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MOFs and their energy applications
Omar M. Yaghi
Department of Chemistry, UC BerkeleyLawrence Berkeley National Laboratory
Kavli Energy Nanosciences Institute, Berkeley
Materials of the 20th century
• Metals, alloys, and composites • Metal oxides• Zeolites• Polymers• Pharmaceuticals• Concrete• Silicon
Materials for the 21th century
• Parallel and serial in their operation• Compartmentalized in their structure • Capable of counting, sorting and coding• Capable of robust dynamics
Simple synthesis and environmentally safe manufacturing
Nanocubes of Metal-Organic Frameworks
+COOH
COOH
Organic Strut Inorganic Zn4O Joint MOF-5
“THE NUMBER WAS so unbelievably high, I thought it had to be a misprint.” Dr. Ulrich
Mueller, BASF
MOF-5 with exceptional surface area (3,000 m2/g), and control of its metrics
and functionality CRYSTALLIZATION PROBLEM”
Nature 1999 Science 2002
+
ORGANIC INORGANIC
RETICULAR SYNTHESIS OF MOFs
MOFs
Nature 2003
UiO-66: Linking Cuboctahedra
J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga, K. P. Lillerud, J. Am. Chem. Soc. 2008,130, 13850-13851.
fcu-a Zr6O4(OH)4(BDC)6
9
Pores without walls lead ultra-high surface area: BET: 6,500 m2/g; Langmuir: 10,000 m2/g for MOF-200
Science 2010
One gram of MOF (size of a US$ coin)has 10,000 m2/gram. This is equivalent to a
soccer field
Progress in the synthesis of ultra-high porous MOFs
Methane:Cleaner than petroleum
Hydrogen: The cleanest fuel
Carbon dioxide:Detrimental to our planet
These molecules are changing the world
Water:Fresh, cleaner water is needed
12 wt% total adsorbed
7.5wt% surface excess
Independent Verification of MOF-177 Hydrogen Uptake Capacity(volumetric and gravimetric measurements verified, shown using gravimetric scale)
77 K
Mercedes-Benz F125! Research Vehicle Technology
The environmentally responsible Mercedes-Benz F125! is capable of handling any traffic situation with zero-emissions
BASF
0
50
100
150
200
250
0 10 20 30 40 50 60 70 80Pressure / bar
working capacity
Upt
ake
/ a.u
.
unused methane
0
50
100
150
200
250
300
working capacityU
ptak
e / a
.u.
unused methane
Working Capacity for Methane Storage
Seungkyu Lee
Hiroyasu Furukawa
Felipe Gandara
100806040Pressure (bar)
Tota
l CH
4 up
take
(cm
3 cm
-3)
200
350
300
250
200
150
100
50
0
MOF-519MOF-520Bulk denisity of CH4
Exceptional uptake of methane in MOF-519 and -520 at 298K
Tonne batches
Scale-Up and Shaping at BASF
Shaped Bodies
Partial list of large companies working on MOFs
MOF structures and patents
Control at the molecular level and outstanding properties
Expand the organic struts and vary metal without changing the
topology
Highest porosity ever recorded (10,000 m2/g)
Hydrogen storage (2.0 % r.t.)Methane storage (>250/250, gL-1bar-1)
Gas separations & others Size and electronic selectivity
Organic and inorganic units together into a large
variety of structures
Precisely designed interiors: space and link
functionality“Crystals as molecules”
Carbon capture in the presence of water
Catalysis
Water harvesting from air
Superacidic MOFs
Largest pore size and opening in porous crystals
From Passive Frameworks to Active Frameworks
2C8H18 + 25O2 = 16CO2 + 18H2O24 kg 81 kg
An approximate calculation of how much carbon dioxide is emitted from one tank of
petrol in an automobile
A 20% mixture of CO2 in CH4 is fed into a bed of Mg-MOF-74. Effluent concentrations are shown, indicating complete retention of CO2 until saturation
CO2 separation (at room temp.) from CH4 in Mg-MOF-74
7
R= CH3NH2CH2NHBocCH2NMeBoc
CH2NH2CH2NHMe
230 °C
Post-synthetic deprotection
Amino-Functionalized IRMOF-74-III are Crystalline and Highly Porous
A. M. Fracaroli, A. M.; Furukawa, H.; Suzuki, M.; Dodd, M.; Okajima, S.; Gándara, F.; Reimer, J. A.; Yaghi, O. M. J. Am. Chem. Soc. 2014, 136, 8863. 12
Breakthrough experiments under wet conditions
IRMOF-74-III-CH2NH2 remains selective towards CO2 in the presence of water
Distribution of linkers in CHA ZIFs
N
HNX
Red = Gray = Green = N
HNX
orN
HN
N
HN
hpr
cha
Breakthrough time of CHA ZIFs did not change under wet conditions
MOF-841 is a good material for water uptake and release
MOF-841
Measure water uptake and release on a TGA/DTA apparatus. Adsorption: 30% RH at 30 oC for 100 min Desorption: 30% RH at 85 oC for 30 min
MOF-801 shows good cycle performance
MOF-801
32
Use MOF-801 with 20 wt% water uptake Temperature swing range: 30-85 oC Desorption process (30 min) is much
faster than adsorption process (1.5-2 h) Quad adsorbent beds system to reduce
the cycle time 1 m3 MOF quad beds, 60% packing
density of MOF (i.e. 1 g/cm3).
wetair
dryair
wet air
heat
purge
cool
water
water
MOF
water adsorption
Personalized water and harvesting water from air
50 L water can be delivered every 30 min, if relative humidity is higher than 30%.
Zr6O4(OH)4(-CO2)6(HCO2)6
H3BTC
MOF-808 as a superacid
(a) (b)
(c)
(d)
MOF-808-P
MOF-808-2.5SO4
SEM, N2 isotherm, pxrd and crystal structure of MOF-808 and MOF-808-2.5SO4
Sulfated MOF-808 is more acidic than sulfuric acid
Covalent organic functionalization and metallation of MOFs
(Zn4O)3(BDC-NH2)3(BTB)4
XRPD patterns for the three MOF reaction products
(Zn4O)3(BDC-NCH-C5H4N2)3(BTB)4
(Zn4O)3(BDC-NH2)3(BTB)4 simulated
(Zn4O)3(BDC-Pd-NCH-C5H4N2)3(BTB)4
(Zn4O)3(BDC-NH2)3(BTB)4 found
Porosity of the ammino-, chelate and Pd- complexed covalently functionalized crystals of MOF
Hydrogenation catalysis at 100 °C
Synthetic strategy for the assembly of cascade catalysts
Metal nanocrystals embedded in single nanocrystals of MOFs
Compartmentalization of matter and function
Metal nanocrystals embedded in single nanocrystals of MOFs
Gabor Somorjai Kyungsu Na Kyungmin Choi
Test reaction using Pt on SiO2
* No catalytic reaction with UiO-66
Pt on SiO2
K. Na, K. M. Choi, O. M. Yaghi*, G. A. Somorjai*, NANO Lett., 2014
Test reaction using Pt on SiO2
* No catalytic reaction with UiO-66
150 °C
K. Na, K. M. Choi, O. M. Yaghi*, G. A. Somorjai*, NANO Lett., 2014
Stability test after the reaction
Pore-size effect on the catalytic selectivity and activity
Sulfonic functionalized Pt⊂SO3H-UiO-66
Successful use of MOFs for high capacitance
The fabrication process of Oh-nano-Ag⊂MOFparticles
Peidong Yang Nick Kornienko Yingbo Zhao
The structure of Al2(OH)2TCPP MOF
SEM and TEM images of the Oh-nano-Ag⊂MOFparticles
Order (crystallinity) and orientation of MOF on the silver nanocrystal interface
One compound of many functionalities
Science 2010
Multivariate metal-organic frameworks (MTV-MOFs)
Control of functionality ratios in MTV-MOF-5-AB series
Percentage of functionality B increases from left to right
Bias for functionality B
Heterogeneity within order
57
http://commons.wikimedia.org/wiki/File:DNA_chemical_structure.svg
Mapping the interior of MTV-MOFs
400% improvement in selectivity for carbon dioxide
0
20
40
60
80
100
120
140
160
180
200
0 100 200 300 400 500 600 700 800 900
Upt
ake
/ cm
3g-
1
Pressure / torr
BTB-OMe
BTB
BTB-NH2
COOH
COOHHOOC
COOH
COOHHOOC
NH2
H2N
NH2
COOH
COOHHOOC
O
O
O
Increasing of H2 uptake by changing functional groups on the BTB linker
25% increase in capacity
Hydrogen storage Methane storage Carbon dioxide caputre Trapping VOC Catalysis Solar to fuels Pure water Chiral separations
3-D ‘DNA’ for counting, sorting and coding of information
MOFs1995
IRMOFs2002
COFs2005
ZIFs2006
METs2008
CATs2009
MTV-MOFs2010
Supercapacitors Ion conduction Proton conduction Transistors
Reticular chemistry and its applications
Drug transport Biomedical imaging Food shelf-life
WEAVED NETs2014
Stimuli responsive Robust dynamics
Nano-MOFs2013
C-C, C-B, C-O,… (300-400 kJ/mol)Covalent Organic Frameworks, 2005
M-O2CR, M-NR2,... (300-350 kJ/mol)Metal-Organic Frameworks, 1998 &1999Zeolitic Imidazolate Frameworks, 2003
M-N bipyridine-type (60-100 kJ/mol) Coordination ‘polymers’, ca. 1955
Hydrogen-bonds (10-20 kJ/mol)Common organic acids
Vander Waals (2-5 kJ/mol)Molecular crystals
Linking Building Blocks into Extended Structures and the “Crystallization Problem”
Control of weak bondsSupramolecular chemistry
Control of strong bondsReticular chemistry
Congratulations!
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