Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation

Propene on palladium

Anna Winiwarter, Luca Silvioli, Soren B. Scott, Kasper Enemark-Rasmussen, Manuel Sariç, Daniel B. Trimarco, Peter C.K. Vesborg, Poul G. Moses, Ifan E.L. Stephens, Brian Seger, Jan Rossmeisl, Ib Chorkendorff*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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Abstract

The efficient partial oxidation of hydrocarbons to valuable chemicals without formation of CO2 is one of the great challenges in heterogeneous catalysis. The ever-decreasing cost of renewable electricity and the superior control over reactivity qualify electrochemistry as a particularly attractive means of addressing this challenge. Yet, to date, little is known about the factors regulating hydrocarbon oxidation at the atomic level. A relevant showcase reaction is propene electro-oxidation to key industrial commodity chemicals, such as acrolein, acrylic acid and propylene oxide. In this study, we investigate the partial electrochemical oxidation of propene on high-surface area Pd electrodes using a combination of electrochemical measurements, advanced product characterization and theoretical modeling. We report a new reaction product, propylene glycol, and high selectivity towards acrolein. We further identify key reaction intermediates and propose a mechanism dictated by the surface coverage of organic species formed in situ, where stable reactant adsorption at low coverage determines the selectivity towards allylic oxidation at high coverage. Our fundamental findings enable advances in partial hydrocarbon oxidation reactions by highlighting atomic surface structuring as the key to selective and versatile electrochemical catalyst design.

Original languageEnglish
JournalEnergy and Environmental Science
Volume12
Issue number3
Pages (from-to)1055-1067
Number of pages13
ISSN1754-5692
DOIs
Publication statusPublished - 2019

Cite this

Winiwarter, Anna ; Silvioli, Luca ; Scott, Soren B. ; Enemark-Rasmussen, Kasper ; Sariç, Manuel ; Trimarco, Daniel B. ; Vesborg, Peter C.K. ; Moses, Poul G. ; Stephens, Ifan E.L. ; Seger, Brian ; Rossmeisl, Jan ; Chorkendorff, Ib. / Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation : Propene on palladium. In: Energy and Environmental Science. 2019 ; Vol. 12, No. 3. pp. 1055-1067.
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title = "Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation: Propene on palladium",
abstract = "The efficient partial oxidation of hydrocarbons to valuable chemicals without formation of CO2 is one of the great challenges in heterogeneous catalysis. The ever-decreasing cost of renewable electricity and the superior control over reactivity qualify electrochemistry as a particularly attractive means of addressing this challenge. Yet, to date, little is known about the factors regulating hydrocarbon oxidation at the atomic level. A relevant showcase reaction is propene electro-oxidation to key industrial commodity chemicals, such as acrolein, acrylic acid and propylene oxide. In this study, we investigate the partial electrochemical oxidation of propene on high-surface area Pd electrodes using a combination of electrochemical measurements, advanced product characterization and theoretical modeling. We report a new reaction product, propylene glycol, and high selectivity towards acrolein. We further identify key reaction intermediates and propose a mechanism dictated by the surface coverage of organic species formed in situ, where stable reactant adsorption at low coverage determines the selectivity towards allylic oxidation at high coverage. Our fundamental findings enable advances in partial hydrocarbon oxidation reactions by highlighting atomic surface structuring as the key to selective and versatile electrochemical catalyst design.",
author = "Anna Winiwarter and Luca Silvioli and Scott, {Soren B.} and Kasper Enemark-Rasmussen and Manuel Sari{\cc} and Trimarco, {Daniel B.} and Vesborg, {Peter C.K.} and Moses, {Poul G.} and Stephens, {Ifan E.L.} and Brian Seger and Jan Rossmeisl and Ib Chorkendorff",
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Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation : Propene on palladium. / Winiwarter, Anna; Silvioli, Luca; Scott, Soren B.; Enemark-Rasmussen, Kasper; Sariç, Manuel; Trimarco, Daniel B.; Vesborg, Peter C.K.; Moses, Poul G.; Stephens, Ifan E.L.; Seger, Brian; Rossmeisl, Jan; Chorkendorff, Ib.

In: Energy and Environmental Science, Vol. 12, No. 3, 2019, p. 1055-1067.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Towards an atomistic understanding of electrocatalytic partial hydrocarbon oxidation

T2 - Propene on palladium

AU - Winiwarter, Anna

AU - Silvioli, Luca

AU - Scott, Soren B.

AU - Enemark-Rasmussen, Kasper

AU - Sariç, Manuel

AU - Trimarco, Daniel B.

AU - Vesborg, Peter C.K.

AU - Moses, Poul G.

AU - Stephens, Ifan E.L.

AU - Seger, Brian

AU - Rossmeisl, Jan

AU - Chorkendorff, Ib

PY - 2019

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N2 - The efficient partial oxidation of hydrocarbons to valuable chemicals without formation of CO2 is one of the great challenges in heterogeneous catalysis. The ever-decreasing cost of renewable electricity and the superior control over reactivity qualify electrochemistry as a particularly attractive means of addressing this challenge. Yet, to date, little is known about the factors regulating hydrocarbon oxidation at the atomic level. A relevant showcase reaction is propene electro-oxidation to key industrial commodity chemicals, such as acrolein, acrylic acid and propylene oxide. In this study, we investigate the partial electrochemical oxidation of propene on high-surface area Pd electrodes using a combination of electrochemical measurements, advanced product characterization and theoretical modeling. We report a new reaction product, propylene glycol, and high selectivity towards acrolein. We further identify key reaction intermediates and propose a mechanism dictated by the surface coverage of organic species formed in situ, where stable reactant adsorption at low coverage determines the selectivity towards allylic oxidation at high coverage. Our fundamental findings enable advances in partial hydrocarbon oxidation reactions by highlighting atomic surface structuring as the key to selective and versatile electrochemical catalyst design.

AB - The efficient partial oxidation of hydrocarbons to valuable chemicals without formation of CO2 is one of the great challenges in heterogeneous catalysis. The ever-decreasing cost of renewable electricity and the superior control over reactivity qualify electrochemistry as a particularly attractive means of addressing this challenge. Yet, to date, little is known about the factors regulating hydrocarbon oxidation at the atomic level. A relevant showcase reaction is propene electro-oxidation to key industrial commodity chemicals, such as acrolein, acrylic acid and propylene oxide. In this study, we investigate the partial electrochemical oxidation of propene on high-surface area Pd electrodes using a combination of electrochemical measurements, advanced product characterization and theoretical modeling. We report a new reaction product, propylene glycol, and high selectivity towards acrolein. We further identify key reaction intermediates and propose a mechanism dictated by the surface coverage of organic species formed in situ, where stable reactant adsorption at low coverage determines the selectivity towards allylic oxidation at high coverage. Our fundamental findings enable advances in partial hydrocarbon oxidation reactions by highlighting atomic surface structuring as the key to selective and versatile electrochemical catalyst design.

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