Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument

Jeffrey Camacho-Bunquin; Payoli Aich; Magali Ferrandon; Andrew “Bean” Getsoian; Ujjal Das; Fulya Dogan; Larry A. Curtiss; Jeffrey T. Miller; Christopher L. Marshall; Adam S. Hock; Peter C. Stair

doi:10.1016/j.jcat.2016.10.017

Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument

Jeffrey Camacho-Bunquin, Payoli Aich, Magali Ferrandon, Andrew “Bean” Getsoian, Ujjal Das, Fulya Dogan, Larry A. Curtiss, Jeffrey T. Miller, Christopher L. Marshall, Adam S. Hock^*, Peter C. Stair

^*Corresponding author for this work

Chemistry

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81 Scopus citations

Abstract

Alkyl-zinc and zinc oxide-type sites were synthesized via atomic layer deposition on high-surface-area silica using an integrated atomic layer deposition-catalysis instrument (I-ALD-CAT). One-cycle ALD experiments using diethylzinc (DEZ) afforded Zn/SiO₂ systems that provided key insights into the reactivity and stability of Zn sites as a function of dispersion at the submonolayer level. The I-ALD-CAT tool design allowed for systematic comparison of the reactivity of different grafted zinc sites. Open-shell 16-electron, tricoordinate ethyl zinc-silica sites exhibit higher activity in propane hydrogenation-dehydrogenation compared to 18-electron, tetracoordinate zinc oxide-type centers. Silica surface saturation with Zn(II) sites (∼75% of a monolayer) results in facile zinc agglomeration and catalyst deactivation under reaction conditions. Reduced DEZ dosing coupled with thermal substrate pretreatment techniques (e.g., dehydration under vacuum) resulted in increased Zn dispersion and produced Zn/SiO₂ catalysts with improved activity and stability under propylene hydrogenation (200 °C) and propane dehydrogenation (550 °C) conditions.

Original language	English (US)
Pages (from-to)	170-182
Number of pages	13
Journal	Journal of Catalysis
Volume	345
DOIs	https://doi.org/10.1016/j.jcat.2016.10.017
State	Published - Jan 1 2017

Keywords

Atomic layer deposition
Dehydrogenation
Hydrogenation
Zinc

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry

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10.1016/j.jcat.2016.10.017

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Camacho-Bunquin, J., Aich, P., Ferrandon, M., “Bean” Getsoian, A., Das, U., Dogan, F., Curtiss, L. A., Miller, J. T., Marshall, C. L., Hock, A. S., & Stair, P. C. (2017). Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument. Journal of Catalysis, 345, 170-182. https://doi.org/10.1016/j.jcat.2016.10.017

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title = "Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument",

abstract = "Alkyl-zinc and zinc oxide-type sites were synthesized via atomic layer deposition on high-surface-area silica using an integrated atomic layer deposition-catalysis instrument (I-ALD-CAT). One-cycle ALD experiments using diethylzinc (DEZ) afforded Zn/SiO2 systems that provided key insights into the reactivity and stability of Zn sites as a function of dispersion at the submonolayer level. The I-ALD-CAT tool design allowed for systematic comparison of the reactivity of different grafted zinc sites. Open-shell 16-electron, tricoordinate ethyl zinc-silica sites exhibit higher activity in propane hydrogenation-dehydrogenation compared to 18-electron, tetracoordinate zinc oxide-type centers. Silica surface saturation with Zn(II) sites (∼75% of a monolayer) results in facile zinc agglomeration and catalyst deactivation under reaction conditions. Reduced DEZ dosing coupled with thermal substrate pretreatment techniques (e.g., dehydration under vacuum) resulted in increased Zn dispersion and produced Zn/SiO2 catalysts with improved activity and stability under propylene hydrogenation (200 °C) and propane dehydrogenation (550 °C) conditions.",

keywords = "Atomic layer deposition, Dehydrogenation, Hydrogenation, Zinc",

author = "Jeffrey Camacho-Bunquin and Payoli Aich and Magali Ferrandon and {“Bean” Getsoian}, Andrew and Ujjal Das and Fulya Dogan and Curtiss, {Larry A.} and Miller, {Jeffrey T.} and Marshall, {Christopher L.} and Hock, {Adam S.} and Stair, {Peter C.}",

note = "Publisher Copyright: {\textcopyright} 2016",

year = "2017",

month = jan,

day = "1",

doi = "10.1016/j.jcat.2016.10.017",

language = "English (US)",

volume = "345",

pages = "170--182",

journal = "Journal of Catalysis",

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publisher = "Academic Press Inc.",

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Camacho-Bunquin, J, Aich, P, Ferrandon, M, “Bean” Getsoian, A, Das, U, Dogan, F, Curtiss, LA, Miller, JT, Marshall, CL, Hock, AS & Stair, PC 2017, 'Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument', Journal of Catalysis, vol. 345, pp. 170-182. https://doi.org/10.1016/j.jcat.2016.10.017

Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument. / Camacho-Bunquin, Jeffrey; Aich, Payoli; Ferrandon, Magali et al.
In: Journal of Catalysis, Vol. 345, 01.01.2017, p. 170-182.

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

TY - JOUR

T1 - Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation

T2 - Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument

AU - Camacho-Bunquin, Jeffrey

AU - Aich, Payoli

AU - Ferrandon, Magali

AU - “Bean” Getsoian, Andrew

AU - Das, Ujjal

AU - Dogan, Fulya

AU - Curtiss, Larry A.

AU - Miller, Jeffrey T.

AU - Marshall, Christopher L.

AU - Hock, Adam S.

AU - Stair, Peter C.

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Alkyl-zinc and zinc oxide-type sites were synthesized via atomic layer deposition on high-surface-area silica using an integrated atomic layer deposition-catalysis instrument (I-ALD-CAT). One-cycle ALD experiments using diethylzinc (DEZ) afforded Zn/SiO2 systems that provided key insights into the reactivity and stability of Zn sites as a function of dispersion at the submonolayer level. The I-ALD-CAT tool design allowed for systematic comparison of the reactivity of different grafted zinc sites. Open-shell 16-electron, tricoordinate ethyl zinc-silica sites exhibit higher activity in propane hydrogenation-dehydrogenation compared to 18-electron, tetracoordinate zinc oxide-type centers. Silica surface saturation with Zn(II) sites (∼75% of a monolayer) results in facile zinc agglomeration and catalyst deactivation under reaction conditions. Reduced DEZ dosing coupled with thermal substrate pretreatment techniques (e.g., dehydration under vacuum) resulted in increased Zn dispersion and produced Zn/SiO2 catalysts with improved activity and stability under propylene hydrogenation (200 °C) and propane dehydrogenation (550 °C) conditions.

AB - Alkyl-zinc and zinc oxide-type sites were synthesized via atomic layer deposition on high-surface-area silica using an integrated atomic layer deposition-catalysis instrument (I-ALD-CAT). One-cycle ALD experiments using diethylzinc (DEZ) afforded Zn/SiO2 systems that provided key insights into the reactivity and stability of Zn sites as a function of dispersion at the submonolayer level. The I-ALD-CAT tool design allowed for systematic comparison of the reactivity of different grafted zinc sites. Open-shell 16-electron, tricoordinate ethyl zinc-silica sites exhibit higher activity in propane hydrogenation-dehydrogenation compared to 18-electron, tetracoordinate zinc oxide-type centers. Silica surface saturation with Zn(II) sites (∼75% of a monolayer) results in facile zinc agglomeration and catalyst deactivation under reaction conditions. Reduced DEZ dosing coupled with thermal substrate pretreatment techniques (e.g., dehydration under vacuum) resulted in increased Zn dispersion and produced Zn/SiO2 catalysts with improved activity and stability under propylene hydrogenation (200 °C) and propane dehydrogenation (550 °C) conditions.

KW - Atomic layer deposition

KW - Dehydrogenation

KW - Hydrogenation

KW - Zinc

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UR - http://www.scopus.com/inward/citedby.url?scp=85002975025&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2016.10.017

DO - 10.1016/j.jcat.2016.10.017

M3 - Article

AN - SCOPUS:85002975025

SN - 0021-9517

VL - 345

SP - 170

EP - 182

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument

Abstract

Keywords

ASJC Scopus subject areas

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