Exploring Low-Temperature Dehydrogenation at Ionic Cu Sites in Beta Zeolite to Enable Alkane Recycle in Dimethyl Ether Homologation

Daniel Ruddy; Carrie Farberow; Seon Ah Kim; Jesse Hensley; Joshua Schaidle; Jeffrey Miller; James Gallagher; Singfoong Cheah

doi:10.1021/acscatal.6b03582

Exploring Low-Temperature Dehydrogenation at Ionic Cu Sites in Beta Zeolite to Enable Alkane Recycle in Dimethyl Ether Homologation

Daniel Ruddy, Carrie Farberow, Seon Ah Kim, Jesse Hensley, Joshua Schaidle, Jeffrey Miller, James Gallagher, Singfoong Cheah

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

13 Scopus Citations

Abstract

Cu-based catalysts containing targeted functionalities including metallic Cu, oxidized Cu, ionic Cu, and Brønsted acid sites were synthesized and evaluated for isobutane dehydrogenation. Hydrogen productivities, combined with operando X-ray absorption spectroscopy, indicated that Cu(I) sites in Cu/BEA catalysts activate C-H bonds in isobutane. Computational analysis revealed that isobutane dehydrogenation at a Cu(I) site proceeds through a two-step mechanism with a maximum energy barrier of 159 kJ/mol. These results demonstrate that light alkanes can be reactivated on Cu/BEA, which may enable re-entry of these species into the chain-growth cycle of dimethyl ether homologation, thereby increasing gasoline-range (C₅₊) hydrocarbon yield. (Chemical Equation Presented).

Original language	American English
Pages (from-to)	3662-3667
Number of pages	6
Journal	ACS Catalysis
Volume	7
Issue number	5
DOIs	https://doi.org/10.1021/acscatal.6b03582 https://doi.org/10.1021/acscatal.6b03582
State	Published - 5 May 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

NREL Publication Number

NREL/JA-5100-67284

Keywords

C-H activation
copper
dehydrogenation
heterogeneous catalysis
zeolites

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title = "Exploring Low-Temperature Dehydrogenation at Ionic Cu Sites in Beta Zeolite to Enable Alkane Recycle in Dimethyl Ether Homologation",

abstract = "Cu-based catalysts containing targeted functionalities including metallic Cu, oxidized Cu, ionic Cu, and Br{\o}nsted acid sites were synthesized and evaluated for isobutane dehydrogenation. Hydrogen productivities, combined with operando X-ray absorption spectroscopy, indicated that Cu(I) sites in Cu/BEA catalysts activate C-H bonds in isobutane. Computational analysis revealed that isobutane dehydrogenation at a Cu(I) site proceeds through a two-step mechanism with a maximum energy barrier of 159 kJ/mol. These results demonstrate that light alkanes can be reactivated on Cu/BEA, which may enable re-entry of these species into the chain-growth cycle of dimethyl ether homologation, thereby increasing gasoline-range (C5+) hydrocarbon yield. (Chemical Equation Presented).",

keywords = "C-H activation, copper, dehydrogenation, heterogeneous catalysis, zeolites",

author = "Daniel Ruddy and Carrie Farberow and Kim, {Seon Ah} and Jesse Hensley and Joshua Schaidle and Jeffrey Miller and James Gallagher and Singfoong Cheah",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acscatal.6b03582",

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T1 - Exploring Low-Temperature Dehydrogenation at Ionic Cu Sites in Beta Zeolite to Enable Alkane Recycle in Dimethyl Ether Homologation

AU - Ruddy, Daniel

AU - Farberow, Carrie

AU - Kim, Seon Ah

AU - Hensley, Jesse

AU - Schaidle, Joshua

AU - Miller, Jeffrey

AU - Gallagher, James

AU - Cheah, Singfoong

PY - 2017/5/5

Y1 - 2017/5/5

N2 - Cu-based catalysts containing targeted functionalities including metallic Cu, oxidized Cu, ionic Cu, and Brønsted acid sites were synthesized and evaluated for isobutane dehydrogenation. Hydrogen productivities, combined with operando X-ray absorption spectroscopy, indicated that Cu(I) sites in Cu/BEA catalysts activate C-H bonds in isobutane. Computational analysis revealed that isobutane dehydrogenation at a Cu(I) site proceeds through a two-step mechanism with a maximum energy barrier of 159 kJ/mol. These results demonstrate that light alkanes can be reactivated on Cu/BEA, which may enable re-entry of these species into the chain-growth cycle of dimethyl ether homologation, thereby increasing gasoline-range (C5+) hydrocarbon yield. (Chemical Equation Presented).

AB - Cu-based catalysts containing targeted functionalities including metallic Cu, oxidized Cu, ionic Cu, and Brønsted acid sites were synthesized and evaluated for isobutane dehydrogenation. Hydrogen productivities, combined with operando X-ray absorption spectroscopy, indicated that Cu(I) sites in Cu/BEA catalysts activate C-H bonds in isobutane. Computational analysis revealed that isobutane dehydrogenation at a Cu(I) site proceeds through a two-step mechanism with a maximum energy barrier of 159 kJ/mol. These results demonstrate that light alkanes can be reactivated on Cu/BEA, which may enable re-entry of these species into the chain-growth cycle of dimethyl ether homologation, thereby increasing gasoline-range (C5+) hydrocarbon yield. (Chemical Equation Presented).

KW - C-H activation

KW - copper

KW - dehydrogenation

KW - heterogeneous catalysis

KW - zeolites

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Exploring Low-Temperature Dehydrogenation at Ionic Cu Sites in Beta Zeolite to Enable Alkane Recycle in Dimethyl Ether Homologation

Abstract

Bibliographical note

NREL Publication Number

Keywords

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