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This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award DE-SC0012702.

Cover design by ICDC for Journal of the American Chemical Society


Methane to Methanol with Cu-Oxo Clusters Supported on a Metal-Organic Framework

The selective oxidation of methane to methanol is the “holy grail” reaction in natural gas upgrade. Very recently, a highly collaborative experimental and theoretical work performed at ICDC (Farha, Hupp, Cramer, Gagliardi, Camaioni, Lercher) reports the synthesis and characterization of Cu-oxo clusters deposited on the nodes of the metal–organic framework NU-1000. This new material was shown to catalyze the conversion of methane to methanol with a carbon selectivity of 45-60%. This study presents a promising first-generation of MOF-based catalysts for selective methane functionalization.
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  1. J. G. Vitillo, A. Bhan, C. J. Cramer, C. C. Lu, and L. Gagliardi, “Quantum Chemical Characterization of Structural Single Fe(II) Sites in MIL-Type Metal Organic Frameworks for Oxidation of Methane to Methanol and Ethane to Ethanol,“ ACS Catal., 2019, Web Publication January 10
    DOI: 10.1021/acscatal.8b04813


  1. J. Ye, C. J. Cramer, and D. G. Truhlar, “Organic Linker Effect on the Growth and Diffusion of Cu Clusters in a Metal–Organic Framework,“ J. Phys. Chem. C, 2018, 122, 26987–26997.
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  2. S. P. Desai, J. Ye, J. Zheng, M. S. Ferrandon, T. E. Webber, A. E. Platero-Prats, J. Duan, P. Garcia-Holley, D. M. Camaioni, K. W. Chapman, M. Delferro, O. K. Farha, J. L. Fulton, L. Gagliardi, J. A. Lercher, R. L. Penn, A. Stein, and C. C. Lu, “Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes,“ J. Am. Chem. Soc., 2018, 140, 15309–15318.
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  3. T. Islamoglu, D. Ray, P. Li, M. B. Majewski, I. Akpinar, X. Zhang, C. J. Cramer, L. Gagliardi, and O. K. Farha, “From Transition Metals to Lanthanides to Actinides: Metal-Mediated Tuning of Electronic Properties of Isostructural Metal–Organic Frameworks,“ Inorg. Chem., 2018, 57, 13246–13251.
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  4. J. Liu, J. Ye, Z. Li, K.-i. Otake , Y. Liao, A. W. Peters, H. Noh, D. G. Truhlar, L. Gagliardi, C. J. Cramer, O. K. Farha, and J. T. Hupp, “Beyond the Active Site: Tuning the Activity and Selectivity of a Metal–Organic Framework-Supported Ni Catalyst for Ethylene Dimerization,“ J. Am. Chem. Soc., 2018, 140, 11174–11178.
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  5. A. Benali, Y. Luo, H. Shin, D. Pahls, and O. Heinonen, “Quantum Monte Carlo Calculations of Catalytic Energy Barriers in a Metallorganic Framework with Transition-Metal-Functionalized Nodes,“ J. Phys. Chem. C, 2018, 122, 16683–16691.
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  6. A.S. Rosen, J.M. Notestein, and R.Q. Snurr, “Comprehensive Phase Diagrams of MoS2 Edge Sites Using Dispersion-Corrected DFT Free Energy Calculations,” J. Phys. Chem. C, 2018, 122, 15318-15329.
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  7. H.A. Doan, Z. Li, O.K. Farha, J.T. Hupp, and R.Q. Snurr, “Theoretical insights into direct methane to methanol conversion over supported dicopper oxo nanoclusters,” Catalysis Today, 2018, 312, 2–9.
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  8. X. Zhang, Z. Huang, M. Ferrandon, D. Yang, L. Robison, P. Li, T.C. Wang, M. Delferro, and O.K. Farha, “Catalytic chemoselective functionalization of methane in a metal−organic framework,” Nature Catalysis, 2018, 1, 356–362.
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  9. J. Ye, R.C. Cammarota, J. Xie, M.V. Vollmer, D.G. Truhlar, C.J. Cramer, C.C. Lu, and L. Gagliardi, “Rationalizing the Reactivity of Bimetallic Molecular Catalysts for CO2 Hydrogenation,” ACS Catal., 2018, 8 (6), 4955–4968.
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  10. X.-P. Wu, L. Gagliardi, and D.G. Truhlar, “Parametrization of Combined Quantum Mechanical and Molecular Mechanical Methods: Bond-Tuned Link Atoms,” Molecules, 2018, 23 (6), article no. 1309.
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  11. M.C. Simons, M.A. Ortuño, V. Bernales, C.A. Gaggioli, C.J. Cramer, A. Bhan, and L. Gagliardi, “C–H Bond Activation on Bimetallic Two-Atom Co-M Oxide Clusters Deposited on Zr-Based MOF Nodes: Effects of Doping at the Molecular Level,” ACS Catalysis, 2018, 8, 2864–2869.
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  12. D. Yang, M.A. Ortuno, V. Bernales, C.J. Cramer, L. Gagliardi, and B.C. Gates, “Structure and Dynamics of Zr6O8 Metal–Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction,” J. Am. Chem. Soc., 2018, 140 (10), 3751–3759.
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  13. S. Pellizzeri, M. Barona, P. Miro, P. Liao, L. Gagliardi, R.Q. Snurr, and R.B. Getman, “Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene,” Catalysis Today, 2018, 312, 149-157.
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  14. J. Ye, L. Gagliardi, C.J. Cramer, and D.G. Truhlar, “Computational screening of MOF-supported transition metal catalysts for activity and selectivity in ethylene dimerization,” Journal of Catalysis, 2018, 360, 160–167.
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  15. B. Yang, L. Gagliardi, and D.G. Truhlar, “Transition states of spin-forbidden reactions,” Physical Chemistry Chemical Physics, 2018, 20, 4129–4136.
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  16. C.D. Malonzo, Z. Wang, J. Duan, W. Zhao, T.E. Webber, Z. Li, I.S. Kim, A. Kumar, A. Bhan, A.E. Platero-Prats, K.W. Chapman, O.K. Farha, J.T. Hupp, A.B.F. Martinson, R.L. Penn, and A. Stein, “Application and Limitations of Nanocasting in Metal–Organic Frameworks,” Inorganic Chemistry, 2018, 57 (5), 2782–2790.
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  17. I.S. Kim, Z. Li, J. Zheng, A.E. Platero-Prats, A. Mavrandonakis, S. Pellizzeri, M. Ferrandon, A. Vjunov, L.C. Gallington, T.E. Webber, N.A. Vermeulen, R.L. Penn, R.B. Getman, C.J. Cramer, K.W. Chapman, D.M. Camaioni, J.L. Fulton, J.A. Lercher, O.K. Farha, J.T. Hupp, and A.B.F. Martinson, “Sinter-Resistant Platinum Catalyst Supported by Metal–Organic Framework,” Angewandte Chemie, 2018, 57 (4), 909–919.
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  18. W. Zhao, Z. Wang, C.D. Malonzo, T.E. Webber, A.E. Platero-Prats, F. Sotomayor, N.A. Vermeulen, T.C. Wang, J.T. Hupp, O.K. Farha, R.L. Penn, K.W. Chapman, M. Thommes, and A. Stein, “Extending the Compositional Range of Nanocasting in the Oxozirconium Cluster-Based Metal–Organic Framework NU-1000—A Comparative Structural Analysis,” Chem. Mater., 2018, 30 (4), 1301–1315.
    DOI: 10.1021/acs.chemmater.7b04893

  19. Y. Cui, M. Rimoldi, A.E. Platero-Prats, K.W. Chapman, J.T. Hupp, and O.K. Farha, “Stabilizing a Vanadium Oxide Catalyst via Supporting on Metal-Organic Framework,” Chem. Cat. Chem., 2018, 10, 1772-1777.
    DOI: 10.1002/cctc.201701658

  20. X.-P. Wu, L. Gagliardi, and D.G. Truhlar, “Combined Quantum Mechanical and Molecular Mechanical Method for Metal-Organic Frameworks: Proton Topologies of NU-1000,” Phys. Chem. Chem. Phys., 2018, 20, 1778-1786.
    DOI: 10.1039/C7CP06751H

  21. V. Bernales, M.A. Ortuno, D.G. Truhlar, C.J. Cramer, and L. Gagliardi, “Computational Design of Functionalized Metal–Organic Framework Nodes for Catalysis,” ACS Central Science, 2018, (4) 1, 5–19.
    DOI: 10.1021/acscentsci.7b00500

  22. W. Zhang, Y. Ma, I.A. Santos-Lopez, J.M. Lownsbury, H. Yu, W.-G. Liu, D.G. Truhlar, C.T. Campbell, and O.E. Vilches, “Energetics of van der Waals Adsorption on the Metal–Organic Framework NU-1000 with Zr6-oxo, Hydroxo, and Aqua Nodes,” J. Am. Chem. Soc., 2018, 140 (1), 328–338.
    DOI: 10.1021/jacs.7b10360


  1. Y. Wang, X. Wang, D.G. Truhlar, and X. He, “How Well Can the M06 Suite of Functionals Describe the Electron Densities of Ne, Ne6+, and Ne8+?” JCTC, 2017, 13 (12), 6068–6077.
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  2. T.E. Webber, W.-G. Liu, S. Puneet Desai, C.C. Lu, D.G. Truhlar, and R.L. Penn, “Role of a Modulator in the Synthesis of Phase-Pure NU-1000,” ACS Appl. Mater. Interfaces, 2017, 9 (45), 39342–39346.
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  3. W.-G. Liu and D.G. Truhlar, “Computational Linker Design for Highly Crystalline Metal–Organic Framework NU-1000,” Chem. Mater., 2017, 29 (19), 8073–8081.
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  4. Y. Wang, X. Jin, H.S. Yu, D.G. Truhlar, X. He,“Revised M06-L functional for improved accuracy on chemical reaction barrier heights, noncovalent interactions, and solid-state physics,” PNAS, 2017, 114 (32), 8487–8492.
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  5. M. Rimoldi, J.T. Hupp, and O.K. Farha, “Atomic Layer Deposition of Rhenium–Aluminum Oxide Thin Films and ReOx Incorporation in a Metal–Organic Framework,” ACS Appl. Mater. Interfaces, 2017, 9 (40), 35067–35074.
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  6. J. Ye, L. Gagliardi, C.J. Cramer, and D.G. Truhlar, “Single Ni atoms and Ni4 clusters have similar catalytic activity for ethylene dimerization,” Journal of Catalysis, 2017, 354, 278–286.
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  7. Z. Li, A.W. Peters, A.E. Platero-Prats, J. Liu, C.-W. Kung, H. Noh, M.R. DeStefano, N.M. Schweitzer, K.W. Chapman, J.T. Hupp, and O.K. Farha, “Fine-Tuning the Activity of Metal–Organic Framework-Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane,” J. Am. Chem. Soc., 2017, 139 (42), 15251–15258.
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  8. R.C. Cammarota, M.V. Vollmer, J. Xie, J. Ye, J.C. Linehan, S.A. Burgess, A.M. Appel, L. Gagliardi, and C.C. Lu, “A Bimetallic Nickel–Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride,” J. Am. Chem. Soc., 2017, 139 (42), 14244–14250.
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  9. R.C. Cammarota, L.J. Clouston, and C.C. Lu, “Leveraging molecular metal–support interactions for H2 and N2 activation,” Coordination Chemistry Reviews, 2017, 334, 100–111.
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  10. J.T. Moore, N.E. Smith, and C.C. Lu, “Structure and dynamic NMR behavior of rhodium complexes supported by Lewis acidic group 13 metallatranes,” Dalton Transactions, 2017, 46 (17), 5689–5701.
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  11. K.D. Vogiatzis, G. Li, E.J.M. Hensen, L. Gagliardi, and E.A. Pidko, “The Electronic Structure of the [Cu3(μ-O)3]2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation,” J. Phys. Chem. C, 2017, 121 (40), 22295–22302.
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  13. M. Yabushita, P. Li, T. Islamoglu, H. Kobayashi, A. Fukuoka, O.K. Farha, and A. Katz, “Selective Metal–Organic Framework Catalysis of Glucose to 5-Hydroxymethylfurfural Using Phosphate-Modified NU-1000,” Ind. Eng. Chem. Res., 2017, 56 (25) 7141–7148.
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  14. P. Liao, R.B. Getman, and R.Q. Snurr, “Optimizing Open Iron Sites in Metal–Organic Frameworks for Ethane Oxidation: A First-Principles Study,” Appl. Mat. Interfaces, 2017, 9 (39), 33484–33492.
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  15. A.E. Platero-Prats, Z. Li, L. C. Gallington, A.W. Peters, J.T. Hupp, O.K. Farha, and K.W. Chapman, “Addressing the characterisation challenge to understand catalysis in MOFs: the case of nanoscale Cu supported in NU-1000,” Faraday Discussions, 2017, 201, 349–362.
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  16. M. Yabushita, P. Li, K.A. Durkin, H. Kobayashi, A. Fukuoka, O.K. Farha, and A. Katz, “Insights into Supramolecular Sites Responsible for Complete Separation of Biomass-Derived Phenolics and Glucose in Metal–Organic Framework NU-1000,” Langmuir, 2017, 33 (17), 4129–4137.
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  17. D.R. Pahls, M.A. Ortuño, P.H. Winegar, C.J. Cramer, and L. Gagliardi, “Computational Screening of Bimetal-Functionalized Zr6O8 MOF Nodes for Methane C–H Bond Activation,” Inorganic Chemistry, 2017, 56 (15), 8739–8743.
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  19. T. Ikuno, J. Zheng, A. Vjunov, M. Sanchez-Sanchez, M.A. Ortuño, D.R. Pahls, J.L. Fulton, D.M. Camaioni, Z. Li, D. Ray, B.L. Mehdi, N.D. Browning, O.K. Farha, J.T. Hupp, C.J. Cramer, L. Gagliardi, and J.A. Lercher, “Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework,” JACS, 2017, 139 (30), 10294–10301.
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  20. S.P. Desai, C.D. Malonzo, T. Webber, J. Duan, A.B. Thompson, S.J. Tereniak, M.R. DeStefano, C.T. Buru, Z. Li, R.L. Penn, O.K. Farha, J.T. Hupp, A. Stein, and C.C. Lu, “Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports,” Faraday Discussions, 2017, 201, 287–302.
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  22. T. Islamoglu, S. Goswami, Z. Li, A. J. Howarth, O. K. Farha, and J. T. Hupp, “Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications,” Accounts of Chemical Research, 2017, 50 (4), 805–813.
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  23. D. Ongari, D. Tiana, S. J. Stoneburner, L. Gagliardi, and B. Smit, “Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks,” Journal of Physical Chemistry C, 2017, 121 (28), 15135–15144.
    DOI: 10.1021/acs.jpcc.7b02302

  24. M. Rimoldi, L.C. Gallington, K.W. Chapman, K. MacRenaris, J.T. Hupp, and O.K. Farha, “Catalytically Active Silicon Oxide Nanoclusters Stabilized in a Metal-Organic Framework,” Chemistry, a European Journal, 2017, 23 (35), 8532–8536.
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  25. J.R. Avila, A.W. Peters, Z. Li, M.A. Ortuno, A.B.F. Martinson, C.J. Cramer, J.T. Hupp, and O.K. Farha, “Atomic layer deposition of Cu(I) oxide films using Cu(II) bis(dimethylamino-2-propoxide) and water,” Dalton Transactions, 2017, 46, 5790–5795.
    DOI: 10.1039/C6DT02572B

  26. Z. Li, A.W. Peters, J. Liu, X. Zhang, N.M. Schweitzer, J.T. Hupp and O.K. Farha, “Size effect of the active sites in UiO-66-supported nickel catalysts synthesized via atomic layer deposition for ethylene hydrogenation,” Inorganic Chemistry Frontiers, 2017, 4, 820–824.
    DOI: 10.1039/C7QI00056A

  27. J.L. Bao, S.O. Odoh, L. Gagliardi, and D.G. Truhlar, “Predicting Bond Dissociation Energies of Transition-Metal Compounds by Multiconfiguration Pair-Density Functional Theory and Second-Order Perturbation Theory Based on Correlated Participating Orbitals and Separated Pairs,” J. Chem. Theory and Comput., 2017, 13, 616–626.
    DOI: 10.1021/acs.jctc.6b01102

  28. K. Duanmu and. D.G. Truhlar, “Validation of Density Functionals for Adsorption Energies on Transition Metal Surfaces,” J. Chem. Theory and Comput., 2017, 3, 835–842.
    DOI: 10.1021/acs.jctc.6b01156

  29. D. Yang, M.R. Momeni, H. Demir, D.R. Pahls, M. Rimoldi, T.C. Wang, O. Farha, J.T. Hupp, C.J. Cramer, B.C. Gates, and L. Gagliardi, “Tuning the properties of metal–organic framework nodes as supports of single-site iridium catalysts: node modification by atomic layer deposition of aluminium ,” Faraday Discussions, 2017, 201, 195–206.
    DOI: 10.1039/C7FD00031F

  30. Z. Li, A.W. Peters, V. Bernales, M.A. Ortuño, N.M. Schweitzer, M.R. DeStefano, L.C. Gallington, A.E. Platero-Prats, K.W. Chapman, C.J. Cramer, L. Gagliardi, J.T. Hupp, and O.K. Farha, “Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature,” ACS Central Science, 2017, 3, 31–38.
    DOI: 10.1021/acscentsci.6b00290

  31. M. Rimoldi, V. Bernales, J. Borycz, A. Vjunov, L.C. Gallington, A.E. Platero-Prats, I.S. Kim, J.L. Fulton, A.B.F. Martinson, J.A. Lercher, K.W. Chapman, C.J. Cramer, L. Gagliardi, J.T. Hupp, and O.K. Farha, “Atomic Layer Deposition in a Metal-Organic Framework: Synthesis, Characterization, and Performance of a Solid Acid,” Chemistry of Materials, 2017, 29, 1058–1068.
    DOI: 10.1021/acs.chemmater.6b03880

  32. R. Rimoldi, A.J. Howarth, M.R. DeStefano, L. Lin, S. Goswami, P. Li, J.T. Hupp, and O.K. Farha, “Catalytic Zirconium/Hafnium-Based Metal–Organic Frameworks,” ACS Catalysis, 2017, 7, 997–1014.
    DOI: 10.1021/acscatal.6b02923


  1. M. Yabushita, P. Li, H. Kobayashi, A. Fukuoka, O.K. Farha, and A, Katz, “Complete furanics–sugar separations with metal–organic framework NU-1000,” Chem. Commun., 2016, 52, 11791–11794.
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  2. A.W. Peters, Z. Li, O.K. Farha, and J.T. Hupp, “Toward Inexpensive Photocatalytic Hydrogen Evolution: A Nickel Sulfide Catalyst Supported on a High-Stability Metal–Organic Framework,” ACS Appl. Mater. Interfaces, 2016, 8, 20675–20681.
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  3. S. Ahn, N.E. Thornburg, Z. Li, T.C. Wang, L.C. Gallington, K.W. Chapman, J.M. Notestein, J.T. Hupp, and O.K. Farha, “Stable Metal–Organic Framework-Supported Niobium Catalysts,” Inorg. Chem., 2016, 55, 11954–11961.
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  4. S.T. Akin, V. Zamudio-Bayer, K. Duanmu∥, G. Leistner, K. Hirsch, C. Bülow, A. Ławicki, A. Terasaki, B. von Issendorff, D.G. Truhlar, J.T. Lau, and M.A. Duncan, “Size-Dependent Ligand Quenching of Ferromagnetism in Co3(benzene)n+ Clusters Studied with X-ray Magnetic Circular Dichroism Spectroscopy,” J. Phys. Chem.Lett., 2016, 7, 4568–4575.
    DOI: 10.1021/acs.jpclett.6b01839

  5. K. Duanmu, J. Friedrich, and D.G. Truhlar, “Thermodynamics of Metal Nanoparticles: Energies and Enthalpies of Formation of Magnesium Clusters and Nanoparticles as Large as 1.3 nm,” J. Phys. Chem. C, 2016, 120, 26110–26118.
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  6. H.S. Yu, S.L. Li, and D.G. Truhlar, “Perspective: Kohn-Sham density functional theory descending a staircase,” J. Chem. Phys., 2016, 145, 130901.
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  7. J.M. Lownsbury, I.A. Santos-López, W. Zhang, C.T. Campbell, H.S. Yu, W.-G. Liu, C.J. Cramer, D.G. Truhlar, T. Wang, J.T. Hupp, and O.K. Farha, “Calcium Vapor Adsorption on the Metal–Organic Framework NU-1000: Structure and Energetics,” J. Phys. Chem. C, 2016, 120, 16850–16862.
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  8. J.L. Bao, X. Zhang, X. Xu, and D.G. Truhlar, “Predicting bond dissociation energy and bond length for bimetallic diatomic molecules: a challenge for electronic structure theory,” Phys. Chem. Chem. Phys., 2016, 19, 5839–5854.
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  9. K. Duanmu, O. Roberto-Neto, F.B.C. Machado, J.A. Hansen, J. Shen, P. Piecuch, and D.G. Truhlar, “Geometries, Binding Energies, Ionization Potentials, and Electron Affinities of Metal Clusters: Mgn0, ± 1, n = 1–7,” J. Phys. Chem. C, 2016, 120, 13275–13286.
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  10. H.S. Yu and D.G. Truhlar, “Oxidation State 10 Exists,” Angewandte Chemie International Ed., 2016, 55, 9004–9006.
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  11. H.S. Yu, X. He, and D.G. Truhlar, “MN15-L: A New Local Exchange-Correlation Functional for Kohn–Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids,” J. Chem. Theory. Comput., 2016, 12, 1280–1293.
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  14. D. Yang, V. Bernales, T. Islamoglu, O.K. Farha, J.T. Hupp, C.J. Cramer, L. Gagliardi, and B.C. Gates, “Tuning the Surface Chemistry of Metal Organic Framework Nodes: Proton Topology of the Metal-Oxide-Like Zr6 Nodes of UiO-66 and NU-1000,” 2016, J. Am. Chem. Soc., 138 (46), 15189–15196.
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  15. S. Pellizzeri, I.A. Jones, H.A. Doan, R.Q. Snurr, and R.B. Getman, “Using Gas-Phase Clusters to Screen Porphyrin-Supported Nanocluster Catalysts for Ethane Oxidation to Ethanol,” Catalysis Letters, 2016, 146, 2566.
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  16. H. Noh, Y. Cui, A.W. Peters, D.R. Pahls, M.A. Ortuño, N.A. Vermeulen, C.J. Cramer, L. Gagliardi, J.T. Hupp, and O.K. Farha, “An Exceptionally Stable Metal–Organic Framework Supported Molybdenum(VI) Oxide Catalyst for Cyclohexene Epoxidation,” J. Am. Chem. Soc., 2016, 138 (44), 14720–14726.
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  17. M.A. Ortuño, V. Bernales, L. Gagliardi, and C.J. Cramer, “Computational Study of First-Row Transition Metals Supported on MOF NU-1000 for Catalytic Acceptorless Alcohol Dehydrogenation,” J. Phys. Chem. C, 2016, 120 (43), 24687–24705.
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  18. A.J. Howarth, A.W. Peters, N.A. Vermeulen, T.C. Wang, J.T. Hupp, and O.K. Farha, “Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks,” 2016, Chem. Mater., 29 (1), 26–39.
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  19. V. Bernales, A.B. League, Z. Li, N.M. Schweitzer, A.W. Peters, R.K. Carlson, J.T. Hupp, C.J. Cramer, O.K. Farha, and L. Gagliardi, “Computationally-Guided Discovery of Catalytic Cobalt-Decorated Metal–Organic Framework for Ethylene Dimerization,” J. Phys. Chem. C, 2016, 120 (41), 23576–23583.
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  20. I.S. Kim, O.K. Farha, J.T. Hupp, L. Gagliardi, K.W. Chapman, C. Cramer, and A.B.F. Martinson, “A Precise and Scalable Post-Modification of Mesoporous Metal-Organic Framework NU-1000 Via Atomic Layer Deposition,” ECS Transactions, 2016, 75 (6), 93–99.
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  21. A.B. Thompson, D.R. Pahls, V. Bernales, L.C. Gallington, C.D. Malonzo, T. Webber, S.J. Tereniak, T.C. Wang, S.P. Desai, Z. Li, I.S. Kim, L. Gagliardi, R.L. Penn, K.W. Chapman, A. Stein, O.K. Farha, J.T. Hupp, A.B.F. Martinson∥, and C C. Lu, “Installing Heterobimetallic Cobalt–Aluminum Single Sites on a Metal Organic Framework Support,” Chem. Mater., 2016, 28 (18) 6753–6762.
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  22. T.-F. Liu, N.A. Vermeulen, A.J. Howarth, P. Li, A.A. Sarjeant, J.T. Hupp, and O.K. Farha, “Adding to the Arsenal of Zirconium-Based Metal–Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation,” Eur. J. Inorg. Chem., 2016, 7, 4349–4352.
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  23. M. Rimoldi, A. Nakamura, N.A. Vermeulen, J.J. Henkelis, A.K. Blackburn, J.T. Hupp, J.F. Stoddart, and O.K. Farha, “A Metal-Organic Framework Immobilised Iridium Pincer Complex,” Chem. Sci., 2016, 7, 4980–4984.
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  24. M. Yabushita, P. Li, V. Bernales, H. Kobayashi, A. Fukuoka, L. Gagliardi, O.K. Farha, and A. Katz, “Unprecedented selectivity in molecular recognition of carbohydrates by a metal-organic framework,” Chem. Commun., 2016, 52, 7094–7097.
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  25. A.E. Platero-Prats, A. Mavrandonakis, L.C. Gallington, Y. Liu, J.T. Hupp, O.K. Farha, C.J. Cramer, and K.W. Chapman, “Structural Transitions of the Metal-Oxide Nodes within Metal− Organic Frameworks: On the Local Structures of NU-1000 and UiO-66,” J. Am. Chem. Soc., 2016, 138 (12), 4178–4185.
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  26. H.S. Yu, X. He, S.L. Li, and D.G. Truhlar, “MN15: A Kohn-Sham Global-Hybrid Exchange-Correlation Density Functional with Broad Accuracy for Multi-Reference and Single-Reference Systems and Noncovalent Interactions,” Chem. Sci., 2016, 7, 5032–5051.
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  27. R.C. Klet, T.C. Wang, L.E. Fernandez, D.G. Truhlar, J.T. Hupp, O.K. Farha, “Synthetic Access to Atomically Dispersed Metals in Metal-Organic Frameworks via a Combined Atomic-Layer-Deposition-in-MOF and Metal Exchange Approach,” Chem. Mater., 2016, 28 (4), 1213–1219.
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  28. A.J. Howarth, Y. Liu, P. Li, Z. Li, T.C. Wang, J.T. Hupp, O.K. Farha, “Chemical, thermal and mechanical stabilities of metal–organic frameworks,” Nat. Rev. Mats., 2016, 1, 15018.
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  29. C.D. Malonzo, S.M. Shaker, L. Ren, S.D. Prinslow, A.E. Platero-Prats, L.C. Gallington, J. Borycz, A.B. Thompson, T.C. Wang, O.K. Farha, J.T. Hupp, C.C. Lu, K.W. Chapman, J.C. Myers, R.L. Penn, L. Gagliardi, M. Tsapatsis, and A. Stein, “Thermal Stabilization of Metal–Organic Framework-Derived Single-Site Catalytic Clusters Through Nanocasting,” J. Am. Chem. Soc., 2016, 138 (8), 2739–2748.
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  30. Z. Li, N.M. Schweitzer, A.B. League, V. Bernales, A.W. Peters, A.B. Getsoian, T.C. Wang, J.T. Miller, A. Vjunov, J.L. Fulton, J.A. Lercher, C.J. Cramer, L. Gagliardi, J.T. Hupp, and O.K. Farha, “Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal-Organic Framework,” J. Am. Chem. Soc., 2016, 138 (6), 1977–1982.
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  31. D. Yang, S.O. Odoh, J. Borycz, T.C. Wang, O.K. Farha, J.T. Hupp, C.J. Cramer, L. Gagliardi, and B.C. Gates, “Tuning Zr6 MOF Nodes as Catalyst Supports: Site Densities and Electron-Donor Properties Influence Molecular Iridium Complexes as Ethylene Conversion Catalysts,” ACS Catalysis, 2016, 6, 235–247.
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  32. T.C. Wang, N.A. Vermeulen, I.S. Kim, A.B.F. Martinson, J.F. Stoddart, J.T. Hupp, and O.K. Farha, “Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000,” Nature Protocols, 2016, 11, 149–162.
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  1. H. Yu and D.G Truhlar, “Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms,” J. Chem. Theory. Comput., 2015, 11, 2968–2983.
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  2. S.T. Madrahimov, J.R. Gallagher, G. Zhang, Z. Meinhart, S.J. Garibay, M. Delferro, J.T. Miller, O.K. Farha, J.T. Hupp, and S.T. Nguyen, “Gas-Phase Dimerization of Ethylene under Mild Conditions Catalyzed by MOF Materials Containing (bpy)NiII Complexes,” ACS Catalysis, 2015, 5, 6713–6718.
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  3. S.T. Dix, J.K. Scott, R.B. Getman, and C.T. Campbell, “Using degrees of rate control to improve selective n-butane oxidation over model MOF-encapsulated catalysts: sterically-constrained Ag3Pd(111),” Faraday Discussions, 2015.
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  4. R. Klet, S. Tussupbayev, J. Borycz, J.R. Gallagher, M.M. Stalzer, J.T. Miller, L. Gagliardi, J.T. Hupp, T.J. Marks, C.J. Cramer, M. Delferro, and O.K. Farha, “Single-Site Organozirconium Catalyst Embeded in a Metal-Organic Framework,” J. Am. Chem. Soc., 2015, 137, 15680–15683.
    DOI: 10.1021/jacs.5b11350

  5. L.J. Clouston, V. Bernales, R.C. Cammarota, R.K. Carlson, E. Bill, L. Gagliardi, and C.C. Lu, “Heterobimetallic Complexes that Bond Vanadium to Iron, Cobalt, and Nickel,” Inorg. Chem., 2015, 54 (24), 11559–11679.
    DOI: 10.1021/acs.inorgchem.5b01631

  6. R.J. Eisenhart, R.K. Carlson, L.J. Clouston, V.G. Young Jr., Y. Chen, E. Bill, L. Gagliardi, and C.C. Lu. “Influence of Copper Oxidation State on the Bonding Electronic Structure of Cobalt-Copper Complexes,” Inorg. Chem., 2015, 54 (23), 11330–11338.
    DOI: 10.1021/acs.inorgchem.5b01950

  7. A.W. Peters, Z. Li, O.K. Farha, and J.T. Hupp, “Atomically Precise Growth of Catalytically Active Cobalt Sulfide on Flat Surfaces and within a Metal-Organic Framework via Atomic Layer Deposition,” ACS Nano., 2015, 9, 8484–8490.
    DOI: 10.1021/acsnano.5b03429

  8. R.C. Cammarota and C.C. Lu, “Tuning Nickel with Lewis Acidic Group 13 Metalloligands for Catalytic Olefin Hydrogenation,” J. Am. Chem. Soc., 2015, 137 (39), 12486–12489.
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  9. R.K. Carlson, S.O. Odoh, S.J. Tereniak, C.C. Lu, and L. Gagliardi, “Can Multiconfigurational Self-Consistent Field Theory and Density Functional Theory Correctly Predict the Ground State of Metal–Metal-Bonded Complexes?” J. Chem. Theory Comput., 2015, 11 (9), 4093–4101.
    DOI: 10.1021/acs.jctc.5b00412

  10. R.J. Eisenhart, P.A. Rudd, N.Planas, D.W. Boyce, R.K. Carlson, W.B. Tolman, E. Bill, L. Gagliardi, and C.C. Lu, “Pushing the Limits of Delta Bonding in Metal–Chromium Complexes with Redox Changes and Metal Swapping,” Inorg. Chem., 2015, 54 (15), 7579–7592.
    DOI: 10.1021/acs.inorgchem.5b01163

  11. L.J. Clouston, V. Bernales, R.K. Carlson, L. Gagliardi, and C.C. Lu, “Bimetallic Cobalt–Dinitrogen Complexes: Impact of the Supporting Metal on N2 Activation,” Inorg. Chem., 2015, 54 (19), 9263–9270.
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  12. D. Yang, S.O. Odoh, T.C. Wang, O.K. Farha, J.T. Hupp, C.J. Cramer, L. Gagliardi, and B.C. Gates, “Metal-organic framework nodes as nearly ideal supports for molecular catalysts: NU-1000- and UiO-66-supported iridium complexes,” J. Am. Chem. Soc., 2015, 137 (23), 7391–7396.
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  13. K. Duanmu and D.G. Truhlar, “Validation of Methods for Computational Catalyst Design: Geometries, Structures, and Energies of Neutral and Charged Silver Clusters,” J. Phys. Chem. C, 2015, 119 (17), 9617–9626.
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  14. H.S. Yu, W. Zhang, P. Verma, X. He, and D.G. Truhlar, “Nonseparable Exchange-Correlation Functional for Molecules, Including Homogeneous Catalysis Involving Transition Metals,” Phys. Chem. Chem. Phys., 2015, 17, 12146–12160.
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  15. R.K. Carlson, D.G. Truhlar, and L. Gagliardi, “Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re2Cl82–,” J. Chem. Theory Comput., 2015, 11 (9), 4077–4085.
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  16. R.B. Siedschlag, V. Bernales, K.D. Vogiatzis, N. Planas, L.J. Clouston, E. Bill, L. Gagliardi, and C.C. Lu, “Catalytic Silylation of Dinitrogen with a Dicobalt Complex,” J. Am. Chem. Soc., 2015,137 (14), 4638-4641.
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  18. R.K. Carlson, G. Li Manni, A.L. Sonnenberger, D.G. Truhlar, and L. Gagliardi, “Multiconfiguration Pair-Density Functional Theory: Barrier Heights and Main Group and Transition Metal Energetics,” J. Chem. Theory Comput., 2015, 11 (1), 82–90.
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  19. J.S. Bao, H.S. Yu, K. Duanmu, M. Makeev, X. Xu, and D.G. Truhlar, “Density Functional Theory of the Water Splitting Reaction on Fe(0): Comparison of Local and Nonlocal Correlation Functionals,” ACS Catalysis, 2015, 5, 2070–2080.
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  20. R.J. Eisenhart, R.K. Carlson, K.M. Boyl, L. Gagliardi, and C.C. Lu, “Synthesis and redox reactivity of a phosphine-ligated dichromium paddlewheel,” Inorg. Chem. Acta., 2015, 424, 336–344.
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  21. T.C. Wang, W. Bury, D.A. Gómez-Gualdrón, N.A. Vermeulen, J.E. Mondloch, P. Deria, K. Zhang, P.Z. Moghadam, A.A. Sarjeant, R.Q. Snurr, J.F. Stoddart, J.T. Hupp, and O.K. Farha, “Ultrahigh Surface Area Zirconium MOFs and Insights into the Applicability of the BET Theory,” J. Am. Chem. Soc., 2015, 137 (10), 3585–3591.
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  22. I.S. Kim, J. Borycz, A. Platero-Plats, S. Tussupbayev, T. Wang, O. Farha, J. Hupp, L. Gagliardi, K. Chapman, C. Cramer, and A. Martinson, “Targeted Single-site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition,” Chem. Mater,. 2015, 27 (13), 4772–4778.
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  1. B. Wang, S.L. Li, and D.G. Truhlar, “Modeling the Partial Atomic Charges in Inogranometallic Molecules and Solids and Charge Redistribution in Lithium-Ion Cathodes,” J. Chem. Theory and Comp., 2014, 10, 5640–5650.
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  2. K. Duanmu and D.G. Truhlar, “Partial Ionic Character Beyond the Pauling Paradigm: Metal Nanoparticles,” J. Phys. Chem. C, 2014, 18, 28069–28074.
    (featured in C & E News).
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This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award DE-SC0012702.

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