1
Supporting Information (SI)
Graphite Oxide- and Graphene Oxide-supported Catalysts for Microwave-assisted
Glucose Isomerisation in Water
Iris K.M. Yu a,b, Xinni Xiong a, Daniel C.W. Tsang a,*, Yun Hau Ng c, James H. Clark b, Jiajun
Fan b, Shicheng Zhang d, Changwei Hu e, Yong Sik Ok f
a Department of Civil and Environmental Engineering, Hong Kong Polytechnic University, Hung
Hom, Kowloon, Hong Kong, China
b Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York,
YO10 5DD, UK
c School of Energy and Environment, City University of Hong Kong, Tat Chee Avenue,
Kowloon, Hong Kong, China
d Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP3),
Department of Environmental Science and Engineering, Fudan University, Shanghai 200433,
China
e Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of
Chemistry, Sichuan University, Chengdu 610064, China
f Korea Biochar Research Center, O-Jeong Eco-Resilience Institute (OJERI) & Division of
Environmental Science and Ecological Engineering, Korea University, Seoul 02841, Republic of
Korea
*Corresponding author: [email protected]
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2019
2
Table S1. Binding energies reported in the literature.
XPS Components Symbols Binding
energies (eV) References
O 1s
Chemisorbed H2O or O2 535.3 [1]
Anhydride, lactone, carboxylic acids O-C=O 533.3 [1]
Hydroxyl, ethers, epoxy C-OH, C-O-C 532.1-532.4 [1, 2]
Al-OH hydroxyl Al-OH 531.4-531.9 [3, 4]
Carbonyl, quinone C=O 530.7 [1]
Al oxide Al-O 530.4 [3]
C 1s
Carboxyl groups, esters, and lactones O-C=O 288.4-290.4 [5, 6]
Ketone, aldehyde C=O 287 [7]
Ether, epoxy C-O-C 286.3 [7]
Alcohol C-OH 285.6 [7]
Sp3-bonded carbon, adventitious
carbon
C sp3, C-C,
C-H 284.5-285 [8, 9]
Sp2-bonded carbon C sp2 284.4-284.8 [6, 7]
Al 2p
Alumina Al2O3 75.8-76 [10, 11]
Bayerite β-Al(OH)3 75 [4]
Gibbsite, Al-O-C γ-Al(OH)3,
Al-O-C 74.4 [4, 12]
Boehmite γ-AlO(OH) 73.9 [4]
Metallic Al Al 72.2-72.8 [10, 12]
References
[1]. H. Valdés, M. Sánchez-Polo, J. Rivera-Utrilla and C.A. Zaror, Langmuir, 2002, 18, 2111-2116.
[2]. B. Yu, X. Wang, X. Qian, W. Xing, H. Yang, L. Ma, Y. Lin, S. Jiang, L. Song, Y. Hu, and S. Lo, 2014, RSC
Adv., 4, 31782-31794.
[3]. I. Iatsunskyi, M. Kempiński, M. Jancelewicz, K. Załęski, S. Jurga and V. Smyntyna, Vacuum, 2015, 113, 52-58.
[4]. J.T. Kloprogge, L.V. Duong, B.J. Wood, R.L. Frost, J. Colloid Interface Sci., 2006, 296, 572-576.
[5]. L., Qian and B. Chen, J. Agr. Food Chem., 2014, 62, 373-380.
[6]. P. Dash, T. Dash, T.K. Rout, A.K. Sahu, S.K. Biswal, and B.K. Mishra, 2016, RSC Adv., 6, 12657–12668.
[7]. K. Ganesan, S. Ghosh, N.G. Krishna, S. Ilango, M. Kamruddin and A.K. Tyagi, Phys. Chem. Chem.
Phys., 2016, 18, 22160-22167.
[8]. M. Lawrinenko, D. Jing, C. Banik and D.A. Laird. Carbon, 2017, 118, 422-430.
[9]. Cardiff University, XPS Analysis - Carbon http://sites.cardiff.ac.uk/xpsaccess/reference/carbon/
[10]. R. Bicker, H. Deger, W. Herzog, K. Rieser, H. Pulm, G. Hohlneicher and H.J. Freund, J. Catal., 1985, 94,
69-78.
[11]. C. Xu, T. Sritharan, S.G. Mhaisalkar, M. Srinivasan and S. Zhang, Appl. Surf. Sci., 2007, 253, 6217-6221.
[12]. M. Bou, J.M. Martin, T. Le Mogne and L. Vovelle, Appl. Surf. Sci., 1991, 47, 149-161.
3
Figure S1. Nitrogen adsorption-desorption isotherms of the prepared samples.
0
50
100
150
200
250
0 0.2 0.4 0.6 0.8 1
N2
adso
rbe
d (c
m³ g
-1)
Relative Pressure (P/Po)
G
GIO
GO
G-Al500
GIO-Al200
GIO-Al500
GO-Al200
GO-Al500
0
10
20
30
40
50
0 0.2 0.4 0.6 0.8 1
N2
adso
rbe
d (c
m³
g-1)
Relative Pressure (P/Po)
G
GIO
GO
G-Al500
GIO-Al200
GO-Al200
(a) (b)
4
Figure S2. SEM images of the prepared samples.
5
Figure S3. (a) C 1s XPS spectra of the prepared samples and curve fitting for the C 1s XPS
spectra of (b) G, (c) GIO, (d) G-Al500, (e) GIO-Al200, (f) GIO-Al500, (g) GO-Al200, and (h)
GO-Al500.
280282284286288290292
Inte
nsi
ty
Binding energy (eV)
GG-Al500GIOGIO-Al200GIO-Al500GO-Al200GO-Al500
280282284286288290292
Inte
nsi
ty
Binding energy (eV)
O-C=O
C-O-C
C sp2
Raw data
Fit data
Background
Area13.2%9.1%
77.7%
280282284286288290292
Inte
nsi
ty
Binding energy (eV)
O-C=OC=OC-O-CC sp3, C-CC sp2Raw dataFit dataBackground
Area10.6%21.9%
16.6%21.4%29.5%
280282284286288290292
Inte
nsi
ty
Binding energy (eV)
O-C=O
C-O-C
C-OH
C sp3, C-C
C sp2
Raw data
Fit data
Background
Area13.4%9.8%
5.1%51.6%20.1%
280282284286288290292
Inte
nsi
ty
Binding energy (eV)
O-C=OC-O-CC-OHC sp3, C-CC sp2Raw dataFit dataBackground
Area18.2%10%
6.4%58.2%7.3%
280282284286288290292
Inte
nsi
ty
Binding energy (eV)
O-C=O
C-O-C
C-OH
C sp3, C-C
C sp2
Raw data
Fit data
Background
Area14.8%13.2%
7.4%58.9%5.6%
280282284286288290292
Inte
nsi
ty
Binding energy (eV)
O-C=OC-O-CC-OHC sp3, C-CC sp2Raw dataFit dataBackground
Area14.4%5.7%
10.6%25.5%43.8%
280282284286288290292
Inte
nsi
ty
Binding energy (eV)
O-C=OC-O-CC-OHC sp3, C-CC sp2Raw dataFit data
Area12.1%11.4%
9.3%51.9%15.3%
(a) (b)
(c) (d)
(e) (f)
(g) (h)
6
Figure S4. (a) O 1s XPS spectra of the prepared samples and curve fitting for the O 1s XPS
spectra of (b) G, (c) GIO, (d) G-Al500, (e) GIO-Al200, (f) GIO-Al500, (g) GO-Al200, and (h)
GO-Al500.
524.4529.4534.4539.4
Inte
nsi
ty
Binding energy (eV)
GG-Al500GIOGIO-Al200GIO-Al500GO-Al200GIO-Al500
526528530532534536538540
Inte
nsi
ty
Binding energy (eV)
O-C=OC-OH, C-O-CRaw dataFit dataBackground
Area48.7%51.3%
526528530532534536538540
Inte
nsi
ty
Binding energy (eV)
O-C=OC-OH, C-O-CRaw dataFit dataBackground
Area14.8%85.2%
526528530532534536538540
Inte
nsi
ty
Binding energy (eV)
O-C=O
Al-OH
Al-O
Raw data
Fit data
Background
Area7.2%76.2%
16.7%
526528530532534536538540
Inte
nsi
ty
Binding energy (eV)
O-C=O
C-OH, C-O-C
Al-OH
Al-O
Raw data
Fit data
Background
Area30.5%49.4%
16.1%4%
526528530532534536538540
Inte
nsi
ty
Binding energy (eV)
O-C=O
C-OH, C-O-C
Al-OH
C=O
Al-O
Raw data
Fit data
Background
Area28.1%27.2%
29.9%2.7%12.1%
526528530532534536538540
Inte
nsi
ty
Binding energy (eV)
O-C=OC-OH, C-O-CAl-OHRaw dataFit dataBackground
Area13.1%30.9%
56%
526528530532534536538540
Inte
nsi
ty
Binding energy (eV)
O-C=OC-OH, C-O-CAl-OHC=ORaw dataFit dataBackground
Area18.5%41.5%
9.9%30%
(a) (b)
(c) (d)
(e) (f)
(g) (h)
7
Figure S5. TEM images of (a) GIO-Al200, (b) GO-Al200, and (c) GO-Al500.
8
Figure S6. Glucose conversion and total carbon resulted from the catalytic conversion of glucose
over different catalysts for (a) 1 min and (b) 20 min (conditions: 0.5 g glucose and 0.25 g catalyst
in 10 ml water or acetone/H2O (1:1 v/v) at 140 oC).
0
20
40
60
80
100
0
10
20
30
40
50
60
70
80
Total carb
on
(mo
l%)
Glu
cose
co
nve
rsio
n (
mo
l%)
Al-GO_Glu_diff. conditions_2018
Glucose conversion Total carbon
Water Acetone/H2O
0
20
40
60
80
100
0
10
20
30
40
50
60
70
80
Total carb
on
(mo
l%)
Glu
cose
co
nve
rsio
n (
mo
l%)
Al-GO_Glu_diff. conditions_2018
Glucose conversion Total carbon
Water Acetone/H2O(a)
(b)
9
Figure S7. Yields of HMF, disaccharide (DS), levoglucosan (LG), levulinic acid (LA), and
formic acid (FA) resulted from the catalytic conversion of glucose over different catalysts for (a)
1 min and (b) 20 min (conditions: 0.5 g glucose and 0.25 g catalyst in 10 ml water or
acetone/H2O (1:1 v/v) at 140 oC).
0
2
4
6
8
10
12
14
16
18
20
Yie
ld (m
ol%
)
Al-GO_Glu_diff. conditions_2018
HMF DS+LG+FA+LA
0
2
4
6
8
10
12
14
16
18
20Y
ield
(mo
l%)
Al-GO_Glu_diff. conditions_2018
HMF DS+LG+FA+LA
(a)
(b)
Water Acetone/H2O
Water Acetone/H2O
10
Figure S8. Fructose as a function of the (a) total Al content and (b-d) distribution of Al species
suggested by XPS curve fitting, as well as (e) BET surface area and (f) total pore volume
(conditions: 0.5 g glucose and 0.25 g catalyst in 10 ml water or acetone/H2O (1:1 v/v) at 140 oC
for 1 and 20 min).
0
5
10
15
20
25
30
35
40
0 50 100 150
Fru
cto
se y
ield
(mo
l%)
BET surface area (m2 g-1)
Al-GO_Glu_2018
H2O, 1 min H2O, 20 minAcetone/H2O, 1 min Acetone/H2O, 20 min
0
5
10
15
20
25
30
35
40
0 0.1 0.2 0.3 0.4
Fru
cto
se y
ield
(mo
l%)
Total pore volume (cm3 g-1)
Al-GO_Glu_2018
H2O, 1 min H2O, 20 minAcetone/H2O, 1 min Acetone/H2O, 20 min
0
5
10
15
20
25
30
35
40
0 20 40 60
Fru
cto
se y
ield
(mo
l%)
γ-Al(OH)3, Al-O-C (%)
Al-GO_Glu_2018
H2O, 1 min H2O, 20 min
Acetone/H2O, 1 min Acetone/H2O, 20 min
0
5
10
15
20
25
30
35
40
0 20 40 60
Fru
cto
se y
ield
(mo
l%)
γ-AlO(OH) (%)
Al-GO_Glu_2018
H2O, 1 min H2O, 20 min
Acetone/H2O, 1 min Acetone/H2O, 20 min
0
5
10
15
20
25
30
35
40
0 20 40 60 80
Fru
cto
se y
ield
(mo
l%)
β-Al(OH)3 (%)
Al-GO_Glu_2018
H2O, 1 min H2O, 20 min
Acetone/H2O, 1 min Acetone/H2O, 20 min
0
5
10
15
20
25
30
35
40
0 10 20 30
Fru
cto
se y
ield
(mo
l%)
Al (%)
Al-GO_Glu_2018
H2O, 1 min H2O, 20 min
Acetone/H2O, 1 min Acetone/H2O, 20 min
(e) (f)
(a) (b)
(c) (d)
11
Figure S9. Fructose yield resulted from the catalytic conversion of glucose over different
catalysts for 20 min at 140±3 oC in an oil bath (conditions: 0.5 g glucose and 0.25 g catalyst in 10
ml water).
0
5
10
15
20
25
30
35
40
45
50
G-Al500 GIO-Al500
Fru
cto
se y
ield
(m
ol%
)
