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

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0 10 20 30 40 50 60 70 80Pressure / bar

working capacity

Upt

ake

/ a.u

.

unused methane

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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

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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

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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

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