computationally driven characterization of magnetism, adsorption, and reactivity in metal-organic...

Computationally Driven Characterization of Magnetism, Adsorption, and Reactivity in Metal-Organic Frameworks Joshua Borycz Gagliardi Group June 10th, 2014

Computationally Driven Characterization of Magnetism, Adsorption, and Reactivity in Metal-Organic Frameworks

Joshua Borycz Gagliardi GroupJune 10th 2016

1

2Multiple levels of computationSmall clusters

Large clusters

Periodic systems

Density function theory (DFT)Wave function theory (WFT)

PBE+U HSEGAMvdW-DF2

Introduction: Computational chemistry

3Classical simulationsUses analytical potential to compute chemical interactionsGenerally include charge and van der Waals interaction

More interaction terms can be included explicitlyHigher order electrostaticsPolarizabilityAllows computation of interactions of thousands of atomsCO2 adsorption

Introduction: Computational chemistry

4Molecular chemistryIntroduction: Metal-Organic Frameworks

diethanolamine (DEA)Metal clusters

Little room for interaction

Complex upon reaction

Solution phase (H2O)

High energy input

Saturated metalsMaterials

Zeolite

Thermally stable

MOFs

Can reach up to 8,000 m2/g surface area

Millions of metal node/organic linker combinations

Large pores and unique reactivity

Hundreds of structures

Difficult to synthesize

~1,000 m2/g surface area

Metal nodeOrganic linker Weiland, R. H. et al. J. Chem. Eng. Data 1997, 42, 1004. www.ccdc.cam.ac.uk/structures www.zeolyst.com Mason,J. A. et al. Energy Environ. Sci. 2011, 4, 3030.

5Metal Organic Frameworks (MOFs)Metal nodes connected by organic linkers

MOFs can have unique environments that sometimes give them very interesting properties1-3Maurice, R.; Verma, P. et al. Inorg. Chem. 2013, 52, 9379. Wriedt, M. et al., J. Am. Chem. Soc. 2013, 135, 4040.Zhang, W. et al. Chem. Rev., 2012, 112, 1163.

Fe

O

C

H

Fe2(dobdc) - dobdc4-=2,5-dioxodobenzene-1,4-dicarboxlatedobdcIntroduction: Metal-Organic Frameworks

6

MagnetismCO2 AdsorptionCatalysis

Ion Exchange

7Molecular Sensors

1.) Wanderley, M.M.; et al. J. Am. Chem. Soc., 2012, 134, 9050. 2.) Leenaerts, O. et al. Phys. Rev. B, 2008, 77, 125416.3.) Liu, D. et al. Inorg. Chem., 2014, 53, 1916.4.) L, Y. et al. ACS Appl. Mater. Interfaces 2014, 6, 4186.5.) Liu, Y.M. et al. ACS Appl. Mater. Interfaces, 2013, 5, 12624.

CHO

Detected Using

Kinetic Radius1,3 Magnetic Moment2

Fluorescence1,3 Resistence4,5

31Why study magnetism?

Cd - 1,1-bi-2-naphthol (BINOL)

Dehydration processes have long been used to change the coordination environment and the dimensionality of a hydrated coordination polymer, thus provoking significant changes in the magnetic properties.64,65 However, this process is often irreversible or produces a collapse in the structure when the solvent is removed.66,67 Reversibility of such structural changes has been successfully achieved only with the use of MOFs.

7

8

Fe(II) spin configurationFe2(dobdc) down 1D channelsMagnetic properties

Fe

O

C

HIntra-ion interactions: Ligand Field SplittingBloch, E.D. et al., Science., 2012, 335, 1606. Maurice, R.; Verma, P. et al., Inorg. Chem., 2013, 52, 9379.

Remi MauricePragyaVerma

Fe(II) likes to be hexacoordinate8

Inter-ion interactions9Ferromagnetic (FM) - dipoles point in same direction

Antiferromagnetic (AFM) - dipoles point in opposite directions

Alignment of atomic dipoles between open-shell metals

isotropic couplingMagnetic properties

Fe(II) likes to be hexacoordinate9

Oxidized Fe2(dobdc)10Fe2(dobdc)

Our recent study1 suggests two Fe2(dobdc) derivatives

Fe2(O)2(dobdc)

Fe2(OH)2(dobdc)Xiao, D.J.; Bloch, E.D.; Mason, J.A.; Queen, W.L.; Hudson, M.R.; Planas, N.; Borycz, J.; et al., Nat. Chem., 2014, 1755. How do these ligands affect the magnetism of Fe2(dobdc)? Fe(II) 2S=4Fe(IV) 2S=4Fe(III) 2S=5

H2O

FeOHFeOFeO

Fe(IV)=O, high spin species are very rare and highly reactive10

11Periodic CalculationsPeriodic boundary conditions

Unit cell is replicated to represent infinite crystal

Cell was chosen to accurately model intrachain and interchain magnetic couplings

abc

Fe

O

C

H

c

12Oxidized Fe2(dobdc) magnetic couplingsFe2(dobdc)Fe2(O)2(dobdc)Fe2(OH)2(dobdc)

Red = Spin up Blue = Spin down cm-1JNNJICPBE+U0.5-1.9HSE2.7-1.0GAM+U2.3-1.7Exp.4.1-1.1

cm-1JNNJICPBE+U-2.40.3HSE-0.60.1GAM+U0.3-1.3

cm-1JNNJICPBE+U-9.9-1.4HSE-4.9-0.8GAM+U-6.9-5.5

Fe

O

C

HBloch, E. D. et al. Science, 2012, 335, 1606.Borycz, J.; Paier, J.; Verma, P. et al. Inorg. Chem. 2016, 55, 4924.

12

Fe

3dO2p

Fe3d

13SuperexchangeAntiferromagnetic coupling will increase with Fe-O-Fe angle and Fe-Fe distanceGoodenough, J. B., Phys. Rev. 1960, 117, 14421451.Park, J. et al. Chem. Phys. Lett. 2013, 4, 2530.Borycz, J.; Paier, J.; Verma, P. et al. Inorg. Chem. 2016, 55, 4924.

FeOFe

yxz

Oxidized Fe2(dobdc) magnetic couplingsPresence of O2- and (OH)- ligands also account for approximately 50% of coupling change

14Magnetism conclusionsFe2(dobdc) contains high-spin Fe(II) ions with weak ligand field splittingFe2(dobdc) has weak magnetic coupling between metal centersOxidizing Fe2(dobdc) shifts magnetic coupling from ferromagnetic to antiferromagneticChange in magnetic coupling occurs both due to geometry changes and presence of O2- and (OH)- ligands

15


Ion Exchange

16

Carbon Capture and Sequestration

Metz, B. et al., Carbon Dioxide Capture and Storage. IPCC report, 2005. Mason, J. A. et al. Energy Environ. Sci. 2011, 4, 3030. Why study CO2 adsorption?

Previous work on CO2 adsorption17

Mg2(dobdc)Compute potential energy curves (PECs)Clusters designed for each atom typeMg2+ open-metal sites interact strongly with CO2General force fields could not accurately model strong interactionAb initio methods were used to parameterize force field

Simulate CO2 Isotherms

Dzubak, A. L. et al. Nature., 2012, 119, 16058.

Allison Dzubak

CO2 adsorption methods18

M2(dobdc)Compute structurePeriodic DFT

Compute potential energy curves (PECs)

Cluster DFT

Parameterize force fieldCompute charges (qi)Optimize Aij, Bij, and Cij with PECsBuckingham PotentialPoint Charges

Simulate CO2 isotherms

Metal-CO2

M2(dobdc) series for carbon captureCO2 adsorption introductionM2(dobdc)Can theory predict accurate CO2 isotherms for MOF-74 with multiple metals?19

Open-metal siteFe

Borycz, J.; Lin, L-C. et al. J. Phys. Chem. C., 2014, 118, 12230.Haldoupis, E.; Borycz, J. et al. J. Phys. Chem. C., 2015, 119, 16058.

CO2 adsorption introductionM2(dobdc)Can theory predict accurate CO2 isotherms for MOF-74 with multiple metals?20

Open-metal siteMn

CoNiCuBorycz, J.; Lin, L-C. et al. J. Phys. Chem. C., 2014, 118, 12230.Haldoupis, E.; Borycz, J. et al. J. Phys. Chem. C., 2015, 119, 16058.

M2(dobdc) series for carbon capture

21

MOF-74: CO2 adsorption results

Classical simulationRestricted open-shell perturbation theoryROMP2

Li-Chiang LinFe2(dobdc)

22MOF-74: CO2 adsorption results

Classical simulationRestricted open-shell perturbation theoryROMP2

Fe2(dobdc)

23

MOF-74: CO2 adsorption results

Classical simulation

Restricted open-shell perturbation theoryROMP2

Mg2(dobdc)Fe2(dobdc)

24

MOF-74: CO2 adsorption resultsM-MOF-74 (M=Mn, Co, Ni, Cu)

DFTWFT

MeOHH2OSolvent effects+

Emmanuel HaldoupisROMP2/ANO-RCC-TZVP PBE-D3/def2-TZVP PBE0-D3/def2-TZVP

25

MOF-74: CO2 adsorption resultsM-MOF-74 (M=Mn, Co, Ni, Cu)PBE0-D3/def2-TZVP

Electron density redistributionMnCoNiCu

Ni

Cu

Electronenters anti-bonding orbital

26CO2 adsorption conclusionsTheory can be used to accurately compute CO2 isotherms for multiple members of the M2(dobdc) seriesCO2 interacts primarily with the open metal sites in M2(dobdc)Ni2+ has strongest CO2 adsorption of those studiedCu2+ is the weakest due to occupancy of anti-bonding orbitalsLeftover solvent may have important effect in measurement/computation of CO2 isothermsIsotherms can be computed by parameterizing only the metal-CO2 interaction

27


Ion Exchange

28http://www.ceresana.com/en/market-studies/plastics/polyethylene-lldpe/Mondloch, J. E. et al. J. Am. Chem. Soc., 2013, 135, 10294. Why study catalysis?Reduces energy input

Ethylene dimerizationC2H4 + C2H4 C4H8Forms 1-buteneWhy MOFs?NU-1000Large pores (30 )High thermal and pH stabilityReactive O-H sites on oxozirconia nodes1-butene is precursor for polyethyleneCommonly used to make plastics



28

29Morris, W. et al. Inorg. Chem. 2012, 51, 6443. Feng, D. et al. Angew. Chem. 2012, 51, 10307. Determine structureNU-1000

TBAPy4 1,3,6,8-tetrakis(p-benzoate)pyrene[Zr6(3-O)8(O)8]8Where do the 16 protons go?HHHHHHHHHHHHHHHHHHHHHHHH

X-ray structures disagree1,2Structure can strongly effect reactivityCompute proton topologies with DFTCompare infrared spectra of computed structures to experiment



29

30Planas, N.; Mondlich, J. E.; Tussupbayev, S.; Borycz, J. et al. Phys. Chem. Lett. 2014, 5, 3716. Structure resultsProton topologiesRelative energies (kJ/mol)ModelEperiodicEclusterGcluster-OH350334299-OH2274274236MIX-Node-S000MIX-L249255235MIX-C139154150MIX-E(30)122146150MIX-E(8)140153147

Theory shows clear indication the MIX-Node-S is most likely configurationCompute IR spectra with MIX-Node-S model and compare to experiment

JosephMondlochNora Planas



30

31Structure resultsMIX-Node-STheory shows clear indication the MIX-Node-S is most likely configurationCompute IR spectra with MIX-Node-S model and compare to experiment

Planas, N.; Mondlich, J. E.; Tussupbayev, S.; Borycz, J. et al. Phys. Chem. Lett. 2014, 5, 3716. Relative energies (kJ/mol)ModelGclusterMIX-Node-S0MIX-S-1-I10.6MIX-S-1-II13.8MIX-S-2a10.2

M06-L/6-311+G(df,p)(C,H,O) SDD (Zr)



31

32Kim, I. S.; Borycz, J. et al. Chem. Mater., 2015, 27, 4772.Mondloch, J. E. et al. J. Am. Chem. Soc., 2013, 135, 10294.Metalation of NU-1000Atomic layer deposition (ALD)

Can we add single-site reactive metals to surface of NU-1000 via ALD?ALD is performed in gas phase at fairly high temperatures (~130 C)

trimethyl indium/aluminum

In Soo Kim



32

33Metalation of NU-1000Cluster model

M06-L/6-311+G(df,p)(C,H,O) SDD (Zr)

Transition stateCompute reaction path to determine viability of Al and In additionCompare to experimental ALD structures



33

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0

S5-172.1S1-33.7S1-29.3S2-65.1TS2-40.6S3-96.8TS3-82.0S4-121.8TS4-94.2TS1-23.0-140-160-180-200S5-132.0

H (298 K)InMe3 & AlMe334

S1

35

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0


HInMe3 & AlMe336

TS1

InMe3 & AlMe337

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0


HInMe3 & AlMe338

S2

39

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0


HInMe3 & AlMe340

TS2

41InMe3 & AlMe3

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0


HInMe3 & AlMe342

S343

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0


HInMe3 & AlMe344

TS3

45InMe3 & AlMe3

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0


HInMe3 & AlMe346

S447

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0


HInMe3 & AlMe348

TS4

49InMe3 & AlMe3

H (kcal/mol)0.0-120-100-80-60-40-200

TS1-17.9

S2-74.7

TS2-56.8

S3-119.0

TS3-107.5

S4-155.0

TS4-122.0


HInMe3 & AlMe350

highest barrier27.7 33.0

S5

51

52Kim, I. S.; Borycz, J. et al. Chem. Mater., 2015, 27, 4772.Metalation of NU-1000Computational structure8 Al/In per Zr6-node

6-7 In per Zr6-nodeExperimental results

Secondary nodes prevent complete saturation via ALDTheory predicted plausible structure based on this experimental comparison



52

53Yang, D.; Odoh, S. O.; Borycz, J. et al. ACS Catal., 2016, 6, 235.Metalation of NU-1000Iridium catalysis

+=

Ethylene dimerizationInspired by work on zeolitesSingle-site catalysts promote ethylene dimerization

HY zeolite cluster

gem-dicarbonyl IR peaks allow comparison of catalytic effectivness

M06-L/def2-SVP(C,H,O) def2-TZVPP SDD (Zr,Ir)IrAl-NU-1000

Samuel OdohDong Yang



53

54

Al + Ir ALD in NU-1000



54

55Catalysis conclusions 2 In/Al atoms can attach to each of the Zr6-nodesTheory can be used to accurately predict the proton topology of Zr6 MOFsThere is a viable reaction pathway that allows InMe3 to form reactive sites on surface of NU-1000Comparison with experimental IR spectra can help to determine proton locationsIr atoms can also be added to surface of NU-1000Attached Ir catalyze ethylene dimerizationAttaching Ir to Al surfaces improves catalytic function



55

Acknowledgments

Alex MartinsonIn Soo KimAna Platero-PratsKarena ChapmanArgonneOmar FarhaJoseph HuppJoseph MondlochRachel KletMartino RimoldiNorthwestern

Johannes LercherAleksei VjunovPNNLDavide TianaUniversity of BathJoachim PaierHumboldt UniversityEmmanuel HaldoupisJeffrey SungMinnesotaSiepmann groupPragya VermaBo WangSjie LuoLaura FernandezTruhlar group

Samat TussupbayevAaron LeagueWill IsleyCramer groupCamille MalonzoStein groupGagliardi groupDavid SemrouniRemi MauriceKostas VogiatzisVarinia Bernales56UC BerkeleyJeffrey LongBerend SmitLi-Chiang LinKyuho Lee



56

Small ModelLarge ModelPeriodic Model

CC

CASSCF/CASPT2GASSCF/GASPT2PBE+U

MCPDFTM06PBE0

M06-LM06-LM11

vdW-DF2vdW-DF2vdW-DF2