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S1.1 BET surface area and pore size
As shown in Table S1, most of the prepared HTlcs have high surface area
(greater than 100 m2 g–1), the only exception being Cu-Al HTlcs (59 m2 g–1
Fig. S3 shows the nitrogen physisorption isotherms and BJH pore size
distributions for the HTlcs, M
).
2+(M3+)O and MO materials. The isotherms of HTlcs
and most of the M2+(M3+)O systems has the characteristic type IV shape indicating
that they are mesoporous materials. Compared to the M2+(M3+
S1.2 The basic strengths and basicity of the catalysts
)O systems, the pore
size distributions of the HTlcs were narrower and the pore diameters were smaller.
The BJH pore diameters and pore volumes confirmed that Cu(Fe)O was an
non-porous material, which explained its low surface area. The BJH pore diameters
and pore volumes also illustrated that most of the prepared MO were non-porous
materials.
CO2 TPD measurements were performed to assess the base site strength and
concentration. Fig.S4 shows the rate of CO2 desorption, normalized to the sample
loading, as a function of temperature for each M2+(M3+)O support and
KF/M2+(M3+)O-cn catalyst. The desorption profiles for the M2+(M3+
For all the KF/M
)O supports
showed one apparent desorption peak with a maximum at 100 °C.
2+(M3+)O-cn samples, with the exception of KF/Co(Cr)O-cn,
only a single apparent desorption feature with a maximum 100 °C was observed.
Above 100 °C, there were no desorption peaks for KF/M2+(M3+)O-cn. The desorption
profiles for KF/M2+(M3+)O-cn were similar to the corresponding supports, falsely
implying that KF doping did not increase the basic strength of prepared
KF/M2+(M3+)O-cn catalysts. However, both the Hammett indicators measurements are
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consistent with increase in base strength upon KF doping. This apparent anomaly
could arise from the high basic strength of KF/M2+(M3+)O-cn resulting in CO2 being
so strongly adsorbed on its surface that it is not desorbed below 500 °C. This
suggestion is consistent with the structure analysis in section 3.2. which showed that
KOH was formed on the surface of KF/M2+(M3+)O-cn catalysts (Eq. (1)-(5)). The
KOH formed would be expected to chemisorb CO2
KF/Co(Cr)O-cn did not show a desorption peak at about 100 °C, illustrating that
the number of base sites may be lower than that of the support alone. The reason for
this may be similar to that for KF/Cr
very strongly.
2O3
-cn (Eq. (6)).
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4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Mg-Al HTlcs
Mg(Al)O
KF/Mg(Al)O
A
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenumber(cm-1)
Ni-Al HTlc
Ni(Al)O
KF/Ni(Al)OB
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Co-Al HTlcs
Co(Al)O
KF/Co(Al)OC
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Cu-Al HTlcs
Cu(Al)O
KF/Cu(Al)OD
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenumber(cm-1)
Mg-Fe HTlcs
Mg(Fe)O
KF/Mg(Fe)OE
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Cu-Fe HTlcs
Cu(Fe)O
KF/Cu(Fe)OF
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenumber(cm-1)
Ni-Fe HTlcs
Ni(Fe)O
KF/Ni(Fe)OG
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Zn-Cr HTlc
Zn(Cr)O
KF/Zn(Cr)OH
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4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Co-Cr HTlcs
Co(Cr)O
KF/Co(Cr)OI
Fig. S1 FTIR spectra of HTlcs, M2+(M3+)O and KF/M2+(M3+
)O-cn.
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4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Mg(OH)2
MgO
KF/MgOA
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Ni(OH)2
NiO
KF/NiOB
4000 3500 3000 2500 2000 1500 1000 500
Tran
smitt
ance
(a.u
.)
Wavenuber(cm-1)
Cu(OH)2
CuO
KF/CuOC
Fig. S2 FTIR spectra of M(OH)2
, MO and KF/MO-cn.
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0.0 0.2 0.4 0.6 0.8 1.00
40
80
120
160
0 10 20 30 40 50 60 70 80 90 1000.000
0.005
0.010
0.015
0.020
0.025
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Mg-Al HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
0 10 20 30 40 50 60 70 80 90 1000.000
0.001
0.002
0.003
0.004
0.005
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Mg(Al)O
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
0 10 20 30 40 50 60 70 80 90 1000.000
0.005
0.010
0.015
0.020
0.025
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption DesorptionQ
uant
ity A
dsor
bed(
cm3 ·g
-1 S
TP)
Relative Pressure (P/Po)
Ni-Al HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
0 10 20 30 40 50 60 70 80 90 100
0.000
0.001
0.002
0.003
0.004
0.005
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption DesorptionQ
uant
ity A
dsor
bed(
cm3 ·g
-1 S
TP)
Relative Pressure (P/Po)
Ni(Al)O
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
0 10 20 30 40 50 60 70 80 90 100
0.000
0.001
0.002
0.003
0.004
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption DesorptionQ
uant
ity A
dsor
bed(
cm3 ·g
-1 S
TP)
Relative Pressure (P/Po)
Co-Al HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
0 10 20 30 40 50 60 70 80 90 100
0.0000
0.0005
0.0010
0.0015
0.0020
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption DesorptionQ
uant
ity A
dsor
bed(
cm3 ·g
-1 S
TP)
Relative Pressure (P/Po)
Co(Al)O
0.0 0.2 0.4 0.6 0.8 1.00
20
40
60
80
100
120
0 10 20 30 40 50 60 70 80 90 100
0.000
0.001
0.002
0.003
0.004
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Cu-Al HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
20
40
60
80
100
120
140
0 10 20 30 40 50 60 70 80 90 1000.0000
0.0004
0.0008
0.0012
0.0016
0.0020
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption DesorptionQ
uant
ity A
dsor
bed(
cm3 ·g
-1 S
TP)
Relative Pressure (P/Po)
Cu(Al)O
Fig.S3-continued
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0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
500
600
0 10 20 30 40 50 60 70 80 90 1000.0000
0.0005
0.0010
0.0015
0.0020
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Mg-Fe HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
500
600
0 10 20 30 40 50 60 70 80 90 1000.0000
0.0005
0.0010
0.0015
0.0020
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Mg(Fe)O
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
0 10 20 30 40 50 60 70 80 90 100
0.000
0.001
0.002
0.003
0.004
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Ni-Fe HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
0 10 20 30 40 50 60 70 80 90 1000.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Ni(Fe)O
0.0 0.2 0.4 0.6 0.8 1.00
50
100
150
200
250
300
350
0 10 20 30 40 50 60 70 80 90 1000.0000
0.0005
0.0010
0.0015
0.0020
0.0025
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption DesorptionQ
uant
ity A
dsor
bed(
cm3 ·g
-1 S
TP)
Relative Pressure (P/Po)
Cu-Fe HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
10
20
30
0 10 20 30 40 50 60 70 80 90 1000.00000
0.00002
0.00004
0.00006
0.00008
0.00010
0.00012
0.00014
0.00016
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Cu(Fe)O
0.0 0.2 0.4 0.6 0.8 1.00
50
100
150
200
250
0 10 20 30 40 50 60 70 80 90 1000.0000
0.0005
0.0010
0.0015
0.0020
0.0025
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption DesorptionQ
uant
ity A
dsor
bed(
cm3 ·g
-1 S
TP)
Relative Pressure (P/Po)
Zn-Cr HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
50
100
150
200
250
300
350
0 10 20 30 40 50 60 70 80 90 100
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
0.0014
pore
vol
ume
( cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Zn(Cr)O
Fig.S3-continued
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0.0 0.2 0.4 0.6 0.8 1.00
50
100
150
200
0 10 20 30 40 50 60 70 80 90 1000.000
0.002
0.004
0.006
0.008
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Co-Cr HTlcs
0.0 0.2 0.4 0.6 0.8 1.00
50
100
150
200
250
0 10 20 30 40 50 60 70 80 90 100
0.0000
0.0005
0.0010
0.0015
0.0020
0.0025
0.0030
0.0035
0.0040
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption DesorptionQ
uant
ity A
dsor
bed(
cm3 ·g
-1 S
TP)
Relative Pressure (P/Po)
Co(Cr)O
0.0 0.2 0.4 0.6 0.8 1.00
100
200
300
400
500
600
0 10 20 30 40 50 60 70 80 90 1000.000
0.001
0.002
0.003
0.004
0.005
0.006
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
MgO
0.0 0.2 0.4 0.6 0.8 1.00
10
20
30
40
50
60
70
0 10 20 30 40 50 60 70 80 90 1000.0000
0.0004
0.0008
0.0012
0.0016
0.0020
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
NiO
0.0 0.2 0.4 0.6 0.8 1.00
40
80
120
160 Fe2O3
0 10 20 30 40 50 60 70 80 90 100
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
0.0012
0.0014
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)0.0 0.2 0.4 0.6 0.8 1.00
10
20
30
40
50
60
Co3O4
0 10 20 30 40 50 60 70 80 90 1000.00000
0.00004
0.00008
0.00012
0.00016
0.00020
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
0.0 0.2 0.4 0.6 0.8 1.00
20
40
60
80
100
120
140
0 10 20 30 40 50 60 70 80 90 1000.0000
0.0001
0.0002
0.0003
0.0004
0.0005
0.0006
0.0007
pore
vol
ume
(cm
3 ·g-
1 ·nm
-1)
pore diameter (nm)
Adsorption Desorption
Qua
ntity
Ads
orbe
d(cm
3 ·g-1
STP
)
Relative Pressure (P/Po)
Cr2O3
Fig. S3 Physisorption isotherms and BJH pore size distribution for HTlcs,
M2+(M3+
)O and MO.
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100 200 300 400 500
0.00
0.01
0.02
0.03
0.04
0.05
TCD
Sign
al (a
.u.)
Temperature (oC)
KF/Mg(Al)O-cn
Mg(Al)O
100 200 300 400 500
0.00
0.01
0.02
0.03
0.04
TCD
Sign
al (a
.u.)
Temperature (oC)
KF/Ni(Al)O-cn
Ni(Al)O
100 200 300 400 500
0.000
0.005
0.010
0.015
0.020
0.025
TCD
Sign
al (a
.u.)
Temperature (oC)
KF/Co(Al)O-cn
Co(Al)O
100 200 300 400 500
0.00
0.01
0.02
TCD
Sign
al (a
.u.)
Temperature (oC)
Cu(Al)O
KF/Cu(Al)O-cn
100 200 300 400 500
0.00
0.01
0.02
0.03
0.04
0.05
TCD
Sign
al (a
.u.)
Temperature (oC)
KF/Mg(Fe)O-cn
Mg(Fe)O
100 200 300 400 500
0.000
0.005
0.010
0.015
0.020
0.025
TCD
Sign
al (a
.u.)
Temperature (oC)
Ni(Fe)O
KF/Ni(Fe)O-cn
100 200 300 400 500
0.000
0.002
0.004
0.006
0.008
0.010
TCD
Sign
al (a
.u.)
Temperature (oC)
KF/Cu(Fe)O-cn
Cu(Fe)O
100 200 300 400 500
0.000
0.005
0.010
0.015
TCD
Sign
al (a
.u.)
Temperature (oC)
Co(Cr)O
KF/Co(Cr)O-cn
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100 200 300 400 500
0.000
0.004
0.008
TCD
Sign
al (a
.u.)
Temperature (oC)
Zn(Cr)O
KF/Zn(Cr)O-cn
Fig.S4 TPD profiles of CO2 adsorbed on M2+(M3+)O and KF/M2+(M3+
)O-cn
materials.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
10 20 30 40 50 60 70 80
*
**
**
**
**
** *
*
*
*
** *
*
**
***
**
*
2θ / ο
0%
20%
40%
60%
80%
100%
Mg-Al HTlcsKMgF3
Fig. S5 XRD patterns of KF/Mg-Al HTlcs with different loading amount of KF.
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Table S1 Nitrogen physisorption data of HTlcs
Entry Catalyst Surface Area (m2 g-1
Pore Volume ) (cm3 g-1
Average pore ) width (Å)
1 Mg-Al HTlcs 140 0.16 45 2 Ni -Al HTlcs 272 0.55 73 3 Co-Al HTlcs 166 0.51 180 4 Cu-Al HTlcs 59 0.17 120 5 Mg-Fe HTlcs 164 0.85 278 6 Ni-Fe HTlcs 182 0.59 181 7 Cu-Fe HTlcs 139 0.47 122 8 Zn-Cr HTlcs 100 0.36 107 9 Co-Cr HTlcs 216 0.33 52
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011