Iridium pair sites anchored to Zr6O8 nodes of the metal–organic framework UiO-66 catalyze ethylene hydrogenation

Babucci, Melike; Conley, Edward T.; Hoffman, Adam S.; Bare, Simon R.; Gates, Bruce C.

doi:10.1016/j.jcat.2022.04.003

Iridium pair sites anchored to Zr₆O₈ nodes of the metal–organic framework UiO-66 catalyze ethylene hydrogenation

Journal Article · Sat Apr 16 00:00:00 EDT 2022 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2022.04.003· OSTI ID:1876091

Babucci, Melike ^[1]; Conley, Edward T. ^[1]; Hoffman, Adam S. ^[2]; ^[2]; ^[1]

Univ. of California, Davis, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Isolated metal pair sites on metal oxide and zeolite supports are drawing attention as catalysts, because—in contrast to single atomically dispersed metals—they provide neighboring metal centers that can act cooperatively. We now report pairs of iridium atoms anchored to the Zr₆O₈ nodes of the metal–organic framework (MOF) UiO-66, synthesized by chemisorption of Ir₂(μ-OCH₃)₂(COD)₂(COD is cyclooctadienyl) followed by removal of the COD ligands. The supported species were characterized with infrared spectra of adsorbed CO combined with iridium LIII-edge extended X-ray absorption fine structure and high-energy-resolution fluorescence detection X-ray absorption near edge (HERFD XANES) spectra. The HERFD XANES spectra were recorded with the sample in a variety of atmospheres in which the iridium pair sites were stable, including CO, H₂, and C₂H₄ + H₂ at temperatures in the range of 35–80 °C. The data provide sensitive measures of the electronic structure of the iridium in the pair sites. The samples were evaluated as catalysts for ethylene hydrogenation, with the pair-sites being more selective for hydrogenation than analogous isolated atomically dispersed iridium, which catalyzes both hydrogenation and isomerization. Metal pair sites on MOFs offer uncharted opportunities for catalysts having reactivities associated with neighboring metal centers.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0012702

OSTI ID:: 1876091

Alternate ID(s):: OSTI ID: 1961428

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 411; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Atomically Dispersed Ruthenium Species Inside Metal–Organic Frameworks: Combining the High Activity of Atomic Sites and the Molecular Sieving Effect of MOFs Ji, Shufang; Chen, Yuanjun; Zhao, Shu Angewandte Chemie International Edition, Vol. 58, Issue 13 https://doi.org/10.1002/anie.201814182	journal	March 2019
Bi-Microporous Metal-Organic Frameworks with Cubane [M ₄ (OH) ₄ ] (M=Ni, Co) Clusters and Pore-Space Partition for Electrocatalytic Methanol Oxidation Reaction Wu, Ya-Pan; Tian, Jun-Wu; Liu, Shan Angewandte Chemie International Edition, Vol. 58, Issue 35 https://doi.org/10.1002/anie.201907136	journal	August 2019
Single-Site Zeolite-Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry Martinez-Macias, Claudia; Chen, Mingyang; Dixon, David A. Chemistry - A European Journal, Vol. 21, Issue 33 https://doi.org/10.1002/chem.201501277	journal	July 2015
High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts Hoffman, Adam S.; Sokaras, Dimosthenis; Zhang, Shengjie Chemistry - A European Journal, Vol. 23, Issue 59 https://doi.org/10.1002/chem.201701459	journal	July 2017
Complete assignment of vibrational spectra of 1,5-cyclooctadiene—a theoretical and experimental infrared and Raman study Zhou, Xuefeng; Pulay, Peter; Hargitai, Richard Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 49, Issue 2 https://doi.org/10.1016/0584-8539(93)80180-I	journal	February 1993
Report of the international workshop on standards and criteria in X-ray absorption spectroscopy No authors listed Physica B: Condensed Matter, Vol. 158, Issue 1-3, p. 701-722 https://doi.org/10.1016/0921-4526(89)90447-X	journal	June 1989
Leveraging molecular metal–support interactions for H2 and N2 activation Cammarota, Ryan C.; Clouston, Laura J.; Lu, Connie C. Coordination Chemistry Reviews, Vol. 334 https://doi.org/10.1016/j.ccr.2016.06.014	journal	March 2017
Synthesis and characterization of tetrairidium clusters in the metal organic framework UiO-67: Catalyst for ethylene hydrogenation Yang, Dong; Gaggioli, Carlo Alberto; Conley, Edward Journal of Catalysis, Vol. 382 https://doi.org/10.1016/j.jcat.2019.11.031	journal	February 2020
Atomically Dispersed Metals on Well-Defined Supports including Zeolites and Metal–Organic Frameworks: Structure, Bonding, Reactivity, and Catalysis Babucci, Melike; Guntida, Adisak; Gates, Bruce C. Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.0c00864	journal	October 2020
Metal–Organic Framework-Based Catalysts with Single Metal Sites Wei, Yong-Sheng; Zhang, Mei; Zou, Ruqiang Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.9b00757	journal	May 2020
Characterization of a Metal–Organic Framework Zr ₆ O ₈ Node-Supported Atomically Dispersed Iridium Catalyst for Ethylene Hydrogenation by X-ray Absorption Near-Edge Structure and Infrared Spectroscopies Babucci, Melike; Hoffman, Adam S.; Bare, Simon R. The Journal of Physical Chemistry C, Vol. 125, Issue 31 https://doi.org/10.1021/acs.jpcc.1c03563	journal	July 2021
Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra Hoffman, Adam S.; Fang, Chia-Yu; Gates, Bruce C. The Journal of Physical Chemistry Letters, Vol. 7, Issue 19 https://doi.org/10.1021/acs.jpclett.6b01825	journal	September 2016
Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis Wang, Zhengyan; Babucci, Melike; Zhang, Yafeng ACS Applied Materials & Interfaces, Vol. 12, Issue 47 https://doi.org/10.1021/acsami.0c16559	journal	November 2020
Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework Peters, Aaron W.; Otake, Kenichi; Platero-Prats, Ana E. ACS Applied Materials & Interfaces, Vol. 10, Issue 17 https://doi.org/10.1021/acsami.8b02825	journal	March 2018
Supported Metal Pair-Site Catalysts Guan, Erjia; Ciston, Jim; Bare, Simon R. ACS Catalysis, Vol. 10, Issue 16 https://doi.org/10.1021/acscatal.0c02000	journal	July 2020
Tuning Zr ₆ Metal–Organic Framework (MOF) Nodes as Catalyst Supports: Site Densities and Electron-Donor Properties Influence Molecular Iridium Complexes as Ethylene Conversion Catalysts Yang, Dong; Odoh, Samuel O.; Borycz, Joshua ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b02243	journal	December 2015
Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids Babucci, Melike; Fang, Chia-Yu; Hoffman, Adam S. ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b02429	journal	September 2017
MgO-Supported Iridium Metal Pair-Site Catalysts Are More Active and Resistant to CO Poisoning than Analogous Single-Site Catalysts for Ethylene Hydrogenation and Hydrogen–Deuterium Exchange Guan, Erjia; Debefve, Louise; Vasiliu, Monica ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b03463	journal	September 2019
The Surface Chemistry of Metal Oxide Clusters: From Metal–Organic Frameworks to Minerals Yang, Dong; Babucci, Melike; Casey, William H. ACS Central Science, Vol. 6, Issue 9 https://doi.org/10.1021/acscentsci.0c00803	journal	August 2020
Multimetallic Catalysis Based on Heterometallic Complexes and Clusters Buchwalter, Paulin; Rosé, Jacky; Braunstein, Pierre Chemical Reviews, Vol. 115, Issue 1 https://doi.org/10.1021/cr500208k	journal	November 2014
Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands Lu, Jing; Serna, Pedro; Aydin, Ceren Journal of the American Chemical Society, Vol. 133, Issue 40 https://doi.org/10.1021/ja206486j	journal	October 2011
Hydrogen Activation and Metal Hydride Formation Trigger Cluster Formation from Supported Iridium Complexes Lu, Jing; Aydin, Ceren; Browning, Nigel D. Journal of the American Chemical Society, Vol. 134, Issue 11 https://doi.org/10.1021/ja211380p	journal	March 2012
Tuning Catalytic Sites on Zr ₆ O ₈ Metal–Organic Framework Nodes via Ligand and Defect Chemistry Probed with tert -Butyl Alcohol Dehydration to Isobutylene Yang, Dong; Gaggioli, Carlo Alberto; Ray, Debmalya Journal of the American Chemical Society, Vol. 142, Issue 17 https://doi.org/10.1021/jacs.0c03175	journal	April 2020
Beyond Radical Rebound: Methane Oxidation to Methanol Catalyzed by Iron Species in Metal–Organic Framework Nodes Simons, Matthew C.; Prinslow, Steven D.; Babucci, Melike Journal of the American Chemical Society, Vol. 143, Issue 31 https://doi.org/10.1021/jacs.1c04766	journal	July 2021
Propane Dehydrogenation Catalyzed by Isolated Pt Atoms in ≡SiOZn–OH Nests in Dealuminated Zeolite Beta Qi, Liang; Babucci, Melike; Zhang, Yanfei Journal of the American Chemical Society, Vol. 143, Issue 50 https://doi.org/10.1021/jacs.1c10261	journal	December 2021
Metal–Organic Framework Nodes as Nearly Ideal Supports for Molecular Catalysts: NU-1000- and UiO-66-Supported Iridium Complexes Yang, Dong; Odoh, Samuel O.; Wang, Timothy C. Journal of the American Chemical Society, Vol. 137, Issue 23, p. 7391-7396 https://doi.org/10.1021/jacs.5b02956	journal	June 2015
Highly Active and Stable Single-Atom Cu Catalysts Supported by a Metal–Organic Framework Abdel-Mageed, Ali M.; Rungtaweevoranit, Bunyarat; Parlinska-Wojtan, Magdalena Journal of the American Chemical Society, Vol. 141, Issue 13 https://doi.org/10.1021/jacs.8b11386	journal	March 2019
Modeling Catalytic Steps on Extra-Framework Metal Centers in Zeolites. A Case Study on Ethylene Dimerization Dinda, Shrabani; Govindasamy, Agalya; Genest, Alexander The Journal of Physical Chemistry C, Vol. 118, Issue 43 https://doi.org/10.1021/jp508141q	journal	October 2014
Design and synthesis of an exceptionally stable and highly porous metal-organic framework Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe Nature, Vol. 402, Issue 6759, p. 276-279 https://doi.org/10.1038/46248	journal	November 1999
A versatile MOF-based trap for heavy metal ion capture and dispersion Peng, Yaguang; Huang, Hongliang; Zhang, Yuxi Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-017-02600-2	journal	January 2018
Optimizing reaction paths for methanol synthesis from CO2 hydrogenation via metal-ligand cooperativity Chen, Yizhen; Li, Hongliang; Zhao, Wanghui Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09918-z	journal	April 2019
Controlling catalytic activity and selectivity for partial hydrogenation by tuning the environment around active sites in iridium complexes bonded to supports Babucci, Melike; Fang, Chia-Yu; Perez-Aguilar, Jorge E. Chemical Science, Vol. 10, Issue 9 https://doi.org/10.1039/C8SC05287E	journal	January 2019
Binuclear homoleptic rhodium carbonyls: Structures, energetics, and vibrational spectra Feng, Xuejun; Xie, Chanyuan; Liu, Zhaohui Dalton Transactions, Issue 14 https://doi.org/10.1039/b814580f	journal	January 2009
Cooperative bimetallic catalysis in asymmetric transformations Park, Jongwoo; Hong, Sukwon Chemical Society Reviews, Vol. 41, Issue 21 https://doi.org/10.1039/c2cs35129c	journal	January 2012
Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation Zhao, Yanyan; Yang, Ke R.; Wang, Zechao Proceedings of the National Academy of Sciences, Vol. 115, Issue 12 https://doi.org/10.1073/pnas.1722137115	journal	March 2018
Crystal structures, 2 nd edition. Vol. 1 by R. W. G. Wyckoff Zemann, J. Acta Crystallographica, Vol. 18, Issue 1 https://doi.org/10.1107/S0365110X65000361	journal	January 1965
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
Dynamic multinuclear sites formed by mobilized copper ions in NO _x selective catalytic reduction Paolucci, Christopher; Khurana, Ishant; Parekh, Atish A. Science, Vol. 357, Issue 6354 https://doi.org/10.1126/science.aan5630	journal	August 2017
Avogadro: an advanced semantic chemical editor, visualization, and analysis platform Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C. Journal of Cheminformatics, Vol. 4, Issue 1 https://doi.org/10.1186/1758-2946-4-17	journal	August 2012

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metal-organic frameworks
x-ray absorption spectroscopy

Iridium pair sites anchored to Zr6O8 nodes of the metal–organic framework UiO-66 catalyze ethylene hydrogenation

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Iridium pair sites anchored to Zr₆O₈ nodes of the metal–organic framework UiO-66 catalyze ethylene hydrogenation