Mixed Matrix Membranes based on PPO and graphene for gas ......Graphene WeightPercentageIncrease...
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Graphene Weight Percentage Increase Filler: XT7 Loading: 0.3 % Filler: XT6 Loading: 1% Filler: XT6 Loading: 5% Filler: XT6 Loading: 15% 0 5 10 15 1 10 100 35°C He CO 2 N 2 Gas permeability (Barrer) Graphene loading (wt%) 0 5 10 15 1 10 100 200 65°C He CO 2 N 2 Gas permeability (Barrer) Graphene loading (wt%) 0 5 10 15 1 10 100 He/CO 2 He/N 2 CO 2 /N 2 Ideal selectivity Graphene loading (wt%) 0 5 10 15 1 10 100 He/CO 2 He/N 2 CO 2 /N 2 Ideal Selectivity Graphene loading (wt%) 0 5 10 15 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 He CO 2 N 2 [P(65°C)-P(35°C)]/P(35°C) Graphene loading (wt%) 0 5 0.8 0.9 1.0 1.1 1.2 1.3 35°C He/CO 2 He/N 2 CO 2 /N 2 / 0 Graphene loading (wt%) 0 5 10 15 0.5 1.0 1.5 65°C He/CO 2 He/N 2 CO 2 /N 2 / 0 Graphene loading (wt%) 0 5 0.8 0.9 1.0 1.1 1.2 1.3 35°C He CO 2 N 2 P/P 0 Graphene loading (wt%) INTRODUCTION SAMPLES PREPARATION FILLER CHARACTERISTICS SEM PICTURES PERMEABILITY & SELECTIVITY CONCLUSIONS In the table below we show the nanofillers geometrical characteristics and the % wt in respect to PPO used in this study. We fabricated new mixed matrix membranes (MMMs) based on poly(2,6-dimethyl-1,4-phenylene oxide), PPO, a dense permeable and hydrogen selective glassy polymer. The MMMs were obtained by adding graphene at different percentages, up to 15% wt , and the gas transport properties were measured via a pure gas permeometer at 35°C and 65°C. Two different graphene nanoparticles, XT6 and XT7, provided by Graphene XT were used for this study. Solid PPO (Sigma Aldrich) was dissolved in chloroform (purity > 99,5%, Sigma Aldrich) at 5% wt and, after the graphene addition, the suspension was sonicated, 15 min. and 1 hr. for XT6 and XT7 respectively, stirred for 1 day and casted in a glassy Petri dish at 50 °C. A post-treatment at 200°C under vacuum for 1 day stabilizes the polymer properties. Filler Type Lateral Dimension Thickness %wt in PPO μm nm XT6 5 6.0-8.0 1.0 - 5.0 - 15.0 XT7 20 2 0.3 • Graphene in small quantities enhances the PPO free volume, permeability & selectivity. • Higher loadings of graphene increase the tortuosity and lower the PPO permeability. • Graphene addition reduces the polymer chain mobility and the temperature-dependence of permeability &selectivity of the polymer, ultimately enhancing its stability. References [1] R.Rea et al., Polymers 2018, 10,19 [2] L.Olivieri et al., Ind. Eng. Chem. Res. 2015, 54 [3] Y, Huang et al., J. Polym. Sci.: Part B: Polym. Phys. 2007, 45 [4]B.M. Yoo et al., Curr. Op. Chem. Eng. 2017, 16 Mixed Matrix Membranes based on PPO and graphene for gas separation R. Rea*, M.G. De Angelis*, S. Ligi°, *M. Giacinti Baschetti* * Università di Bologna, ° Graphene XT s.a.s Sample #1 Sample #2 Sample #3 Sample #4 Sample #1 Sample #2 Sample #3 Sample #4 P 0 = PPO permeability α 0 = PPO selectivity
Transcript of Mixed Matrix Membranes based on PPO and graphene for gas ......Graphene WeightPercentageIncrease...
Graphene Weight Percentage Increase
Filler: XT7
Loading: 0.3 %
Filler: XT6
Loading: 1%
Filler: XT6
Loading: 5%
Filler: XT6
Loading: 15%
0 5 10 151
10
100
35°C
He CO
2
N2
Ga
s p
erm
eab
ilit
y (
Ba
rre
r)
Graphene loading (wt%)
0 5 10 151
10
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65°C
He CO
2
N2
Ga
s p
erm
eab
ilit
y (B
arr
er)
Graphene loading (wt%)
0 5 10 151
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100 He/CO
2
He/N2
CO2/N
2
Ideal sele
cti
vit
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Graphene loading (wt%)
0 5 10 151
10
100
He/CO2
He/N2
CO2/N
2
Ideal
Sele
cti
vity
Graphene loading (wt%)
0 5 10 15-0.2
-0.1
0.0
0.1
0.2
0.3
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0.5
0.6
0.7
0.8 He CO
2
N2
[P(6
5°C
)-P
(35
°C)]
/P(3
5°C
)
Graphene loading (wt%)
0 50.8
0.9
1.0
1.1
1.2
1.3
35°C He/CO2
He/N2
CO2/N
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0 5 10 150.5
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He/N2
CO2/N
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0 50.8
0.9
1.0
1.1
1.2
1.3
35°C He CO
2
N2
P/P
0
Graphene loading (wt%)
INTRODUCTION
SAMPLES PREPARATION FILLER CHARACTERISTICS
SEM PICTURES
PERMEABILITY & SELECTIVITY
CONCLUSIONS
In the table below we show the nanofillers geometrical
characteristics and the %wt in respect to PPO used in this study.
We fabricated new mixed matrix membranes (MMMs) based on poly(2,6-dimethyl-1,4-phenylene oxide), PPO, a dense permeable and hydrogen
selective glassy polymer. The MMMs were obtained by adding graphene at different percentages, up to 15%wt , and the gas transport properties
were measured via a pure gas permeometer at 35°C and 65°C.
Two different graphene nanoparticles, XT6 and XT7, provided by
Graphene XT were used for this study. Solid PPO (Sigma Aldrich)
was dissolved in chloroform (purity > 99,5%, Sigma Aldrich) at 5%wt
and, after the graphene addition, the suspension was sonicated, 15
min. and 1 hr. for XT6 and XT7 respectively, stirred for 1 day and
casted in a glassy Petri dish at 50 °C. A post-treatment at 200°C
under vacuum for 1 day stabilizes the polymer properties.
Filler Type Lateral Dimension Thickness %wt in PPOμm nm
XT6 5 6.0-8.0 1.0 - 5.0 - 15.0
XT7 20 2 0.3
• Graphene in small quantities enhances the PPO free volume, permeability & selectivity.
• Higher loadings of graphene increase the tortuosity and lower the PPO permeability.
• Graphene addition reduces the polymer chain mobility and the temperature-dependence of
permeability &selectivity of the polymer, ultimately enhancing its stability.
References
[1] R.Rea et al., Polymers 2018, 10,19
[2] L.Olivieri et al., Ind. Eng. Chem. Res. 2015, 54
[3] Y, Huang et al., J. Polym. Sci.: Part B: Polym. Phys. 2007, 45
[4]B.M. Yoo et al., Curr. Op. Chem. Eng. 2017, 16
Mixed Matrix Membranes based on PPO and graphene for gas separation
R. Rea*, M.G. De Angelis*, S. Ligi°, *M. Giacinti Baschetti** Università di Bologna, ° Graphene XT s.a.s
Sample #1 Sample #2 Sample #3 Sample #4
Sample #1 Sample #2
Sample #3 Sample #4
P0 = PPO permeabilityα0 = PPO selectivity
