Supporting information
Co embedded within biomass-derived mesoporous N-doped carbon as an acid-resistant and chemoselective catalyst for transfer hydrodeoxygenation of biomass with formic acid
Huanhuan Yang,a Renfeng Nie,* a Wang Xia, a Xiaolong Yu, a Dingfeng Jin, b Xinhuan Lu , a Dan Zhou, a Qinghua Xia* a
a Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, & Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, School of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, P.R. ChinabCollege of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China
* Corresponding authorsRenfeng Nie, Hubei University, Wuhan 430062, P.R. ChinaTel/Fax: 86-27-88662747Email: [email protected] Xia, Hubei University, Wuhan 430062, P.R. ChinaTel/Fax: 86-27-88662747Email: [email protected]
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2017
0.0 0.2 0.4 0.6 0.8 1.00
40
80
120
160
200
240
Stotal=0.26 m2/gDv=0.045 cm3/g
Volu
me
(cm
3 /g S
TP)
Relative pressure (p/p0)
(a)
0.0 0.2 0.4 0.6 0.8 1.00
40
80
120
160
200
240
1 100.0000.0050.0100.0150.0200.0250.030
(b)
Stotal=225.1 m2/gDv=0.138 cm3/gDp= 7.1 nm
Volu
me
(cm
3 /g S
TP)
Relative pressure (p/p0)
dV/d
(w) (
cm3 /g
•m)
Pore width (nm)
0.0 0.2 0.4 0.6 0.8 1.00
40
80
120
160
200
240
1 100.00
0.01
0.02
0.03
(c)
Stotal=380.9 m2/gDv=0.254 cm3/gDp= 4.3 nm
Volu
me
(cm
3 /g S
TP)
Relative pressure (p/p0)
dV/d
(w) (
cm3 /g
•m)
Pore width (nm)
0.0 0.2 0.4 0.6 0.8 1.00
40
80
120
160
200
240
1 100.000.010.020.030.040.05
(d)
Stotal=367.7 m2/gDv=0.331 cm3/gDp= 4.2 nm
Volu
me
(cm
3 /g S
TP)
Relative pressure (p/p0)dV
/d(w
) (cm
3 /g•m
)
Pore width (nm)
Fig. S1 Nitrogen sorption isotherms of (a) Co@NC-500, (b) Co@NC-600, (c) Co@NC-700 and (d) Co@NC-800.
Table S1 Pore structure of the [email protected] Stotal (m2/g) Pore volume (cm3/g) Average pore diameter (nm)
Co@NC-500 0.26 0.045 -Co@NC-600 225.1 0.138 7.1Co@NC-700 380.9 0.254 4.3Co@NC-800 367.7 0.331 4.2
Table S2 Chemical compositions of Co@NC-x catalysts.a
Atomic concentration (%)Catalysts ID/IG C N O Co
Co loading (wt. %) b
Co@NC-500 1.05 72.02 10.01 17.50 0.47 6.13Co@NC-600 1.08 78.01 5.60 15.84 0.55 5.71Co@NC-700 1.35 84.45 4.92 10.11 0.52 4.66Co@NC-800 1.12 85.64 2.65 11.22 0.49 3.04
a Atomic concentrations were detected in XPS analysis.b Detected by TG analysis.
4000 3600 3200 2800 2400 2000 1600 1200 800 400
12101580
~3400
Tran
smitt
ance
/ %
Wavenumber / cm-1
Co@NC-800 Co@NC-700 Co@NC-600 Co@NC-500
Fig. S2 FT-IR spectra of (a) Co@NC-500, (b) Co@NC-600, (c) Co@NC-700 and (d) Co@NC-800.
0 200 400 600 800 1000 1200 1400
O1s
N1s
Inte
nsity
(a.u
.)
Binding Energy (eV)
C1s
Co2p
Fig. S3 XPS wide-scan spectrum of Co@NC-700.
Table S3 Structural properties of [email protected] atomic percentage (%) Relative atomic percentage
(%)Catalysts N (398.5 eV)
N (400.1 eV)
N (401.1 eV)
N (403.3 eV) Co0 Co-O Co-N
Co@NC-500 51.58 48.15 - - 12.37 72.03 15.6Co@NC-600 49.11 38.96 7.92 4.01 16.21 65.94 17.86Co@NC-700 47.35 17.45 26.58 8.63 19.94 58.83 21.24Co@NC-800 45.21 12.54 42.24 0 26.02 59.12 14.86
Fig. S4 TEM images of (a) Ni/NCB-600, (b) Ni/NCB-900, (c) Ni/CB and (d) Ni/AC.
The insets in images (a-d) are corresponding histograms of Co particle size
distribution.
Fig. S5 Elemental mapping of Co@NC-700.
100 200 300 400 500 600 700
Co@N-700 Co@NC-700 Co@C-700
Sign
al (a
.u.)
T (oC)
300.7
384
379
Fig. S6 CO2-TPD analysis of Co@N-700, Co@NC-700 and Co@C-700.
100 200 300 400 500 600 700 8000
20
40
60
80
100
120
Wei
ght /
%
T / oC
79.4%
20.6%
Fig. S7 TG result of Co@N-700 in air atmosphere.
Fig. S8 TEM image of Co@N-700.
10 20 30 40 50 60 70 80 90
Co3O4
Co
C(002)
In
tens
ity /
a.u.
2 Theta / o
Fig. S9 XRD patterns of Co@N-700.
Table S4 Effect of amount of Co@NC-700 on transfer HDO of vanillin.Entry Catalyst amount/ mol% Conversion/% MMP selectivity/%1 0 1.1 -2 1.6 14.1 1003 4.7 25.3 1004 7.9 95.6 100a Reaction conditions: vanillin (0.5 mmol), FA (200 mg), H2O (10 mL), 0.5 MPa N2, 180 oC, 4h.
(a)
(b)
Fig. S10 TEM images of (a, b) Co/AC.
400 450 500 550 600 650 700
0.00
0.02
0.04
0.06
0.08
0.10
Ab
sorb
ance
Wavelength (nm)
Co/AC Co@NC-700
518 nmCo ion singal
Fig. S11 UV-vis spectra of filtrate of Co@NC-700 and Co/AC.
10 20 30 40 50 60 70 80
Co3O4
CoC
Inte
nsity
/ a.
u.
2 Theta / o
Fresh Co/AC Used Co/AC
Fig. S12. XRD patterns of (a) fresh and (b) used Co/AC.
Co@NC-700 (7.9 mol% Co)FA (2.8 g), 180 oC, 4 h
CHO
OOH
CH3
OOH
CH2OH
OOH
1.06g, Conv.=92.7 % Sele.=100 %Sele.=~0 %
+
Fig. S13 Gram-scale transfer HDO of vanillin over Co@NC-700 with FA as hydrogen source.Reaction conditions: vanillin (1.06 g, 7 mmol), FA (2.8 g), catalyst (7.9 mol% Co), H2O (100 mL), 0.5 MPa N2, 180 oC, 4h.
260 280 300 320 340 360 380 4000.0
0.5
1.0
1.5
2.0
2.5
Abso
rban
ce /
a.u.
Wavelength / nm
500
600
700
800
original solution
Fig. S14 The UV-vis spectra of vanillin adsorption on Co@NC-x.