Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal-Organic Framework for Ethylene Dimerization

Varinia Bernales; Aaron B. League; Zhanyong Li; Neil M. Schweitzer; Aaron W. Peters; Rebecca K. Carlson; Joseph T. Hupp; Christopher J. Cramer; Omar K. Farha; Laura Gagliardi

doi:10.1021/acs.jpcc.6b07362

Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal-Organic Framework for Ethylene Dimerization

Varinia Bernales, Aaron B. League, Zhanyong Li, Neil M. Schweitzer, Aaron W. Peters, Rebecca K. Carlson, Joseph T. Hupp, Christopher J. Cramer, Omar K. Farha^*, Laura Gagliardi

^*Corresponding author for this work

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

81 Scopus citations

Abstract

The catalytic performance of a cobalt(II) single-site catalyst supported on the zirconia-like nodes of the metal organic-framework (MOF) NU-1000 is herein characterized by quantum chemical methods and compared to an iso-structural analogue incorporating nickel(II) as the active transition metal. The mechanisms of atomic layer deposition in MOFs and of catalysis are examined using density functional theory. We compare the catalytic activity of Co and Ni installed on the zirconia-like nodes for ethylene dimerization, considering three plausible pathways. Multiconfigurational wave function theory methods are employed to further characterize the electronic structures of key transition states and intermediates. Finally, we report confirmation of Co catalytic activity for ethylene dimerization from experiments that were prompted by the computational prediction.

Original language	English (US)
Pages (from-to)	23576-23583
Number of pages	8
Journal	Journal of Physical Chemistry C
Volume	120
Issue number	41
DOIs	https://doi.org/10.1021/acs.jpcc.6b07362
State	Published - Oct 20 2016

Funding

We thank Dr. Konstantino, D. Vogiatzis, and Dr. Manuel A. Ortu?o for helpful discussions. This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DESC0012702).

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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title = "Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal-Organic Framework for Ethylene Dimerization",

abstract = "The catalytic performance of a cobalt(II) single-site catalyst supported on the zirconia-like nodes of the metal organic-framework (MOF) NU-1000 is herein characterized by quantum chemical methods and compared to an iso-structural analogue incorporating nickel(II) as the active transition metal. The mechanisms of atomic layer deposition in MOFs and of catalysis are examined using density functional theory. We compare the catalytic activity of Co and Ni installed on the zirconia-like nodes for ethylene dimerization, considering three plausible pathways. Multiconfigurational wave function theory methods are employed to further characterize the electronic structures of key transition states and intermediates. Finally, we report confirmation of Co catalytic activity for ethylene dimerization from experiments that were prompted by the computational prediction.",

author = "Varinia Bernales and League, {Aaron B.} and Zhanyong Li and Schweitzer, {Neil M.} and Peters, {Aaron W.} and Carlson, {Rebecca K.} and Hupp, {Joseph T.} and Cramer, {Christopher J.} and Farha, {Omar K.} and Laura Gagliardi",

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AU - Bernales, Varinia

AU - League, Aaron B.

AU - Li, Zhanyong

AU - Schweitzer, Neil M.

AU - Peters, Aaron W.

AU - Carlson, Rebecca K.

AU - Hupp, Joseph T.

AU - Cramer, Christopher J.

AU - Farha, Omar K.

AU - Gagliardi, Laura

PY - 2016/10/20

Y1 - 2016/10/20

N2 - The catalytic performance of a cobalt(II) single-site catalyst supported on the zirconia-like nodes of the metal organic-framework (MOF) NU-1000 is herein characterized by quantum chemical methods and compared to an iso-structural analogue incorporating nickel(II) as the active transition metal. The mechanisms of atomic layer deposition in MOFs and of catalysis are examined using density functional theory. We compare the catalytic activity of Co and Ni installed on the zirconia-like nodes for ethylene dimerization, considering three plausible pathways. Multiconfigurational wave function theory methods are employed to further characterize the electronic structures of key transition states and intermediates. Finally, we report confirmation of Co catalytic activity for ethylene dimerization from experiments that were prompted by the computational prediction.

AB - The catalytic performance of a cobalt(II) single-site catalyst supported on the zirconia-like nodes of the metal organic-framework (MOF) NU-1000 is herein characterized by quantum chemical methods and compared to an iso-structural analogue incorporating nickel(II) as the active transition metal. The mechanisms of atomic layer deposition in MOFs and of catalysis are examined using density functional theory. We compare the catalytic activity of Co and Ni installed on the zirconia-like nodes for ethylene dimerization, considering three plausible pathways. Multiconfigurational wave function theory methods are employed to further characterize the electronic structures of key transition states and intermediates. Finally, we report confirmation of Co catalytic activity for ethylene dimerization from experiments that were prompted by the computational prediction.

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Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal-Organic Framework for Ethylene Dimerization

Abstract

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