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Title: Investigating the effect of metal nuclearity on activity for ethylene hydrogenation by metal-organic-framework-supported oxy-Ni(II) catalysts

Abstract

Metal-organic frameworks (MOFs), thanks to their well-defined coordination sites, are promising for studying catalytically active structures. Here, to understand the effect of metal nuclearity in MOF-supported catalysts, we adjusted the nuclearity of oxy-Ni(II) supported on the zirconia-like nodes of MOF NU-1000 by modulating the Ni loading, where the organic linkers served to prevent node-to-node migration of grafted nickel ions. At the single-node level, we grafted auxiliary structural linkers, naphthalene dicarboxylate, to reduce the number of binding/grafting sites. We found higher catalytic rates at higher Ni loading for ethylene hydrogenation on a per-nickel-ion basis, despite the similar chemical environment of Ni(II) at different loadings; catalysts consisting mainly of pairs of nickel ions were more reactive than those of single nickel ions. These observations illustrate the need for at least two proximal nickel ions for effective catalysis – presumably one for hydrogen binding and heterolytic splitting and one for ethylene binding and activation.

Authors:
 [1];  [2];  [2];  [3];  [1];  [1]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States)
  2. Univ. of Chicago, IL (United States)
  3. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Northwestern University; National Science Foundation (NSF)
OSTI Identifier:
1909339
Grant/Contract Number:  
AC02-06CH11357; SC0012702; NSF ECCS-2025633; NSF DMR-1720139; FG02-03ER15457; SC0001329
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 407; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metal-organic frameworks; MOFs; Nickel catalysts; Ethylene hydrogenation; Catalyst nuclearity; Active sites

Citation Formats

Wang, Qining, Pengmei, Zihan, Pandharkar, Riddhish, Gagliardi, Laura, Hupp, Joseph T., and Notestein, Justin M. Investigating the effect of metal nuclearity on activity for ethylene hydrogenation by metal-organic-framework-supported oxy-Ni(II) catalysts. United States: N. p., 2022. Web. doi:10.1016/j.jcat.2022.01.033.
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Wang, Qining, Pengmei, Zihan, Pandharkar, Riddhish, Gagliardi, Laura, Hupp, Joseph T., & Notestein, Justin M. Investigating the effect of metal nuclearity on activity for ethylene hydrogenation by metal-organic-framework-supported oxy-Ni(II) catalysts. United States. https://doi.org/10.1016/j.jcat.2022.01.033
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Wang, Qining, Pengmei, Zihan, Pandharkar, Riddhish, Gagliardi, Laura, Hupp, Joseph T., and Notestein, Justin M. Fri . "Investigating the effect of metal nuclearity on activity for ethylene hydrogenation by metal-organic-framework-supported oxy-Ni(II) catalysts". United States. https://doi.org/10.1016/j.jcat.2022.01.033. https://www.osti.gov/servlets/purl/1909339.
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@article{osti_1909339,
title = {Investigating the effect of metal nuclearity on activity for ethylene hydrogenation by metal-organic-framework-supported oxy-Ni(II) catalysts},
author = {Wang, Qining and Pengmei, Zihan and Pandharkar, Riddhish and Gagliardi, Laura and Hupp, Joseph T. and Notestein, Justin M.},
abstractNote = {Metal-organic frameworks (MOFs), thanks to their well-defined coordination sites, are promising for studying catalytically active structures. Here, to understand the effect of metal nuclearity in MOF-supported catalysts, we adjusted the nuclearity of oxy-Ni(II) supported on the zirconia-like nodes of MOF NU-1000 by modulating the Ni loading, where the organic linkers served to prevent node-to-node migration of grafted nickel ions. At the single-node level, we grafted auxiliary structural linkers, naphthalene dicarboxylate, to reduce the number of binding/grafting sites. We found higher catalytic rates at higher Ni loading for ethylene hydrogenation on a per-nickel-ion basis, despite the similar chemical environment of Ni(II) at different loadings; catalysts consisting mainly of pairs of nickel ions were more reactive than those of single nickel ions. These observations illustrate the need for at least two proximal nickel ions for effective catalysis – presumably one for hydrogen binding and heterolytic splitting and one for ethylene binding and activation.},
doi = {10.1016/j.jcat.2022.01.033},
journal = {Journal of Catalysis},
number = ,
volume = 407,
place = {United States},
year = {Fri Feb 04 00:00:00 EST 2022},
month = {Fri Feb 04 00:00:00 EST 2022}
}
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https://doi.org/10.1016/j.jcat.2022.01.033
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Works referenced in this record:

Doping Metal–Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction, and Organic Photocatalysis
journal, August 2011

  • Wang, Cheng; Xie, Zhigang; deKrafft, Kathryn E.
  • Journal of the American Chemical Society, Vol. 133, Issue 34, p. 13445-13454
  • DOI: 10.1021/ja203564w

Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework
journal, February 2016

  • Li, Zhanyong; Schweitzer, Neil M.; League, Aaron B.
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b12515

Engineering the Coordination Sphere of Isolated Active Sites to Explore the Intrinsic Activity in Single-Atom Catalysts
journal, January 2021

Highly Active Heterogeneous Catalyst for Ethylene Dimerization Prepared by Selectively Doping Ni on the Surface of a Zeolitic Imidazolate Framework
journal, April 2021

  • Chen, Cailing; Alalouni, Mohammed R.; Dong, Xinglong
  • Journal of the American Chemical Society, Vol. 143, Issue 18
  • DOI: 10.1021/jacs.1c02272

Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature
journal, November 2016

Metal–Organic Framework Thin Films as Platforms for Atomic Layer Deposition of Cobalt Ions To Enable Electrocatalytic Water Oxidation
journal, December 2015

  • Kung, Chung-Wei; Mondloch, Joseph E.; Wang, Timothy C.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 51
  • DOI: 10.1021/acsami.5b06901

Toward Inexpensive Photocatalytic Hydrogen Evolution: A Nickel Sulfide Catalyst Supported on a High-Stability Metal–Organic Framework
journal, August 2016

  • Peters, Aaron W.; Li, Zhanyong; Farha, Omar K.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 32
  • DOI: 10.1021/acsami.6b04729

Titration of Zr3(μ-OH) Hydroxy Groups at the Cornerstones of Bulk MOF UiO-67, [Zr6O4(OH)4(biphenyldicarboxylate)6], and Their Reaction with [AuMe(PMe3)]
journal, May 2012

  • Larabi, Cherif; Quadrelli, Elsje Alessandra
  • European Journal of Inorganic Chemistry, Vol. 2012, Issue 18, p. 3014-3022
  • DOI: 10.1002/ejic.201200033

Cobalt-Based Metal-Organic Frameworks and Their Derivatives for Hydrogen Evolution Reaction
journal, November 2020

Metal–Organic Framework Nodes as Nearly Ideal Supports for Molecular Catalysts: NU-1000- and UiO-66-Supported Iridium Complexes
journal, June 2015

  • Yang, Dong; Odoh, Samuel O.; Wang, Timothy C.
  • Journal of the American Chemical Society, Vol. 137, Issue 23, p. 7391-7396
  • DOI: 10.1021/jacs.5b02956

Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal–Organic Frameworks
journal, January 2021

Microwave‐Assisted Synthesis as an Efficient Method to Enhance the Catalytic Activity of Zr‐Based Metal Organic Framework UiO‐66 in a Heterocyclization Reaction
journal, November 2019

  • Nguyen, Linh Ho Thuy; Nguyen, Trang Thi Thu; Dang, Y. Thi
  • Asian Journal of Organic Chemistry, Vol. 8, Issue 12
  • DOI: 10.1002/ajoc.201900556

Stable Metal–Organic Framework-Supported Niobium Catalysts
journal, October 2016

Unexpected “Spontaneous” Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles
journal, December 2020

  • Yang, Ying; Zhang, Xuan; Kanchanakungwankul, Siriluk
  • Journal of the American Chemical Society, Vol. 142, Issue 50
  • DOI: 10.1021/jacs.0c10367

Atomically Dispersed Pd Supported on Zinc Oxide for Selective Nonoxidative Ethanol Dehydrogenation
journal, January 2020

  • Ouyang, Mengyao; Cao, Sufeng; Yang, Shize
  • Industrial & Engineering Chemistry Research, Vol. 59, Issue 6
  • DOI: 10.1021/acs.iecr.9b05202

Highly Active Gas Phase Organometallic Catalysis Supported Within Metal–Organic Framework Pores
journal, July 2020

  • Peralta, Ricardo A.; Huxley, Michael T.; Evans, Jack D.
  • Journal of the American Chemical Society, Vol. 142, Issue 31
  • DOI: 10.1021/jacs.0c05286

Ethylene Polymerization over Metal–Organic Framework Crystallites and the Influence of Linkers on Their Fracturing Process
journal, March 2019

  • Rivera-Torrente, Miguel; Pletcher, Paul D.; Jongkind, Maarten K.
  • ACS Catalysis, Vol. 9, Issue 4
  • DOI: 10.1021/acscatal.9b00150

Insights into the Structure–Activity Relationships in Metal–Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation
journal, July 2020

Pushing the Limits on Metal–Organic Frameworks as a Catalyst Support: NU-1000 Supported Tungsten Catalysts for o -Xylene Isomerization and Disproportionation
journal, June 2018

  • Ahn, Sol; Nauert, Scott L.; Buru, Cassandra T.
  • Journal of the American Chemical Society, Vol. 140, Issue 27
  • DOI: 10.1021/jacs.8b04059

Solar Light Photocatalytic Degradation of Nitrite in Aqueous Solution Over CdS Embedded on Metal–Organic Frameworks
journal, May 2015

Accurate Coulomb-fitting basis sets for H to Rn
journal, January 2006

  • Weigend, Florian
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 9
  • DOI: 10.1039/b515623h

Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts
journal, September 2015

Catalysis by Metal Organic Frameworks: Perspective and Suggestions for Future Research
journal, January 2019

Mechanistic insights into alkene chain growth reactions catalyzed by nickel active sites on ordered microporous and mesoporous supports
journal, January 2020

  • Joshi, Ravi; Saxena, Arunima; Gounder, Rajamani
  • Catalysis Science & Technology, Vol. 10, Issue 21
  • DOI: 10.1039/D0CY01186J

Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 49
  • DOI: 10.1002/anie.201505625

Stabilized Vanadium Catalyst for Olefin Polymerization by Site Isolation in a Metal–Organic Framework
journal, July 2018

  • Comito, Robert J.; Wu, Zhenwei; Zhang, Guanghui
  • Angewandte Chemie International Edition, Vol. 57, Issue 27
  • DOI: 10.1002/anie.201803642

Selective sulfoxidation of aryl sulfides by coordinatively unsaturated metal centers in chromium carboxylate MIL-101
journal, May 2009

Oligomerization of Light Olefins Catalyzed by Brønsted-Acidic Metal–Organic Framework-808
journal, June 2019

  • Liu, Ping; Redekop, Evgeniy; Gao, Xiang
  • Journal of the American Chemical Society, Vol. 141, Issue 29
  • DOI: 10.1021/jacs.9b03867

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

First-principles investigation of dimethyl-functionalized MIL-53(Al) metal–organic framework for adsorption and separation of xylene isomers
journal, January 2021

  • Yousefzadeh Borzehandani, Mostafa; Abdulmalek, Emilia; Abdul Rahman, Mohd Basyaruddin
  • Journal of Porous Materials, Vol. 28, Issue 2
  • DOI: 10.1007/s10934-020-01016-6

Catalytic dehydrogenation of isobutane over supported MoOx/K-Al2O3
journal, May 2021

Metal–Organic Framework Supported Single Site Chromium(III) Catalyst for Ethylene Oligomerization at Low Pressure and Temperature
journal, December 2018

Surface Thermolytic Behavior of Nickel Amidinate and Its Implication on the Atomic Layer Deposition of Nickel Compounds
journal, June 2019

Vanadium Supported on Alumina and/or Zirconia Catalysts for the Selective Transformation of Ethane and Methanol
journal, March 2018

  • Benomar, Souhila; Massó, Amada; Solsona, Benjamín
  • Catalysts, Vol. 8, Issue 4
  • DOI: 10.3390/catal8040126

Low-Temperature CO Oxidation over Cu-Based Metal-Organic Frameworks Monitored by using FTIR Spectroscopy
journal, May 2012

Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework
journal, January 2018

  • Islamoglu, Timur; Otake, Ken-ichi; Li, Peng
  • CrystEngComm, Vol. 20, Issue 39
  • DOI: 10.1039/C8CE00455B

Structure and Dynamics of Zr 6 O 8 Metal–Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction
journal, February 2018

  • Yang, Dong; Ortuño, Manuel A.; Bernales, Varinia
  • Journal of the American Chemical Society, Vol. 140, Issue 10
  • DOI: 10.1021/jacs.7b13330

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework
journal, March 2018

  • Peters, Aaron W.; Otake, Kenichi; Platero-Prats, Ana E.
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 17
  • DOI: 10.1021/acsami.8b02825

Sustained Water Oxidation by a Catalyst Cage-Isolated in a Metal-Organic Framework
journal, May 2013

  • Nepal, Binod; Das, Siddhartha
  • Angewandte Chemie International Edition, Vol. 52, Issue 28
  • DOI: 10.1002/anie.201301327

A Sn IV –Porphyrin-Based Metal–Organic Framework for the Selective Photo-Oxygenation of Phenol and Sulfides
journal, June 2011

  • Xie, Ming-Hua; Yang, Xiu-Li; Zou, Chao
  • Inorganic Chemistry, Vol. 50, Issue 12
  • DOI: 10.1021/ic200295h

Salicylaldimine-Based Metal–Organic Framework Enabling Highly Active Olefin Hydrogenation with Iron and Cobalt Catalysts
journal, September 2014

  • Manna, Kuntal; Zhang, Teng; Carboni, Michaël
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja507947d

Fe/Ni Metal–Organic Frameworks and Their Binder-Free Thin Films for Efficient Oxygen Evolution with Low Overpotential
journal, June 2016

  • Wang, Lu; Wu, Yizhen; Cao, Rui
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 26
  • DOI: 10.1021/acsami.6b05375

Node-Accessible Zirconium MOFs
journal, December 2020

  • Lu, Zhiyong; Liu, Jian; Zhang, Xuan
  • Journal of the American Chemical Society, Vol. 142, Issue 50
  • DOI: 10.1021/jacs.0c09782

Energy-adjustedab initio pseudopotentials for the second and third row transition elements
journal, January 1990

  • Andrae, D.; H�u�ermann, U.; Dolg, M.
  • Theoretica Chimica Acta, Vol. 77, Issue 2
  • DOI: 10.1007/BF01114537

Synthetic strategies of supported atomic clusters for heterogeneous catalysis
journal, November 2020

Enhancing Four-Carbon Olefin Production from Acetylene over Copper Nanoparticles in Metal–Organic Frameworks
journal, June 2020

  • Redfern, Louis R.; Lo, Wei-Shang; Dillingham, Ian J.
  • ACS Applied Materials & Interfaces, Vol. 12, Issue 28
  • DOI: 10.1021/acsami.0c08244

Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium
journal, November 2019

  • Choi, Hyeju; Peters, Aaron W.; Noh, Hyunho
  • ACS Applied Energy Materials, Vol. 2, Issue 12
  • DOI: 10.1021/acsaem.9b01664

Ammonia Capture within Zirconium Metal–Organic Frameworks: Reversible and Irreversible Uptake
journal, April 2021

  • Liu, Jian; Lu, Zhiyong; Chen, Zhijie
  • ACS Applied Materials & Interfaces, Vol. 13, Issue 17
  • DOI: 10.1021/acsami.1c02370

A stable low-temperature H2-production catalyst by crowding Pt on α-MoC
journal, January 2021

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