Supporting Information
Ternary CoAgPd Nanoparticles Confined inside the Pores of MIL-101 as
Efficient Catalyst for Dehydrogenation of Formic Acid
Nan Cao,a Wei Luo, a,b Kai Hu a *and Gongzhen Chenga
Table of Contents
page
Figure
1
1Table
3
Calculation
4
Reference
5
Figure:
(a )
120
(b )
ln k = -2 9 1 2 .0 (1 /T )+ 2 1 .0
1 2 .7
1 2 .6
80
A ctiv atio n E n erg y
-1
E a= 2 4 .2 1 k J m o l
1 2 .5
60
ln k
V (C O
+ H2) ( m L )
2
100
1 2 .8
T
T
T
T
40
20
=
=
=
=
o
1 2 .4
1 2 .3
50 C
o
60 C
o
70 C
o
80 C
1 2 .2
1 2 .1
1 2 .0
0
0
5
10
15
tim e (m in )
20
0 .0 0 2 8
25
0 .00 2 9
0 .0 0 3 0
0 .0 03 1
1 /T
Figure S1. (a) Time course plots for hydrogen generation by the decomposition of
FA/SF by Co9Ag21Pd70@MIL-101 at
50 °C, 60 °C, 70 °C, 80 °C. (b) Plot of ln k
versus 1/T during the FA/SF decomposition over Co9Ag21Pd70@MIL-101 at different
temperatures. (catalyst=100 mg, FA=140 mg, SF=70 mg)
(b )
(a )
H2
in te n s ity (i.u .)
i n te n s it y ( i.u .)
CO
standard gas
sam ple
CO2
0
2
4
tim e (m in )
6
8
0 .0
0.5
1.0
1 .5
2.0
2.5
tim e (m in )
Figure S2. (a) GC spectrum using TCD for evolved gas from FA/FS aqueous solution
over Co9Ag21Pd70@MIL-101 at 50 °C. (b) GC spectrum using FID-Methanator for the
standard mixture gas of H2, CO2 and CO, and evolved gas from FA/FS aqueous
solution over Co9Ag21Pd70@MIL-101 at 50 °C.(catalyst=100 mg, FA=140 mg,
SF=70 mg)
1
90
FA
FA/NaF=4
FA/NaF=2
FA/NaF=1
FA/NaF=0.5
FS
80
V(CO2+H2) (mL)
70
60
50
40
30
20
10
0
0
10
20
30
40
time (min)
50
60
70
Figure S3. Gas generation by decomposition of FA/SF with different FA/SF mass
ratios vs time catalyzed by Co9Ag21Pd70@MIL-101 at 50 °C. (catalyst=100 mg,
FA=140 mg)
90
80
V(CO2+H2) (mL)
70
60
50
1st
2nd
3rd
40
30
20
10
0
0
5
10 15 20 25 30 35 40 45 50 55 60 65 70
time (min)
Figure S4. Recyclability test Co9Ag21Pd70@MIL-101 catalyst for the decomposition
of FA/SF at 50 °C.(catalyst=100 mg, FA=140 mg, SF=70 mg)
Table:
Table S1. ICP-AES results of CoAgPd@MIL-101 catalysts
Catalyst
Co-Ag-Pd initial composition
Co-Ag-Pd final composition
Co6Ag8Pd86@MIL-101
10:9:81
6:8:86
Co9Ag21Pd70@MIL-101
10:27:63
9:21:70
Co17Ag24Pd59@MIL-101
10:45:45
17:24:59
Co21Ag24Pd55@MIL-101
10:63:27
21:24:55
Co33Ag15Pd52@MIL-101
30:21:49
33:15:52
Co54Ag11Pd35@MIL-101
50:15:35
54:11:35
Co68Ag13Pd19@MIL-101
70:9:21
68:13:19
Co89Ag7Pd4@MIL-101
90:3:7
89:7:4
Table S2. Pore volume and surface area of MIL-101 and Co9Ag21Pd70@MIL-101.
Sample
MIL-101
Co9Ag21Pd70@MIL-101
Surface Area(m2g-1)
3913
2033
wt %
-15.4
Pore volume(m3g-1)
2.135
1.142
Table S3. Comparison of activities of different catalysts for hydrogen generation from
FA/SF
Catalyst
T (°C)
TOF (h-1)
FA:FS
AuPd@ED-MIL-101
90
106
3:1
-
[S1]
Ag20Pd80@MIL-101
80
848
9:2
27.08
[S1]
Ag18Pd82@ZIF-8
80
580
3:1
51.38
[S2]
Co9Ag21Pd70@MIL-101
50
98
9:2
24.21
This work
Ni18Ag24Pd58/C
50
85
1:1
20.5
[S4]
Pd/H-BETA
50
59.2
10:0
-
[S5]
Co0.30Au0.35Pd0.35/C
25
80
5:0
-
[S6]
Pd/C
25
64
5:4
-
[S7]
AuPd–CeO2/N-rGO
25
52.9
5:0
-
[S8]
Ni0.40Au0.15Pd0.45/C
25
12.4
1:0
-
[S9]
Ea (kJ/mol)
Reference
3
Calculation methods:
where Patm is the atmospheric pressure, VH2 is the generated volume of H2 within 20
min, R is the universal gas constant, T is the temperature when the catalysis reaction
performed, nNPs is the molar number of catalyst, t is the reaction times (20min) in
hour.
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