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

Matthew C. Simons; Manuel A. Ortuño; Varinia Bernales; Carlo Alberto Gaggioli; Christopher J. Cramer; Aditya Bhan; Laura Gagliardi

doi:10.1021/acscatal.8b00012

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

Matthew C. Simons, Manuel A. Ortuño, Varinia Bernales, Carlo Alberto Gaggioli, Christopher J. Cramer, Aditya Bhan, Laura Gagliardi

Research output: Contribution to journal › Article › peer-review

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Abstract

Cluster-based density functional theory calculations show that energy barriers for the dissociative adsorption of propane on two-cation, Co-M oxide clusters supported on Zr-based nodes of NU-1000, a metal-organic framework material, vary from 57 to 9 kcal mol^-1 based on the identity of the dopant. Systematic changes in spin density and positive partial charge on oxygen atoms bridging the two metal atoms (Co-O-M) are noted upon addition of dopants to cobalt, with increasing values of both giving lower enthalpic barriers to C-H scission. These observed correlations can be rationalized in terms of concepts applicable to bulk systems and provide target materials for synthesis.

Original language	English (US)
Pages (from-to)	2864-2869
Number of pages	6
Journal	ACS Catalysis
Volume	8
Issue number	4
DOIs	https://doi.org/10.1021/acscatal.8b00012
State	Published - Apr 6 2018

Bibliographical note

Funding Information:
This work was supported by the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702). The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources.

Publisher Copyright:
© 2018 American Chemical Society.

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title = "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",

abstract = "Cluster-based density functional theory calculations show that energy barriers for the dissociative adsorption of propane on two-cation, Co-M oxide clusters supported on Zr-based nodes of NU-1000, a metal-organic framework material, vary from 57 to 9 kcal mol-1 based on the identity of the dopant. Systematic changes in spin density and positive partial charge on oxygen atoms bridging the two metal atoms (Co-O-M) are noted upon addition of dopants to cobalt, with increasing values of both giving lower enthalpic barriers to C-H scission. These observed correlations can be rationalized in terms of concepts applicable to bulk systems and provide target materials for synthesis.",

author = "Simons, {Matthew C.} and Ortu{\~n}o, {Manuel A.} and Varinia Bernales and Gaggioli, {Carlo Alberto} and Cramer, {Christopher J.} and Aditya Bhan and Laura Gagliardi",

note = "Funding Information: This work was supported by the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702). The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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T2 - Effects of Doping at the Molecular Level

AU - Simons, Matthew C.

AU - Ortuño, Manuel A.

AU - Bernales, Varinia

AU - Gaggioli, Carlo Alberto

AU - Cramer, Christopher J.

AU - Bhan, Aditya

AU - Gagliardi, Laura

N1 - Funding Information: This work was supported by the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702). The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. Publisher Copyright: © 2018 American Chemical Society.

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Y1 - 2018/4/6

N2 - Cluster-based density functional theory calculations show that energy barriers for the dissociative adsorption of propane on two-cation, Co-M oxide clusters supported on Zr-based nodes of NU-1000, a metal-organic framework material, vary from 57 to 9 kcal mol-1 based on the identity of the dopant. Systematic changes in spin density and positive partial charge on oxygen atoms bridging the two metal atoms (Co-O-M) are noted upon addition of dopants to cobalt, with increasing values of both giving lower enthalpic barriers to C-H scission. These observed correlations can be rationalized in terms of concepts applicable to bulk systems and provide target materials for synthesis.

AB - Cluster-based density functional theory calculations show that energy barriers for the dissociative adsorption of propane on two-cation, Co-M oxide clusters supported on Zr-based nodes of NU-1000, a metal-organic framework material, vary from 57 to 9 kcal mol-1 based on the identity of the dopant. Systematic changes in spin density and positive partial charge on oxygen atoms bridging the two metal atoms (Co-O-M) are noted upon addition of dopants to cobalt, with increasing values of both giving lower enthalpic barriers to C-H scission. These observed correlations can be rationalized in terms of concepts applicable to bulk systems and provide target materials for synthesis.

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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

Abstract

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Energy Frontier Research Center For Inorganometallic Catalyst Design (DE-SC0012702)

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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

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Energy Frontier Research Center For Inorganometallic Catalyst Design (DE-SC0012702)

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