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: refinenie@163.comQinghua Xia, Hubei University, Wuhan 430062, P.R. ChinaTel/Fax: 86-27-88662747Email: xiaqh518@aliyun.com

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

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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

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1 100.0000.0050.0100.0150.0200.0250.030

(b)

Stotal=225.1 m2/gDv=0.138 cm3/gDp= 7.1 nm

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me

(cm

3 /g S

TP)

Relative pressure (p/p0)

dV/d

(w) (

cm3 /g

•m)

Pore width (nm)

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TP)

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(w) (

cm3 /g

•m)

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1 100.000.010.020.030.040.05

(d)

Stotal=367.7 m2/gDv=0.331 cm3/gDp= 4.2 nm

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3 /g S

TP)

Relative pressure (p/p0)dV

/d(w

) (cm

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)

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 Co@NC-x.Samples 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 Co@NC-x.Relative 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.