DFT investigation of hydroperoxide decomposition over copper and cobalt sites within metal-organic frameworks

Patrick Ryan; Ivan Konstantinov; Randall Q. Snurr; Linda J. Broadbelt

doi:10.1016/j.jcat.2011.10.019

DFT investigation of hydroperoxide decomposition over copper and cobalt sites within metal-organic frameworks

Patrick Ryan, Ivan Konstantinov, Randall Q. Snurr^*, Linda J. Broadbelt

^*Corresponding author for this work

Chemical and Biological Engineering

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

27 Scopus citations

Abstract

Experimental results in the literature show that two metal-organic frameworks (MOFs) containing copper and cobalt nodes are active for hydroperoxide decomposition, which is an important reaction in auto-oxidation processes. Density functional theory (DFT) calculations reported here for these systems suggest that the metal sites in the interior of these MOFs are not the active sites for this type of reaction due to the steric effects of the adjacent linkers. This implies that the experimental catalysis observed may occur on the exterior surface of the MOF crystals. Additional calculations with a copper paddlewheel node show that, despite being able to form complexes with hydroperoxides, the metal sites in copper paddlewheels do not catalyze hydroperoxide decomposition. Preliminary calculations involving undercoordinated metal atoms as a model for metal sites on the MOF exterior crystal surface suggest that these sites could be catalytically active.

Original language	English (US)
Pages (from-to)	95-102
Number of pages	8
Journal	Journal of Catalysis
Volume	286
DOIs	https://doi.org/10.1016/j.jcat.2011.10.019
State	Published - Feb 2012

Funding

This research was supported by a 3 M Fellowship and by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy Grant No. DE-FG02-03ER15457 . This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231. The authors thank Professor Jeremy Harvey for use of his minimum energy crossing point (MECP) code.

Keywords

Catalysis
DFT
Haber-Weiss cycle
Metal-organic framework
Peroxide decomposition

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry

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10.1016/j.jcat.2011.10.019

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title = "DFT investigation of hydroperoxide decomposition over copper and cobalt sites within metal-organic frameworks",

abstract = "Experimental results in the literature show that two metal-organic frameworks (MOFs) containing copper and cobalt nodes are active for hydroperoxide decomposition, which is an important reaction in auto-oxidation processes. Density functional theory (DFT) calculations reported here for these systems suggest that the metal sites in the interior of these MOFs are not the active sites for this type of reaction due to the steric effects of the adjacent linkers. This implies that the experimental catalysis observed may occur on the exterior surface of the MOF crystals. Additional calculations with a copper paddlewheel node show that, despite being able to form complexes with hydroperoxides, the metal sites in copper paddlewheels do not catalyze hydroperoxide decomposition. Preliminary calculations involving undercoordinated metal atoms as a model for metal sites on the MOF exterior crystal surface suggest that these sites could be catalytically active.",

keywords = "Catalysis, DFT, Haber-Weiss cycle, Metal-organic framework, Peroxide decomposition",

author = "Patrick Ryan and Ivan Konstantinov and Snurr, {Randall Q.} and Broadbelt, {Linda J.}",

note = "Funding Information: This research was supported by a 3 M Fellowship and by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy Grant No. DE-FG02-03ER15457 . This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231. The authors thank Professor Jeremy Harvey for use of his minimum energy crossing point (MECP) code. ",

year = "2012",

month = feb,

doi = "10.1016/j.jcat.2011.10.019",

language = "English (US)",

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pages = "95--102",

journal = "Journal of Catalysis",

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AU - Ryan, Patrick

AU - Konstantinov, Ivan

AU - Snurr, Randall Q.

AU - Broadbelt, Linda J.

N1 - Funding Information: This research was supported by a 3 M Fellowship and by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy Grant No. DE-FG02-03ER15457 . This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231. The authors thank Professor Jeremy Harvey for use of his minimum energy crossing point (MECP) code.

PY - 2012/2

Y1 - 2012/2

N2 - Experimental results in the literature show that two metal-organic frameworks (MOFs) containing copper and cobalt nodes are active for hydroperoxide decomposition, which is an important reaction in auto-oxidation processes. Density functional theory (DFT) calculations reported here for these systems suggest that the metal sites in the interior of these MOFs are not the active sites for this type of reaction due to the steric effects of the adjacent linkers. This implies that the experimental catalysis observed may occur on the exterior surface of the MOF crystals. Additional calculations with a copper paddlewheel node show that, despite being able to form complexes with hydroperoxides, the metal sites in copper paddlewheels do not catalyze hydroperoxide decomposition. Preliminary calculations involving undercoordinated metal atoms as a model for metal sites on the MOF exterior crystal surface suggest that these sites could be catalytically active.

AB - Experimental results in the literature show that two metal-organic frameworks (MOFs) containing copper and cobalt nodes are active for hydroperoxide decomposition, which is an important reaction in auto-oxidation processes. Density functional theory (DFT) calculations reported here for these systems suggest that the metal sites in the interior of these MOFs are not the active sites for this type of reaction due to the steric effects of the adjacent linkers. This implies that the experimental catalysis observed may occur on the exterior surface of the MOF crystals. Additional calculations with a copper paddlewheel node show that, despite being able to form complexes with hydroperoxides, the metal sites in copper paddlewheels do not catalyze hydroperoxide decomposition. Preliminary calculations involving undercoordinated metal atoms as a model for metal sites on the MOF exterior crystal surface suggest that these sites could be catalytically active.

KW - Catalysis

KW - DFT

KW - Haber-Weiss cycle

KW - Metal-organic framework

KW - Peroxide decomposition

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DFT investigation of hydroperoxide decomposition over copper and cobalt sites within metal-organic frameworks

Abstract

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ASJC Scopus subject areas

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