hhydrogen storage in metal-organic frameworks · hhydrogen storage in metal-organic frameworks...
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Omar M. YaghiDepartment of Chemistry
Center for Reticular ChemistryUCLA
Progress report, May 07
HYDROGEN STORAGE IN METAL-ORGANIC FRAMEWORKS
This presentation does not contain any proprietary, confidential, or otherwise restricted information
Project ST10
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OverviewOverviewTimelineProject start date: 5/1/2005Project end date: 4/30/2009
BudgetTotal project funding: DOE $1.6 MFunding received FY 05: $112 KFunding for FY 06: 150 KFunding for FY 07: 430 K
Barriers addressedTechnical barriers addressed:
Improved gravimetric and volumetric density of hydrogen uptakeHydrogen capacity and fast kinetics at 77KImproved hydrogen binding energySynthesis scale up of MOFs to cubic meters
Technical system targets by 2010:Gravimetric capacity: 6 wt% and 1.5 kWh/L; Volume capacity: 45gH/L; operating temperature: -30° to 45°C
Partners (depends on funding)Juergen Eckert (UCSB)Joe Hupp (NW)Randy Snurr (NW)
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Objectives and important directionsObjectives and important directionsA. DESIGING POROSITY1) Increased binding energy2) Increase surface area without increase of dead volume3) Cycling and kinetics of hydrogen charge and discharge4) Impact of open-metal sites on binding energy and uptake
capacity5) Impregnation with polymers and nano-particles of light
metals
B. MOFs AS MOLECULAR FUEL TANKS1) Scale up of favored MOFs2) Transfer of samples to DOE for independent verification of
data3) Establish a standard for hydrogen storage measurements
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Reticular chemistry is concerned with linking of molecular building blocks (organic molecules, inorganic clusters, dendrimers, peptides, proteins,...) into predetermined structures in which such units are repeated and are held together by strong bonds.
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DESIGN OF POROSITYControl of the organic link’s functionalityVariation in metal-oxide units’ size and compositionControl of pore-metricsExposition of metal-sites within the poresStrategies for achieving high surface areasControl of dead volume
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Maurits Escher
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H2 Adsorption in Non-Catenated MOFs
Functionality has little impact on uptake
IRMOF-1
IRMOF-3 IRMOF-6
IRMOF-2
IRMOF-8
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H2 Adsorption in Non-Catenated MOFs
Functionality has little impact on uptake
IRMOF-18 IRMOF-20
MOF-177
IRMOF-1
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IRMOF-1 IRMOF-8
IRMOF-9
IRMOF-13
H2 Adsorption in Catenated MOFs
Catenation increases uptake by 40% relative to non-catenated
IRMOF-11
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IRMOF-62: Design of highly catenated MOF with Pore size favored for hydrogen
O
OH
O
HO
3.5 Zn(NO3)2•4H2O1 eq. Et3N
DMF
P3212a = 31.114(1) Å, c = 39.280(3) ÅCell Volume: 32931.2(2) ųd = 0.691 g cm-3
MOF-5 like frameworkQuadra-interpenetratingSmall channel can be seen along crystallographic c-axis (5.2 Å in diameter)Utilization of “edge” (diyne link)
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OPEN METAL SITESDesign within MOF frameworksImpact on uptake capacityImpact on adsorption energy
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MOFs with open metal sites
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Cu2(ATC)·6H2O Cu2(ATC)
JACS 2001 (Banglin Chen)
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MOF-505
MOF-74MOF-199
IRMOF-1 IRMOF-13
H2 Uptake by MOFs with Open-Metal Sites
Open metal sites increase uptake by 70%
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Hydrogen Adsorption SitesInelastic neutron scattering (reported last
review)X-ray single crystal structure on N2 and ArSingle crystal neutron diffraction
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Single crystal X-ray diffraction at 30 K for Ar guest
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Single Crystal Neutron Diffraction
Data collected on VIVALDI (ILL) on 0.5 mm3 crystal sealed under D2
Appearance of D2 on α(CO2)3 site at 50 K, additional D2 appears on β(ZnO)3 at 5 K
J. Howard and O. Yaghi , Chem. Commun. 2006
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Design of surfaces replete with adsorption sites
Can high surface area and reduced dead volume (i.e. good volumetric capacity) be achieved in one material?
Uptake capacities of MOFs under high pressure conditions and 77K
4. Reversibility of uptake
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0
300
600
900
1200
1500
0 0.2 0.4 0.6 0.8 1
Am
ount
sor
bed
(mg/
g)
P/P0
N2 sorptionN2 desorption
Surface area = 4,500 m2/g(5,500 m2/g)
Pore volume = 1.59 cm3/g ( 0.69 cm3/cm3)
N2 adsorption isotherm for Zn4O(BTB)2
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Zn4O(BBC)2
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MOF-200:Zn4O(BBC)2
Trigonal, P-3a = b = 51.45 Åc = 41.80 ÅV = 95,822.1 Å3
S.A. = ‘8,000’ m2/g
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0
10
20
30
40
50
60
70
80
0 10 20 30 40 50 60 70 80 90Pressure (bar)
Gra
vim
etric
Upt
ake
(mg/
g)
MOF-177 IRMOF-20 IRMOF-1 IRMOF-6
IRMOF-11 HKUST-1 MOF-74
7.5 wt % Hydrogen uptake at 77K
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MOF volumetric H2 uptake at 77 K
0
5
10
15
20
25
30
35
40
0 10 20 30 40 50 60 70 80 90Pressure (bar)
Volu
met
ric U
ptak
e (g
/L)
IRMOF-20 MOF-177
IRMOF-6 IRMOF-1
HKUST-1 MOF-74
IRMOF-11
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10
20
30
40
50
60
70
80
0 1000 2000 3000 4000 5000 6000Surface Area (m2/g)
Upt
ake
(mg/
g)
MOF-74
HKUST-1
IRMOF-11
IRMOF-6IRMOF-1
IRMOF-20
MOF-177
Correlation of uptake with surface area
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Isosteric Heats of Adsorption
MOFs combining open metal sites with 7-8 Angstroms pore size are most favored
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H2 Adsorption (high-P)Poor room temperature uptake
d = 0.884
wt% mg/g mmol/g cc/g cc/cc g/L
77 K 3.3 33 16.5 370 327 29.2
298 K 0.4 4 2 45 40 3.5
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Kinetic Profile of Uptake and Release of hydrogen
(Fueling Time)
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Completely Reversible Charge/Discharge of Hydrogen Adsorption in IRMOF-11
Fueling time 2.5 minutes
99.5
100.0
100.5
101.0
101.5
102.0
0 20 40 60 80 100 120 140
time (min)
mas
s (%
)
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Blue: applied pressure, red: weight change (without buoyancy correction)
Typical IRMOF-62 kinetic profile(Fueling time 2 minutes)
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Absolute adsorbed amount
Surface excess amount
Independent Verification of MOF-177 Hydrogen Uptake Capacity
(volumetric and gravimetric measurements verified, shown using gravimetric
scale)
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IRMOF-62 Surface area: 2650 m2/g, Pore volume: 0.95 cm3/g
Red: IRMOF-62Blue: MOF-177
Filled symbols: adsorption Open symbols: desorption
Absolute adsorbed amount
Surface excess amount
Volumetric H2 uptake for IRMOF-62
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MOFMOFHydrogen Storage Capacities (50 bar, 77K)Hydrogen Storage Capacities (50 bar, 77K)
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Nanocubes as molecular fuel tanksBASOCUBES
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Coordination with theory (Prof. Bill Goddard, Caltech)Impregnation strategies: (a) polar polymers, (b) clusters of lights metals, and organo-metallic complexes Design of soft chemi-sorption within the pores: Proximal Lewis acid-Lewis base sites
Strategies for increasing adsorption energy
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Strategy 1:
Binding Li to six membered rings
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High room temperature hydrogen uptake (5%wt) in Li-doped Zn-MOF systems
0 20 40 60 80 1000
1
2
3
4
5
6
H 2 upt
ake
amou
nt (w
t%)
Pressure (bar)
At 300 K
Triangle: pure MOFs, Star: Li-doped MOFs
Cyan: MOF6, Blue: MOF10, Green: MOF16, Red: MOF22, Black: MOF30
C6Li
C5Li
C5.3Li
C5.5Li
C5LiPredictions (Han and Goddard, Caltech)
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Strategy 2A:
Impregnation with metal complexes having open metal sites
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Proof of ConceptSuccessful Impregnation of CpW(CO)3 in MOF-5
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Carbonyl groups can be removed by heating under vacuum, leaving behind open metal sites of W
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Strategy 2B:
Impregnation with polymers containing conjugation
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Polymer impregnation MOF-177
Polymerization of monomer in MOF-177
1,4-Diphenylbutadiyne
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Impregnation
Polydiphenyl-butadiyne(PDPB)
MOF-177 + PDPB
A
B C
A. Single crystal of PDPBB. MOF-177 + PDPBC. Sliced MOF-177 +
PDPB
Sliced face
1957 cm-1
1947 cm-1
C≡C stretching
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Strategy 3:
Chemisorption douce
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Fully Reversible Splitting of H2
+H2
- H2
Heating to >100o C quantitatively reverses H2 dissociation with change in color.
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Covalent Organic Frameworks (COFs)
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COF-1
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Science 2005
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COF-5
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COF-108: Density = 0.17 g/cm3
Surface area = 4,700 m2/g Science 2007
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It’s all in the angle (145°)
145° 145°
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ZIF-8 sod
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Thermal stability of ZIFs
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Chemical stability of ZIF-8
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K. S. Park, A. P. Côté, J. Y. Choi, R. Huang, F. J. Uribe-Romo, H. K. Chae, M. O’Keeffe, O. M. Yaghi, Proc. Nat. Acad. Sci. USA, 2006, 103, 10186-10191.
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ZIF-100 ZIF-105
Trigonal Zn metal site next to Z-F bond both pointing to the center of pore
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PROGRESS
1.Tuning porosity lead to tripling of hydrogen uptake in MOFs (excess 7.5% wt, absolute 12% wt)2.The 35 grams H2/L achieved in MOF-177, clearly indicates that dead volume is none issue for MOFs3.MOFs exhibit fast kinetics (1-3 minutes for charging and discharging)4.MOF materials porosity and uptake are stable to charge/discharge cycling5.Cubic meter scale of useful MOFs is now developed by BASF
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FUTURE WORK
1. Higher adsorption energy by:(a) Design of Lewis-acid and Lewis-base sites (b) Doping with Li and impregnation with early
T.M. complexes(c) Acetylene MOFs for high surface areas and
stronger binding of hydrogen2. Application of high throughput and characterization
methods to search for specific structures3. Testing new materials :
(a) Zeolite imidazolate Frameworks (ZIFs)(b) Covalent organic frameworks (COFs)
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Dr. C. Knobler Dr. A. Côté
Dr. H. El-Kaderi
Dr. N. Aratani Dr. R. Banerjee
Dr. O. El-Kaderi Dr. H. HayashiDr. H. Furukawa
Dr. B. Ramachandran Dr. Q. Wei D. Tranchemontagne F. Uribe-Romo B. WangI. E. RaudaA. Phan
J. Mendoza-Cortés K. ParkQ. LiJ. R. Hunt
S. DuhovicL. DudekE. ChoiD. Britt
Dr. Z. Ni
Current Group MembersThanks for putting up with Professor
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C E N T E R F O R R E T I C U L A R C H E M I S T R Y
U C L A □ C N S I □ B A S F