Metal-Organic Frameworks

2010. 8.25
2010 @KAIST ,


Introduction Synthesis of MOFs Characteristics of MOFs Applications

Introduction

What is Metal-organic framework (MOF)?

Metal-Organic Frameworks are crystalline compounds consisting of metal ions or clusters coordinated to often rigid organic molecules to form one-, two-, or threedimensional structures that can be porous (Wikipedia.org) Coordination polymers(CP), Metal-organic frameworks(MOF) Porous coordination network(PCN) Porous coordination polymer(PCP) MIL (Material from Institute Lavoisier) POST-1 HKUST-1 UMCM-1

Crystal Growth & Design, 9, 2969-2970 (2009)

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Evolution of Coordination Polymers (or MOFs)

1960s Early 1990s Middle 1990s
Copper 4,4-bipyridyl complex that exhibited extended metal-organic interactions

1,5-Dihydroxynaphthalene2,6-dicarboxylic acid formed coordination polymers with Zn, Ni, Al, and Fe+3

Addressed as MOFs, coordination polymers, or supramolecular structures

Tomic et al. J. Appl. Polym. Sci. 9, 3745 (1965) Bailar et al. Prep. Inorg. React. 1, 1 (1964).
Yaghi et al. J. Am. Chem. Soc. 117, 10401 (1995) Hoskins and Robson, J. Am. Yaghi et al. Nature, 378, 703 (1995).

Chem. Soc. 112, 1546 (1990)

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A Various Organic Linkers

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A Various Organic Linkers

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Isoreticular IRMOFs and Unique Properties

Applications: - Gas storage/separtion - Catalysts/Adsorbents - Drug delivery - Sensor - Templates

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Metal-organic framework, MOF-5(IRMOF-1)

Highly Stable and Porous MOF

1.4-BDC + Zn2+ [Zn4O(RCO2)6] MOF-5

Void/Cavity

+ Linker
O OH

SBU

H2BDC =
HO O

Linker Flexibility

Benzene dicarboxylic acid Yaghi et al. Nature 402, 276-279 (1999)

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Sorption Properties of MOF-5

Sorption Isotherms Pore volume VP = 1.04 cm3/g = 0.60 cm3/cm3 Surface area SL = 2,900 m2/g Faujasite VP = 0.48 cm3/g SL = 500 m2/g

amount sorbed (mg/g)

P/P0
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MOF-177 : [Zn4(O)(BTB)2.15DEF.3H2O]

H3BTB + Zn(NO3)2 6 (H2O) Zn4(O)(BTB)2 15DEF 3H2O MOF-177

*BTB: 1,3,5-benzenetribenzoate
Chae, H. K.; Kim, J.; Go, Y.; Eddaoudi, M.; A. J. Matzger; Yaghi, O. M. Nature 2004, 427, 523.
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N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)

1500

Amount sorbed (mg/g)

1200 900 600 300 0 0 0.2 0.4 P/P

N2 sorption N2 desorption

Surface area = 4500 m2/g Pore volume = 1.59 cm3/g (0.69 cm3/cm3)

0.6
0

0.8

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Yaghi
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Ultrahigh Porosity in Metal-Organic Frameworks

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Kim et al., Science, 329, 424 (2010)

A Chromium Terephthalate MIL-101

MIL-101: {Cr3F(H2O)2O[C6H4(CO2)2]3nH2O}, n~25
Giant cell volume ~702,000 Langmuir surface area ~5900 m2/g Large pore size 30-34

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Ferey et al., Science, 309, 2040 (2005)

Porous Coordination Polymers

A rigid metalorganic coordination framework [Co2(4,4'-bipy)3(NO3)4]4H2O]n

Angew. Chem., Int. Ed. 36, 1725 (1997)

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A Chemically Functionalizable MOF, Cu3(BTC)2(H2O)3]n

HKUST-1
S.Y. Chui et al., Science, 283, 1148 (1999)
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SBET = 1390 m2/g 17

New Types of Crystalline Porous Hybrids

Metal-Organic Polyhedra (MOP)

Zeolite Imidazolate Frameworks

Eddaoudi et al. J.ACS 2001

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ZIF-20 Hayashi et al. Nat. Mat. 2007

Heading To Market With MOFs

On The Road German adventurer Zietlow poses in Egypt in November 2006 during his Now In Stores A worker packages MOF 28,000-mile driving expedition in a naturalmaterials produced in kilogram batches at gas-fueled vehicle. The vehicle was equipped BASF's pilot plant, in Ludwigshafen, Germany with fuel tanks that were modified with MOF compounds to increase their storage capacity Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate (left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed. Each compound contains smaller and larger nanometer-sized cages, accessible via interconnecting windows. The MIL-100 small cage is 25 in diameter; MIL-100 large cage, 29 ; MIL-101 small cage, 29 ; MIL-101 large cage, 34 . Cr is yellow, C is white, O is red, and H2O is green.

Methane Hoarder This framework compound, dubbed PCN-14, is composed of dicopper paddlewheel units and linkers based on an anthracene derivative. Among porous materials, PCN-14 holds the record for methane storage. Cu is turquoise, C is gray, and O is red

C&EN Cover 2008.05

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The pervasive chemistry of metal-organic frameworks

Chem. Soc. Chem. 38, 1213 (2009)

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Synthesis

Solvothermal/Hydrothermal synthesis Microwave or Sonochemical synthesis Electrochemical synthesis Ionothermal synthesis

How to design or synthesize ?

Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids

If appropriate SBUs and ligands chose, desired MOF can be formed depending on reaction condition

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Solvothermal Syntheses of MOFs

Small scale, slow reaction??

Mueller et al. J. Mater. Chem.,16, 626 (2006)

Yaghi et al. Nature 402, 276-279 (1999)

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Synthesis Solvothermal bomb placed in autoclave at 10~100bar and 100oC for 1-4days Scale: 30 ~500mg Reaction control: Manual Monitoring: None

In Situ Diffraction Study of solvothermal Crystallization

Millange et al. Angew. Chem. Int. Ed. 48, 1 (2009)

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Microwave (or sonochemical) Syntheses of MOFs

MOF-5

Ahn et al. Chem. Commun. 6336 (2008)

HKUST-1

Jhung et al. Adv. Mater. 19, 121 (2007)

Hwang et al. Micropor. Mesopor. Mater. 119, 331 (2009)

Rapid synthesis of MOFs through microwave-irradiation - Homogeneous and selective heating - fast nucleation and crystallization
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Microwave Synthesis of MIL-101(Cr)

Microwave synthesis at 483 K for 1 40 min 1.0 Cr(NO3)39H2O: 1.0 BDC: 1.0 HF: 280 H2O (BDC = terephthalic acid)
(a) (b)

1 min

TEM

200nm 10 min 200nm

(c) (d)

Nanoparticles

20 min

40 min 500nm 500nm

MIL-101: {Cr3F(H2O)2O[C6H4(CO2)2]3nH2O}, n~25

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Jhung et al. Adv. Mater. 19, 121 (2007)

Ionothermal syntheses of MOFs

Russell E. Morris Chem. Commun. 2990 (2009)

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High-throughput Syntheses of Cobalt Succinates

pH, Temperature, Concentration and Time

Forster et al. Angew. Chem. Int. Ed. 44, 7608 (2005)

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Electrochemical Synthesis of HKUST-1

150 min at a 12-19V, 1.3A SBET 1820 m2/g Mueller et al. J. Mater. Chem.,16, 626 (2006)

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Large Scale Syntheses of MOFs

Muller et al. Chem. Soc. Rev. 38, 1284 (2009)

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Nanoscale Syntheses of MOFs

Surfactant-assisted synthesis of nanoscale Gadolinium MOFs CTAB/1-hexanol/n-heptane/water Microemulsions Ga2(bhc)H2O)6

Lin et al. Angew. Chem. Int. Ed. 47, 129 (2008) Lin et al. Eur. J. Inorg. Chem. 3725 (2010)

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Computational Design of MILs

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Mellot-Draznieks et al. Z. Anorg. Allg. Chem. 630, 2599 (2004)

How Molecules turn into MOFs

Crystal growth of HKUST-1 by AFM

R. Morris ChemPhysChem 10, 327 (2009) Attfield et al. Angew. Chem. Int. Ed.
47, 8525 (2008)

Whittingham et al. Crytstal Growth Design 6, 2419 (2006)

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Characteristics of MOFs

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Functions of MOFs (Nanospace laboratory)

Kitagawa et al.
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Angew. Chem. Int. Ed., 43, 2334 (2004)

Guest-induced transformation of MOFs

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Dynamic frameworks and Breathing of MOFs

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Gerard Ferey, Chem. Soc. Rev. 37, 191 (2008)

Zeolite A Imidazolate Frameworks (ZIF)

CO2 Sorption Isothems at 298 K

CH4

Breakthrough curves CH4 LTA Topology CO2

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Yaghi and co-workers, Nature Mater., 6, 501 (2007)

Applications

Hydrogen storage capacities of MOFs

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40

Hydrogen storage of HKUST-1

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Carbon Dioxide Capture of MOFs

MOF-177

Adsorption isotherms of MIL-101 at 303 K

40 800
Amount adsorbed (cm /g)

CO2 Sponge!
600

Amount adsorbed (mmol/g)

30

400

20

200

10

176 wt% at 303 K and 50 bars

0 0 10 20 30 40 0 50 Pressure (bar)

Chang et al. Langmuir, 24, 7245 (2008)

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Sulfur Sorption of HKUST-1

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Summary of catalytic reaction employing MOFs

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Catalytic Oxidation of Sulfides with H2O2 over MIL-101

Formation of CUS
F,OH F,OH

Cr Cr Cr

at 150oC
Cr

Cr Cr

- 2H2O H2O H2O

CUS

CUS

nCUS = ca. 1 mmol/g

m3-O bridged Cr(III) trimer

Sulfoxidation

Appl. Cata. A: Gen. 2009

aThe

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reaction time was 12 h. bH2O2/benzyl phenyl sulfide = 2. cH2O2 efficiency (%) = 100 x (mole of oxygenated products)/(total mole of H2O2 converted).

Chiral Catalysis in MOF

CdCl2 + L [Cd3Cl6L3](1) Ti(OiPr)4

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Kim et al. 404, 982 (2000)

W. Lin, J. Am. Chem. Soc., 127, 8940(2005)

Water Resistance of HKUST-1

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Water Resistance of MOFs

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Surface Functionalization of Cr-MIL-101

a d

e b c

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Chang et al. Angew Chem. Int. Ed. 47, 4144-4148, 2008 (Cover Figure)

Knoevenagel Condensation over Amine-grafted MIL-101

O + Ph H NC CO2Et H CO2Et

353 K

Ph

CN + H2O

100 80 60 40 20 0 0 5 10 15 20
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15

Conversion of CEA (%)

APS-SBA-15 (reference)

Reaction time (h)

cf. ED: ethylene diamine, DETA: diethylene triamine, APS: 3-aminopropyl- triethoxysilane
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Reaction conditions: 1 mmol of benzaldehyde, 1 mmol of ethylcyanoacetate, and 20 mg of catalyst in 25 ml of cyclohexane at 80oC

Post-functionalization of MOFs

Cohen, Chem. Soc. Rev. 38, 1315 (2009)

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Depostion of MOFs on Surfaces

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Thin Films of HKUST-1 on Functionalized Surfaces

XRD Patterns of HKUST-1

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Layer-by-Layer growth of Interpenetrated MOFs

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Sensor Device of HKUST-1

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Molecular Sieve Membrane of ZIF-7

Bim: benzimidazolate

Microwave-assisted secondary growth of ZIF-7

Soladite topology, ZIF-7(Zni(bim)2) Hydrophobic, thermally stable small pore(0.3nm)

CO2 0.33nm H2 0.29nm

ZIF-7 membrane showed a high H2 selectivity for targeting H2/CO2 separation

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Drug Delivery of MILs

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Future of MOFs

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Chemistry & Industry 2008