Hydrogen Adsorption and Storage on Porous Materials K. M. Thomas. School of Chemical Engineering and Advanced Materials Newcastle University United Kingdom H2FC SUPERGEN Conference Birmingham University, 16-18 th December 2013
Hydrogen Adsorption and Storage on Porous Materials
K. M. Thomas.
School of Chemical Engineering and Advanced Materials
Newcastle University
United Kingdom
H2FC SUPERGEN Conference
Birmingham University,
16-18th December 2013
Structure of Presentation • Background on the Hydrogen Economy • H2 adsorption capacities for carbon,
polymer and metal organic framework porous materials
• Quantum kinetic molecular sieving of H2 and D2
• H2 surface interaction energy, adsorption enthalpies at zero surface coverage
• Hysteretic adsorption of H2 on porous metal organic frameworks
• Conclusions
Why are we considering the possibility of the hydrogen economy?
• We are close to, or at, peak oil production
• Future decline in petroleum reserves
will probably lead to high cost of petroleum
• Security of supply issues, environment
• Medium Term Replacement: Shale gas
• Longer term: Hydrogen
Current Hydrogen Use
• Hydrogen is widely used in industry where safety issues and use can be controlled. It is distributed in pipelines over a limited area to different chemical processes.
• The problems arise in the use of hydrogen for transport applications
• Storage of hydrogen with a 300 mile refuelling range is an unsolved problem. The problem is fitting the required volume of the fuel tank into a car
Hydrogen Storage
• Storage Amount for vehicles:
• 5 – 13 kg
Storage Methods:
• Compressed Gas (~ 700 bar)
• Liquid Hydrogen (20 K)
• Storage on Solid State Materials
• Other Factors; refuelling time, driving distance range, safety
Storage of Solid State Materials
• Metal Hydrides
• Porous Materials
a) carbons
b) zeolites
c) porous polymers
d) metal organic framework materials
The Variation of H2 Adsorption at Saturation
(wt%) and 77 K versus BET Surface Area
Updated version Dalton Trans 2009, 1487-1505
0 1000 2000 3000 4000 5000 6000
0
1
2
3
4
5
6
7
8
9H
2 A
dso
rb
ed
at
Hig
h P
ress
ure
an
d 7
7 K
/w
t%
BET N2Surface Area/ m
2 g
-1
MOFs
Carbons
Zeolites
Silicas(MCM-41)
Polymers/PAFs
B doped carbon
COFs
Variation of H2 Adsorption at Saturation and 77 K versus Total Pore Volume
0 1 2 3 40
2
4
6
8
H2 A
dso
rb
ed
at
Hig
h P
ress
ure
an
d 7
7 K
/w
t%
Total Pore Volume/ cm3
g-1
MOFs
Liquid H2
Carbons
Polymers/PAFs
Line for liquid H2
Updated version
Dalton Trans 2009.1487.
Acidic forms H4L1, H4L
2, and H4L3 (left) of the ligands viewed along
the c axes (middle) and along the a axes (right) of the structures Cu
blue, C grey, H white, O red. Angew. Chemie, Int. Ed. (2006), 45(44), 7358.
JACS 2009. 131.2159
Hydrogen Adsorption Capacities
• 7-12 wt% maximum surface excess hydrogen can be adsorbed at 77 K
• The highest values (MOF200, MOF210 and NU100) are achieved for very low density materials, which, as a consequence, have low volumetric capacities
The Variation of H2 Adsorption at Saturation (gL-1)and 77 K versus BET
Surface Area for MOFs
0 1000 2000 3000 4000 5000 60000
10
20
30
40
50
60
Volumetric
Volumetric 80 bar
H2 V
olu
metr
ic C
ap
city
g L
-1
BET Surface Area/ m2 g
-1
Comparison of Hydrogen isobars on Porous Metal Organic Framework and
Carbon Materials
-200 -180 -160 -140 -120 -100 -80
0
20
40
60
80
100
Am
ou
nt
Ad
sorb
ed/
%
T/o
C
E MOF
C
M MOF
AC
Zhao et al, Science 2004, 304, 1012
Hydrogen adsorption at ambient temperatures
• Usually very small amounts (< 1 wt%) of hydrogen are adsorbed at room temperature and up to 100 bar.
• Multivalent manganese hydrazide gels are reported 1.8 wt% at 85 bar 298 K and titanium hydrazide 2.63 wt% at 143 bar and 298 K
• Temperature dependence of adsorption is now the key issue
• H2–surface interactions need to be increased
Aspects of hydrogen adsorption
• Quantum effects for porous carbons and metal organic frameworks
• Enhanced surface interactions in metal organic frameworks
• Hysteretic hydrogen adsorption in metal organic framework materials
Quantum Effects in Adsorption • Kinetic Isotope Molecular Sieving • This occurs when the differences between the
adsorptive and the pore sizes are similar to the de Broglie wavelength.
• First experimental observation was for H2 and D2 adsorption on a carbon molecular sieve used for air separation and the corresponding activated carbon substrate.(J Phys Chem B 2006,110,9947)
• In the case of carbons the pores size is not known precisely but probe molecules show that molecular cross sections of 4.5 A are the upper limit (J Phys Chem B 2001,105, 10619)
• In contrast, the pore sizes in MOFs are known from crystallographic studies.
Stretched Exponential Model
)(1 kt
e
t eM
M
The SE model is described by the following equation:
where Mt is the uptake at time t, Me is the equilibrium
uptake, k is the rate constant and is the exponential
parameter of the adsorption process.
Comparison of H2 and D2 Adsorption and Desorption on CMS T3A at 77 K
0.0
0.2
0.4
0.6
0.8
1.0
0 2000 4000 6000 8000 10000 12000 14000
0.0
0.2
0.4
0.6
0.8
1.0 M
t/M
e
H2
SE model
D2
SE model
a)
Time / s
H2
SE model
D2
SE model
b)
Pressure Increment
1-2 kPa
Pressure decrement
2-1 kPa
Normalised
kinetic profiles
The variation of the ratio of the rate constants for H2 and D2 adsorption (kD2/kH2) with pressure
and surface coverage on CMS T3A at 77 K
0 20 40 60 80 100
1.0
1.2
1.4
1.6
1.8
2.0
2.2
kD
2/k
H2
Pressure / kPa
Adsorption
Desorption
0.0 0.2 0.4 0.6 0.8 1.01.0
1.2
1.4
1.6
1.8
2.0
2.2
kD
2/k
H2
H2 n/nm
Zhao, X.B; Villar-Rodil, S.; Fletcher, A. J.; Thomas, K. M.
J Phys. Chem.B (2006), 110(20), 9947-9955.
H2 and D2 Adsorption on Two Mixed Metal Organic Frameworks with
Formula Zn3(bdc)3[Cu(salen)]
• Interactions with open metal centres and
• Confinement in porosity <6Å.
• Quantum effects are observed when the difference between adsorptive (H2 and D2) and pores sizes are similar to the de Broglie wavelengths (1.76 and 2.49 A)
• Zn3(bdc)3[Cu(Pyen)] J Am. Chem. Soc. 2008, 130(20), 6411-6423.
H2 and D2 Isotherms for Adsorption on Zn3(bdc)3[Cu(Pyen)] at 77.3 and 87.3 K
0 20 40 60 80 100
0
1
2
3
4
5
Am
ou
nt
Ad
sorb
ed/
mm
ol
g-1
Pressure/ kPa
D2 (77.3 K)
H2 (77.3 K)
D2 (87.3 K)
H2 (87.3 K)
Virial Equation
ln(n/p) =A0 + A1n + A2n2 -----
where n is the amount adsorbed at pressure p and the first virial coefficient A0 is related to the Henry’s law constant K0 by the equation K0 = exp(A0).
Zhao et al J Phys. Chem. B (2005), 109(18), 8880-8888
Virial Graphs for H2 and D2 Adsorption on Zn3(bdc)3[Cu(Pyen)]
0.000 0.001 0.002 0.003 0.004 0.005
-17
-16
-15
-14
-13
-12
ln(n
/p)
/ln
(mo
l g
-1 P
a-1)
n/ mol g-1
D2 (87.3 K)
H2 (87.3 K)
D2 (77.3 K)
H2 (77.3 K)
D2 (77.3 K) (HR)
H2 (77.3 K) (HR)
Comparison of H2 and D2 Adsorption Enthalpies as a function of amount adsorbed for Zn3(bdc)3[Cu(Pyen)]
0.000 0.001 0.002 0.003
9
10
11
12
QS
T/
kJ
mo
l-1
n/mol g-1
H2
D2
2 H2 or D2 molecules per
Cu in formula unit
Quantum Kinetic Effects for H2 and D2 Adsorption on
Zn3(bdc)3[Cu(Pyen)]
• 2-dimensional porous structure in the bc crystallographic plane
Double Exponential (DE) Kinetic Model for Two Types of Pores
tktk
e
t eAeAM
M21 111 11
Mt = mass uptake at time t
Me = mass uptake at equilibrium
A1 = fractional contribution of process 1
k1 = rate constant for process 1
k2 = rate constant for process 2
tk
e
t eM
M11
LDF and SE Models
)(1 kt
e
t eM
M
Comparison of H2 and D2 Normalised Kinetic Profiles for pressure increment 0.2-0.4 kPa for Zn3(bdc)3[Cu(Pyen)] at 77.3 K
0 500 1000 1500 2000 2500 3000 3500 4000
0.0
0.2
0.4
0.6
0.8
1.0
0 500 1000 1500 2000 2500 3000 3500 4000
-0.02
0.00
0.02
Re
sid
ua
lsM
t/Me
Time/ s
D2
DEmodel
H2
DEmodel
77.3 K
Pressure
0.2-0.4 kPa
D2
H2
Comparison of H2 and D2 Normalised Kinetic Profiles for pressure increment 0.2-0.5 kPa for Zn3(bdc)3[Cu(Pyen)] at 87.3 K
0 200 400 600 800 1000 1200 1400
0.0
0.2
0.4
0.6
0.8
1.0
0 200 400 600 800 1000 1200 1400
-0.02
0.00
0.02
Time/ s
Mt/M
e
D2
DEmodel
H2
DEmodel
87.3 K
Pressure
0.2 - 0.5 kPa
Re
sid
ua
ls
D2
H2
Variation of ln(k) for H2 and D2 Adsorption with Amount Adsorbed at 77.3 K
0.0 0.5 1.0 1.5 2.0 2.5 3.0
-8
-7
-6
-5
-4ln
(k)/
ln
(s-1)
Amount Adsorbed/ mmol g-1
k1 D
2 (77.3 K)
k2 D
2 (77.3 K)
k1 H
2 (77.3 K)
k2 H
2 (77.3 K)
Linear Regression k1 D
2
Linear Regression k2 D
2
Linear Regression k1 H
2
Linear Regression k2 H
2
Variation of ln(k) for H2 and D2 Adsorption with Amount Adsorbed at 87.3 K
0.0 0.5 1.0 1.5 2.0 2.5
-6
-5
-4
ln(k
)/ l
n(s
-1)
Amount Adsorbed / mmol g-1
k1 D
2 (87.3 K)
k2 D
2 (87.3 K)
k1 H
2 (87.3 K)
k2 H
2 (87.3 K )
Linear Regression k1 H
2
Linear Regression k2 H
2
Linear Regression k1 D
2
Linear Regression k2 D
2
Activation Energies for the Two Kinetic Components for Zn3(bdc)3[Cu(Pyen)]
Gas
Slow component, ln(k1, n=0)/ ln(s-1)
Ea/ kJ mol-1
77.3 K 87.3 K
H2 -8.475 ± 0.042 -6.111 ± 0.047 13.35 0.59
D2 -7.957 ± 0.015 -5.740 ± 0.023 12.52 0.47
Gas Fast component, ln(k2, n=0)/ln(s-1)
Ea/ kJ mol-1 77.3 K 87.3 K
H2 -6.320 ± 0.042 -4.805 ± 0.027 8.56 0.41
D2 -5.966 ± 0.017 -4.542 ± 0.031 8.04 0.35
c axis pores
b axis pores
The Variation of Activation Energy with Amount Adsorbed
0.0 0.5 1.0 1.5 2.0
6
8
10
12
Ea
/ k
J m
ol-1
Amount Adsorbed/ mmol g-1
EaH2k1
EaH2k2
EaD2k1
EaD2k2
Influence of Pore Size: H2 Adsorption Zn3(bdc)3[Cu(PyCy)]
N
N N
NO O
Cu
RR
A homochiral mixed metal organic framework with Enatioselective separation.
Adsorption on a Mixed Metal Organic Framework Zn3(bdc)3[Cu(PyCy)]
0 200 400 600 800 1000
0
1
2
3
4A
mount
Adso
rbed
/mm
ol
g-1
Pressure/mbar
n H2 77.3 K
n D2 77.3 K
n H2 87.3 K
n D2 87.3 K
Virial Graphs for H2 and D2 Adsorption on Zn3(bdc)3[Cu(PyCy)]
0.000 0.001 0.002 0.003 0.004
-18
-17
-16
-15
-14
-13
-12ln
(n/p
)/ln
(mol
g-1
Pa
-1)
n/mol g-1
H2Lnnp77K
D2lnp77K
H2lnnp87K
D2lnnp87K
2 molecules per Cu
Comparisons of enthalpies of adsorption (kJ mol-1) of H2 and D2 on Zn3(bdc)3[Cu(Pyen)] and Zn3(bdc)3[Cu(PyCy)] at zero surface coverage
Zn3(bdc)3[Cu(Pyen)]
H2 12.29
D2 12.44
Zn3(bdc)3[Cu(PyCy)]
H2 9.65
D2 9.76
The Qst at zero surface coverage, which is a measure
of the H2-surface interaction influenced by
a) the narrow porosity or
b) Surface chemistry?
Comparison of D2 Normalised Kinetic Profiles for pressure increment 0.2-0.5 kPa for
Zn3(bdc)3[Cu(Pyen)] Zn3(bdc)3[Cu(PyCy)] at 87.3 K
0 500 1000 1500 2000 2500
0.0
0.2
0.4
0.6
0.8
1.0
Mt/M
e
Time/ s
Zn(bdc)3(PyCy), D
2 at 2 - 5 mbar, 87.3 K
Zn(bdc)3(Pyen), D
2 at 2 - 5 mbar, 87.3 K
Comparison of D2 Normalised Kinetic Profiles for pressure increment 10-15 kPa for
Zn3(bdc)3[Cu(Pyen)] Zn3(bdc)3[Cu(PyCy)] at 77.3 K
0 200 400 600 800 1000 1200 1400 1600 1800
0.0
0.2
0.4
0.6
0.8
1.0M
t/Me
Time/ s
MtMePyen
MtMePycy
H2 kinetics at P 100 -- 150 mbar, 77 K
Comparisons of adsorption of H2 and D2 on Zn3(bdc)3[Cu(Pyen)] and Zn3(bdc)3[Cu(PyCy)]
• Crystallographic studies show smaller pore sizes and adsorption kinetics for Zn3(bdc)3[Cu(PyCy)] are slower than for Zn3(bdc)3[Cu(Pyen)] indicating narrower porosity.
• nD2/nH2 ratios do not vary greatly with surface coverage and are ~1.1 at 77 and 87 K
• Isosteric Enthalpies for adsorption at Zero Surface Coverage are higher for Zn3(bdc)3[Cu(Pyen)] than for Zn3(bdc)3[Cu(PyCy)]
• The Qst at zero surface coverage is very sensitive to the spatial and/or electronic environments around Cu2+ sites which influence interactions with hydrogen molecules. Smaller pores do not necessarily increase Qst
Hydrogen Adsorption on
Porous Materials Zhao et al, Science 2004,
304, 1012
0
2
4
6
8
10
0 200 400 600 800 1000
0
1
2
3
4
AC
AC
C
C
AA
mou
nt
Ad
sorb
ed
/ m
mol
g-1
Pressure/ mbar
M
M
E
E
B
Hydrogen Desorption
0 50 100 150 500 1000 1500 2000 2500 3000 3500 4000
80
84
88
92
96
100
40
50
60
70
80
90
100
Am
ou
nt
Ad
sorb
ed/
%
Time/s
H2 amount adsorbed
on E at 49 mbar
Pre
ssu
re/
mb
ar
P
Comparison of Hydrogen isobars on Porous Metal Organic Framework and
Carbon Materials
-200 -180 -160 -140 -120 -100 -80
0
20
40
60
80
100
Am
ou
nt
Ad
sorb
ed/
%
T/o
C
E MOF
C
M MOF
AC
Possible Mechanism
• Adsorption of hydrogen may result in stiffening of the metal organic framework. In this case the desorption should change with hydrogen loading
• Thermally activated structural change
How can we improve the adsorption capacity and temperature dependence?
• Larger pore volumes,
• Cage structures
• Narrow windows in the structure
• Surface chemistry: Unsaturated metal centres,
H2 adsorption at 77 K on NPC-4
0 5000 10000 15000 20000
0
1
2
3
4
5
H2 s
urf
ace e
xcess u
pta
ke (
wt
%)
Pressure (mbar)
Adsorption at 77K
Desorption at 77K
H2 adsorption on NPC-4 at 77 K
Absolute uptake =5.03 wt% at 20 bar
H2 density in pores = 0.0644 g cm
-3
H2 adsorption at 77 K on NPC-4
0 5000 10000 15000 20000
0
1
2
3
4
5
20 bar 2 nd
20 bar 1st
Su
rfa
ce
Ex
ce
ss
H2
Up
tak
e (
wt%
)
Pressure (mbar)
H2 adsorption at 195 K
0 5000 10000 15000 20000
0.0
0.5
1.0
1.5
2.0
H2 adsorption on NPC-4 at 195 K
Adsorption
Desorption
Su
rfa
ce
Ex
ce
ss
Up
tak
e a
t 1
95
K (
wt%
)
Pressure (mbar)
Absolute uptake = 1.86 wt% at 19 bar
Conclusions
• High pressure hydrogen capacity on a weight basis correlates with pore volume and surface area for all porous materials
• Hydrogen capacity on a volumetric basis has only limited correlation at surface areas up to 2000 m2 g-1
• Quantum kinetic molecular sieving effects are observed for H2 and D2 for all porous materials
Conclusions: Surface Interactions
• Mechanisms for improving temperature dependence of hydrogen adsorption on metal organic frameworks involve ; surface chemistry modification: for example, stronger adsorption on open or unsaturated metal centres is an example (Kubas type interactions).
• Adsorption on the metal centres shows the relationship between adsorption characteristics and stoichiometry of the H2-surface interaction consistent with adsorption on both sides of the CuO2N2 Salen pillars in Zn3(bdc)3[Cu(salen)]
• However, most interactions observed so far are not strong enough for true Kubas coordination
Conclusions
• Qst values are sensitive to the spatial and/or electronic environments around Cu2+ sites, which influence interactions with hydrogen molecules.
• Cage structures with narrow windows have some interesting temperature dependent characteristics, which are being investigated further
Acknowledgements • Adsorption Studies: X. B. Zhao, B. Xiao, A. Putkham,
J. Bell, R. Gill, A. J. Fletcher, M. Kennedy, J Armstrong and T Rexer.
• Synthesis and Structure Zn3(bdc)3[Cu(Pyen)], Zn3(bdc)3[Cu(PyCy)] B. Chen, K. Hong, E. B. Lobkovsky, E. J. Hurtado, S. Xiang, M-H Xie, C. D Wu,
• Synthesis and Structures of Ni2(bpy)3.(NO3)4 phases
D. Bradshaw, J. Barrio and M. J. Rosseinsky
• M. Schroder (Nottingham University, Angew. Chemie. 2006, 45, 7358; Chem. Comm. 2008,6108; JACS 2009,131,2159) and R. Morris (St Andrews University; JACS 2007, 129.1203 and Nature Chem 2009 and 2011)