Conversion of furfural into cyclopentanone over Ni-Cu ... · 1 Supporting Information for...

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)

Electronic Supplementary Material (ESI) for Green ChemistryThis journal is © The Royal Society of Chemistry 2013

2

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.


3

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.


4

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.


5

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


6

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.


7

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.


8

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.


9

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.


10

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


12

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]


13

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.


14

6. NMR, MS and GC Traces

Fig S10. 1H and 13C NMR spectra of 4-hydroxy-2-cyclopentenone.

O

OH

O

OH


15

Fig S11. 1H NMR and 13C NMR spectra of bicyclopentyl.


16

Fig S12. 1H and 13C NMR spectra of 2-cyclopentenone.

、

O

O


17

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


18

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


19

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


20

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)


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).


21

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


22


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)


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)


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


23

m/z 102 (M+, 0%), 71 (100), 43 (43)


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


24

(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


25

Fig S29. GC trace of furfural hydrogenation (Fig 4, line a, left).

O

OH


26

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


27

Fig S32. GC trace of furfural hydrogenation in 1,4-dioxane (Fig 4, line d, left).

O O


28

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


29

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


30

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


31

Fig S39. The photo of the black solid observed (Table 1, entry 6).


Conversion of furfural into cyclopentanone over Ni-Cu ... · 1 Supporting Information for...

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