%), 54 (29), 53 (30).
The corresponding 1H NMR. 13C NMR and MS, spectra are shown in Fig S12 and
S14.
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3. Optimization of Reaction Conditions
Scheme S1 Conversion of furfural in water.
Table S2 Conversion of furfural over nickel-based catalyst under H2 atmosphere.a
Entry Catalysts Conv. (%) Seletivity of products (%)
1 2 3 4 5
1 Ni/SiO2 29 35 n.d n.d n.d n.d
2 Ni/Al2O3 >99 3 17 n.d n.d 44
3 Ni/AC >99 2 5 4 n.d 18
4 Ni/ZSM-5 52 29 n.d n.d n.d 3
5 Ni/SBA-15 42 36 n.d 1 4 n.d a Reaction conditions: 10 g 5 wt% furfural aqueous solution, 0.2 g catalyst (10 wt% nickel), 160 oC, 2 MPa
H2, 4 h. Results are based on carbon balance. n.d: not detected by GC.
Table S3 Effect of additives on the hydrogenation of furfural.a
Entry Additives pH b Conv. (%) Distribution of products (%)
1 2 3 4 5
1 Na2CO3 11.0 >99 n.d n.d n.d 40 36
2 Na2HPO4 9.2 >99 2 1 n.d 36 28
3 none 7.0 >99 62 3 17 n.d n.d
4 NaH2PO4 4.8 >99 40 1 6 n.d n.d
5 AcOH 3.3 94 40 2 3 n.d n.d
6 c H3PO4 1.4 - n.d n.d n.d 40 36 a Reaction conditions: 10 g 5 wt% furfural aqueous solution, 0.2 g NiCu-50/SBA-15, 0.1 mmol additive,
160 oC, 4 MPa H2, 4 h. AcOH: acetic acid. Results were based on carbon balance. n.d: not detected by GC.
b pH values were determined at room temperature. c 1 mmol H3PO4, black solid was observed.
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0
10
20
30
40
50
60
70
Sel
ecti
vity
of
cycl
op
enta
no
ne
(%)
H2O1,4-dioxane/H2O1,4-dioxaneCH3OHCH2Cl2Solvent
Fig S7. Hydrogenation of furfural over NiCu-50/SBA-15 in different solvents.
80 100 120 140 160 1800
10
20
30
40
50
60
70
80
Sel
ecti
vity
of
mai
n p
rod
uct
s (%
)
Reaction temperature (oC)
cyclopentanone
cyclopentanol
2-methyltetrahydrofuran
furfuryl alcohol
tetrahydrofurfuryl alcohol
0
10
20
30
40
50
60
70
80
90
100C
on
vers
ion
of
furf
ura
l (%
)
Fig S8. Hydrogenation of furfural over NiCu-50/SBA-15 at different reaction
temperature.
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4. Control Experiments
Table S4 Control experiments under different reaction conditions.a
Entry Substrates Catalyst Atmosphere Yield of CPO+CPL (%) Yield of HCP (%)
1 furfural Y H2 65 n.d
2 furfural Y N2 n.d n.d
3 furfural N H2 n.d n.d
4 furfural N N2 n.d n.d
5 FA Y H2 36 n.d
6 FA Y N2 n.d 60
7 FA N H2 n.d 52
8 FA N N2 n.d 52
9b FA N N2 n.d n.d
10b furfural Y H2 n.d n.d
11c FA N N2 trace n.d
12c furfural Y H2 n.d n.d
13 THFA Y H2 n.d. n.d.
14 MF Y H2 n.d. n.d. a Reaction conditions: 10 g 5 wt% aqueous solution, 0.2 g NiCu-50/SBA-15, 160 oC, 4 h, 0.1 MPa N2 or 4
MPa H2. FA: furfuryl alcohol. CPO: cyclopentanone. HCP: 4-hydroxy-2cyclopentenone. THFA:
tetrahydrofurfuryl alcohol. MF: 2-methyl furan. Y: In the presence of NiCu-15/SBA-15. N: Without
catalyst. n.d: not detected by GC. b in 1,4-dioxane. c at 80 oC.
Table S5 Conversion of furfuryl alcohol in the presence of different ketones.a
Entry Additives b Conv. (%) Selectivity of products (%)
1 2 3 5
1
>99 n.d 20 1 13
2
>99 n.d 24 4 17
3
>99 n.d 8 3 17
4
>99 n.d 22 3 14
a Reaction conditions: 10 g 5 wt% furfural aqueous solution, 0.2 g NiCu-50/SBA-15, 160 oC, 4 MPa H2, 4 h.
n.d: not detected by GC. b The amount of ketone was equal to that of furfuryl alcohol.
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Kinetic experiments
Kinetic experiments were performed in a Parr stainless steel autoclave. For a
typical procedure, a solution of furfuryl alcohol (2.5 g, 0.025 mol) in water (50 mL, H2O
or D2O) was put in a 600 mL Parr stainless steel autoclave. The reactor was sealed and
purged with H2 for 4 times to exclude air, and then it was heated to 120 oC. Samples were
taken every six minutes and analyzed by GC based on internal standard method.
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5. Preparation of Cycloalkanes
5.1 Hydrodeoxygenation of Cyclopentanone into Cyclopentane
Hydrogenation of cyclopentanone was carried out in a 60 mL stainless steel
autoclave equipped with a magnetic stirrer, a pressure gauge and automatic temperature
control apparatus. A typical procedure was as follows: the reactor was initially loaded
with cyclopentanone (10.0 g, 0.2 mol) and Ru/ZSM-5 (3.0 g) catalyst. After the reactor
was sealed and purged with H2 for 4 times to exclude air, the reactor was heated to 180 oC and purged with 4 MPa of H2. 36 h later, the reactor was cooled down to room
temperature. The conversion and selectivity of cyclopentane were determined by area
normalization method (conversion: 89%, selectivity: 96%).
5.2 Self-condensation of Cyclopentanone
A typical procedure was as follows: Cyclopentanone (1100 mL) and sodium
hydroxide aqueous solution (110 mL, 10 wt %) was loaded in reactor, and stirred for 10 h
under reflux. Then the mixture was cooled and allowed to separate in two layers. The
organic phase was analyzed (conversion: 67%, selectivity: 97%), then distilled under
reduced pressure to offer 2-cyclopentylidenecyclopentanone (554.9 g, yield 60%).
5.3 Production of Bicyclopentyl via Catalytic Hydrogenation
Hydrogenation of 2-cyclopentylidenecyclopentanone was carried out in a 600 mL
batch autoclave reactor (Parr Instrument Co.) equipped with an external temperature and
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stirring controller. A typical procedure was as follows: the reactor was initially loaded
with 2-cyclopentylidenecyclopentanone (30.0 g, 0.2 mol) and Ru/ZSM-5 (3.0 g) catalyst.
After the reactor was sealed and purged with H2 for 4 times to exclude air, the reactor
was heated to 180 oC and purged with 4 MPa of H2. 36 h later, the reactor was cooled
down to room temperature. The mixture was filtrated and dried by anhydrous sodium
sulfate to afford the product (colorless oil, 25.2 g, yield 91%). 1H NMR (400 MHz,
CDCl3) δ = 1.72 (s, 4H), 1.59-1.49 (m, 10H), 1.12 (s, 4H).13C NMR (100 MHz, CDCl3) δ
= 46.5, 32.0, 25.5. m/z 138 (M+, 13%), 96 (67), 95 (65), 82 (68), 81 (47), 69 (43), 68
(98), 67 (100) The corresponding MS, 1H NMR and 13C NMR spectra are shown in Fig
S15 and S11.
Fig S9. Total schematic description for the production of cycloalkanes.
Table S6 Chemical and physical properties of bicyclopentyl.
Property Value Reference
Chemical Formula C10H18 -
Molecular weight 138.2 g/mol Calculated
Freezing Point -35 oC (1 atm, air) [S1]
Boiling Point 190 oC [S2,S4]
Density 0.8664 g/cm-3 (30 oC) [S5]
Viscosity
4.22 cs (-34 oC)
[S3] 1.35 cs (38 oC)
0.72 cs (99 oC)
Aniline point 36.5 oC [S4]
Thermal Decomp temp 399 oC [S3]
Luminometer number 52.2 [S3]
Net Heat of Combustion
18297 b.t.u/lb
132864 b.t.u./gal [S3]
42.530 MJ/kg
37.029 MJ/L Calculated from [S3]
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References:
[S1] A. J. Streiff, A. R. Hulme, P. A. Cowie, N. C. Krouskop, F. D. Rossini, Anal. Chem.,
1955, 27, 411-415.
[S2] A. R. Lepley, Anal. Chem., 1962, 34, 322-325.
[S3] L. I. B. M. H. Gollis, B. J. Gudzinowicz, S. D. Koch, J. O. Smith, R. J. Wineman, J.
Chem. Eng. Data, 1962, 7, 311-316.
[S4] G. E. Goheen, J. Am. Chem. Soc., 1941, 63, 744-749.
[S5] A. Weissler, J. Am. Chem. Soc., 1949, 71, 419-421.
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6. NMR, MS and GC Traces
Fig S10. 1H and 13C NMR spectra of 4-hydroxy-2-cyclopentenone.
O
OH
O
OH
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Fig S11. 1H NMR and 13C NMR spectra of bicyclopentyl.
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Fig S12. 1H and 13C NMR spectra of 2-cyclopentenone.
、
O
O
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m/z 98 (M+, 100%), 97 (41), 70 (75), 55 (54), 44 (40), 43 (45), 42 (95)
30 40 50 60 70 80 90 100 1100
50
100
32
39
42
50
53
55
70
98
Fig S13. Mass spectrum of 4-hydroxy-2-cyclopentenone.
m/z 82 (M+, 100%), 54 (29), 53 (30)
(Text File) Scan 201 (2.354 min): 12050303.D\ data.ms30 35 40 45 50 55 60 65 70 75 80 85 90
0
50
100
32 38
39
40 42 44
5052
53
55
57 60 62 66 80
81
82
83
Fig S14. Mass spectrum of 2-cyclopentenone.
m/z 138 (M+, 13%), 96 (67), 95 (65), 82 (68), 81 (47), 69 (43), 68 (98), 67 (100)
(Text File) Scan 1087 (6.595 min): 12021801.D\ data.ms30 40 50 60 70 80 90 100 110 120 130 140 150
0
50
100
32
39
41
51
55
67
79
82 96
103
109
115 123
138
Fig S15. Mass spectrum of bicyclopentyl.
O
O
OH
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m/z 84 (M+, 65%), 56 (31), 55 (100)
(Text File) Scan 159 (2.172 min): 11061501.D\ data.ms30 40 50 60 70 80 90 100
0
50
100
31
39
40
41
42
43 50 53
55
56
57 61 63 66 69 73 83
84
85
m/z 86 (M+, 74%), 84 (4), 58 (27), 57 (100)
(Text File) Scan 147 (2.120 min): H2O18.D\ data.ms30 40 50 60 70 80 90 100
0
50
100
32
39
41
4244
45 50 53
55
57
58
59 62 66 7185
86
87
Fig S16. MS traces of cyclopentanone obtained in ordinary water and H218O.
In H218O
In Ordinary Water
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m/z 98 (M+, 100%), 97 (32), 70 (73), 55 (51), 44 (42), 43 (46), 42 (80)
30 40 50 60 70 80 90 100 1100
50
100
32
39
42
50
53
55
70
98
m/z 102 (M+, 100%), 100 (28), 98 (2), 72 (80), 57 (68), 45 (54), 44 (59), 42 (62)
30 40 50 60 70 80 90 100 1100
50
100
32
39
42
45
50
53
55
57
72
7583
102
Fig S17. MS traces of 4-hydroxy-2-cyclopentenone obtained in ordinary water and
H218O.
In Ordinary Water
In H218O
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m/z 102 (M+, 100%), 100 (90), 98 (5),72 (89), 57 (77), 45 (54), 44 (91), 42 (96)
(Text File) Scan 950 (5.601 min): 11082201.D\ data.ms30 40 50 60 70 80 90 100 110
0
50
100
31
33
39
42
4651
53
57
59 62 68
71
72
7583
100
102
Fig S18. The oxygen exchange between 4-hydroxy-2-cyclopentenone and water (160 oC,
4 h, no catalyst, H2 atmosphere).
m/z 86 (M+, 68%), 84 (35), 57 (100), 55 (71), 41 (49)
(Text File) Scan 134 (2.063 min): 12041240.D\ data.ms30 40 50 60 70 80 90 100
0
50
100
32 38
39
40
41
42 44
4650 53
55
56
57
58
59 61 63 65 69 71 83
84
85
86
87
Fig S19. The oxygen exchange between cyclopentanone and water (160 oC, 4 h, no
catalyst, H2 atmosphere).
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m/z 68 (M+, 100%), 39 (76)
(Text File) Scan 300 (1.384 min): 11071403-g.D\ data.ms30 34 38 42 46 50 54 58 62 66 70 74 78
0
50
100
31
32
36
38
39
40 43
44 57
68
69
Fig S20. Mass spectrum of furan.
m/z 82 (M+, 100%), 81 (61), 53 (49)
(Text File) Scan 327 (1.501 min): 11071403-g.D\ data.ms30 35 40 45 50 55 60 65 70 75 80 85 90
0
50
100
32
38
39
40 4351
53
54
81
82
83
Fig S21. Mass spectrum of 2-methyltetrahydrofuran.
m/z 86 (M+, 8%), 57 (100)
O
O
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(Text File) Scan 141 (2.094 min): 11061501.D\ data.ms30 40 50 60 70 80 90 100
0
50
100
32 38
39 4142
44
45 49 51 53 55
57
58
59 61 63 65
6769
7184
86
Fig S22. Mass spectrum of cyclopentanol.
m/z 84 (M+, 63%), 56 (31), 55 (100)
(Text File) Scan 157 (2.163 min): 11061501.D\ data.ms30 40 50 60 70 80 90 100
0
50
100
31 38
39
40
41
42
43 50 53
55
56
57 60 62 65 67 69 73 81 83
84
85
Fig S23. Mass spectrum of cyclopentanone.
m/z 98 (M+, 100%), 97 (53), 96 (49), 95 (54), 81 (49), 69 (29), 53 (33), 41 (31)
(Text File) Scan 237 (2.510 min): 11071401.D\ data.ms30 40 50 60 70 80 90 100 110
0
50
100
31
3239
42
44 49
51
53
5558 67
69
71
8195
98
99
Fig S24. Mass spectrum of furfuryl alcohol.
OH
O
O OH
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m/z 102 (M+, 0%), 71 (100), 43 (43)
(Text File) Scan 324 (2.887 min): 11090702.D\ data.ms30 40 50 60 70 80 90 100 110
0
50
100
3132
39
41
43
4450 57 61
70
71
73 83 101
Fig S25. Mass spectrum of tetrahydrofurfuryl alcohol.
m/z 132 (M+, 0%), 101 (94), 83 (25), 57 (100), 55 (34)
(Text File) Scan 1515 (8.050 min): 11011201-1.D\ data.ms30 40 50 60 70 80 90 100 110 120 130
0
50
100
3141
43
53
55
57
6169 73
83
101
119
Fig S26. Mass spectrum of (tetrahydrofuran-2,5-diyl)dimethanol.
m/z 98 (M+, 100%), 83 (24), 70 (35), 69 (57), 56 (27), 55 (83)
O OH
O OH
OH
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(Text File) 143 (3.905 ): 12111203-1.D\data.ms
50 60 70 80 90 100 1100
50
100
5153
55
56
5760 62 65
67
69
70
7174 77
80
81
83
84 95
98
99
Fig S27. Mass spectrum of 2-methylcyclopentanone.
m/z 112 (M+, 86%), 111 (29), 97(40), 95 (100)
(Text File) 427 (4.844 ): 12102301.D\data.ms
60 80 100 120 140 160 180 200 2200
50
100
51
556569
79
84
95
112
207
Fig S28. Mass spectrum of (5-methylfuran-2-yl)methanol.
O
O OH
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Fig S29. GC trace of furfural hydrogenation (Fig 4, line a, left).
O
OH
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Fig S30. GC trace of furfural hydrogenation at 80 oC (Fig 4, line b, left).
Fig S31. GC trace of furfural hydrogenation with Na2CO3 as additive (Fig 4, line c, left).
O O
O OH
O OH
O OH O OH
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Fig S32. GC trace of furfural hydrogenation in 1,4-dioxane (Fig 4, line d, left).
O O
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Fig S33. GC trace of furfural hydrogenation in 1,4-dioxane / water (Fig 4, line e, left).
Fig S34. GC trace of furfuryl alcohol conversion in water (Fig 4, line a right).
O O
O
O
HO
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Fig S35. GC trace of furfuryl alcohol conversion at 80 oC (Fig 4, line b, right).
Fig S36. GC trace of furfuryl alcohol conversion using Na2CO3 as additive (Fig 4, line c,
right).
O OH
O OH
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Fig S37. GC trace of furfuryl alcohol conversion in 1,4-dioxane (Fig 4, line d, right).
Fig S38. GC trace of furfuryl alcohol conversion in 1,4-dioxane / water (Fig 4, line e,
right).
O OH
O
HO
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31
Fig S39. The photo of the black solid observed (Table 1, entry 6).
Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2013