Comparing the reaction profiles of single iron catalytic sites in enzymes and in reticular frameworks for methane-to-methanol oxidation

Jenny G. Vitillo; Connie C. Lu; Aditya Bhan; Laura Gagliardi

doi:10.1016/j.xcrp.2023.101422

Comparing the reaction profiles of single iron catalytic sites in enzymes and in reticular frameworks for methane-to-methanol oxidation

Jenny G. Vitillo, Connie C. Lu, Aditya Bhan, Laura Gagliardi

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

Abstract

The design of synthetic inorganic catalysts mimicking the first coordination spheres of enzymatic cofactors often results in lower yields and selectivity than their biological counterparts. In this study, we exploit Kohn-Sham density functional methods to compare the reaction profiles of four single iron-based catalysts for the direct oxidation of methane to methanol: two biomimetic models based on two enzymes (cytochrome P450 and taurine dioxygenase [TauD]) and two synthetic reticular frameworks (iron-BEA zeolite and tri-iron oxo-center-based metal-organic framework). Both the biomimetic and inorganic catalysts show almost zero selectivity toward methanol for methane conversions >1% at ambient temperature. This study highlights that iron's first coordination shell can influence selectivity toward methanol but to a limited extent. In the absence of methanol protection strategies, high selectivity can be reached only by mimicking the reaction microenvironment of enzymes beyond the first coordination shell of iron.

Original language	English (US)
Article number	101422
Journal	Cell Reports Physical Science
Volume	4
Issue number	6
DOIs	https://doi.org/10.1016/j.xcrp.2023.101422
State	Published - Jun 21 2023

Bibliographical note

Funding Information:
This work was partially supported by the Inorganometallic Catalyst Design Center; an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0012702; and by the Catalyst Design for Decarbonization Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0023383. The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. Conceptualization, J.G.V.; methodology, J.G.V.; investigation, J.G.V.; writing – original draft, J.G.V.; writing – review & editing, J.G.V. C.C.L. A.B. and L.G.; funding acquisition, L.G.; supervision, J.G.V. The authors declare no competing interests. We support inclusive, diverse, and equitable conduct of research.

Funding Information:
This work was partially supported by the Inorganometallic Catalyst Design Center ; an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences , under award no. DE-SC0012702 ; and by the Catalyst Design for Decarbonization Center , an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences , under award no. DE-SC0023383 . The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources.

Publisher Copyright:
© 2023 The Author(s)

Keywords

C–H bond activation
MOFs
P450
TauD
catalysis
density functional theory
enzymes
methane-to-methanol
selectivity
zeolites

Publisher link

10.1016/j.xcrp.2023.101422

Find It

Find It at U of M Libraries

Cite this

@article{e6795ab507274a49b0a82643ca0eeaf2,

title = "Comparing the reaction profiles of single iron catalytic sites in enzymes and in reticular frameworks for methane-to-methanol oxidation",

abstract = "The design of synthetic inorganic catalysts mimicking the first coordination spheres of enzymatic cofactors often results in lower yields and selectivity than their biological counterparts. In this study, we exploit Kohn-Sham density functional methods to compare the reaction profiles of four single iron-based catalysts for the direct oxidation of methane to methanol: two biomimetic models based on two enzymes (cytochrome P450 and taurine dioxygenase [TauD]) and two synthetic reticular frameworks (iron-BEA zeolite and tri-iron oxo-center-based metal-organic framework). Both the biomimetic and inorganic catalysts show almost zero selectivity toward methanol for methane conversions >1% at ambient temperature. This study highlights that iron's first coordination shell can influence selectivity toward methanol but to a limited extent. In the absence of methanol protection strategies, high selectivity can be reached only by mimicking the reaction microenvironment of enzymes beyond the first coordination shell of iron.",

keywords = "C–H bond activation, MOFs, P450, TauD, catalysis, density functional theory, enzymes, methane-to-methanol, selectivity, zeolites",

author = "Vitillo, {Jenny G.} and Lu, {Connie C.} and Aditya Bhan and Laura Gagliardi",

note = "Funding Information: This work was partially supported by the Inorganometallic Catalyst Design Center; an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0012702; and by the Catalyst Design for Decarbonization Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0023383. The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. Conceptualization, J.G.V.; methodology, J.G.V.; investigation, J.G.V.; writing – original draft, J.G.V.; writing – review & editing, J.G.V. C.C.L. A.B. and L.G.; funding acquisition, L.G.; supervision, J.G.V. The authors declare no competing interests. We support inclusive, diverse, and equitable conduct of research. Funding Information: This work was partially supported by the Inorganometallic Catalyst Design Center ; an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences , under award no. DE-SC0012702 ; and by the Catalyst Design for Decarbonization Center , an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences , under award no. DE-SC0023383 . The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. Publisher Copyright: {\textcopyright} 2023 The Author(s)",

year = "2023",

month = jun,

day = "21",

doi = "10.1016/j.xcrp.2023.101422",

language = "English (US)",

volume = "4",

journal = "Cell Reports Physical Science",

issn = "2666-3864",

publisher = "Cell Press",

number = "6",

}

TY - JOUR

T1 - Comparing the reaction profiles of single iron catalytic sites in enzymes and in reticular frameworks for methane-to-methanol oxidation

AU - Vitillo, Jenny G.

AU - Lu, Connie C.

AU - Bhan, Aditya

AU - Gagliardi, Laura

N1 - Funding Information: This work was partially supported by the Inorganometallic Catalyst Design Center; an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0012702; and by the Catalyst Design for Decarbonization Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0023383. The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. Conceptualization, J.G.V.; methodology, J.G.V.; investigation, J.G.V.; writing – original draft, J.G.V.; writing – review & editing, J.G.V. C.C.L. A.B. and L.G.; funding acquisition, L.G.; supervision, J.G.V. The authors declare no competing interests. We support inclusive, diverse, and equitable conduct of research. Funding Information: This work was partially supported by the Inorganometallic Catalyst Design Center ; an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences , under award no. DE-SC0012702 ; and by the Catalyst Design for Decarbonization Center , an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences , under award no. DE-SC0023383 . The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. Publisher Copyright: © 2023 The Author(s)

PY - 2023/6/21

Y1 - 2023/6/21

N2 - The design of synthetic inorganic catalysts mimicking the first coordination spheres of enzymatic cofactors often results in lower yields and selectivity than their biological counterparts. In this study, we exploit Kohn-Sham density functional methods to compare the reaction profiles of four single iron-based catalysts for the direct oxidation of methane to methanol: two biomimetic models based on two enzymes (cytochrome P450 and taurine dioxygenase [TauD]) and two synthetic reticular frameworks (iron-BEA zeolite and tri-iron oxo-center-based metal-organic framework). Both the biomimetic and inorganic catalysts show almost zero selectivity toward methanol for methane conversions >1% at ambient temperature. This study highlights that iron's first coordination shell can influence selectivity toward methanol but to a limited extent. In the absence of methanol protection strategies, high selectivity can be reached only by mimicking the reaction microenvironment of enzymes beyond the first coordination shell of iron.

AB - The design of synthetic inorganic catalysts mimicking the first coordination spheres of enzymatic cofactors often results in lower yields and selectivity than their biological counterparts. In this study, we exploit Kohn-Sham density functional methods to compare the reaction profiles of four single iron-based catalysts for the direct oxidation of methane to methanol: two biomimetic models based on two enzymes (cytochrome P450 and taurine dioxygenase [TauD]) and two synthetic reticular frameworks (iron-BEA zeolite and tri-iron oxo-center-based metal-organic framework). Both the biomimetic and inorganic catalysts show almost zero selectivity toward methanol for methane conversions >1% at ambient temperature. This study highlights that iron's first coordination shell can influence selectivity toward methanol but to a limited extent. In the absence of methanol protection strategies, high selectivity can be reached only by mimicking the reaction microenvironment of enzymes beyond the first coordination shell of iron.

KW - C–H bond activation

KW - MOFs

KW - P450

KW - TauD

KW - catalysis

KW - density functional theory

KW - enzymes

KW - methane-to-methanol

KW - selectivity

KW - zeolites

UR - http://www.scopus.com/inward/record.url?scp=85162078274&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85162078274&partnerID=8YFLogxK

U2 - 10.1016/j.xcrp.2023.101422

DO - 10.1016/j.xcrp.2023.101422

M3 - Article

AN - SCOPUS:85162078274

SN - 2666-3864

VL - 4

JO - Cell Reports Physical Science

JF - Cell Reports Physical Science

IS - 6

M1 - 101422

ER -

Comparing the reaction profiles of single iron catalytic sites in enzymes and in reticular frameworks for methane-to-methanol oxidation

Abstract

Bibliographical note

Keywords

Publisher link

Find It

Other files and links

Fingerprint

Cite this