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

Purdue University
Argonne National Laboratory

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

15 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.

NLR 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.",

year = "2017",

month = may,

day = "5",

doi = "10.1021/acscatal.6b03582",

language = "American English",

volume = "7",

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journal = "ACS Catalysis",

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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

UR - https://www.scopus.com/pages/publications/85020862146

U2 - 10.1021/acscatal.6b03582

DO - 10.1021/acscatal.6b03582

M3 - Article

AN - SCOPUS:85020862146

SN - 2155-5435

VL - 7

SP - 3662

EP - 3667

JO - ACS Catalysis

JF - ACS Catalysis

IS - 5

ER -

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

Abstract

Bibliographical note

NLR Publication Number

Keywords

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