Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2-CO co-feeds on Cu and Cu-tandem electrocatalysts

Xingli Wang; Jorge Ferreira de Araujo; Wen Ju; Alexander Bagger; Henrike Schmies; Stefanie Kuhl; Jan Rossmeisl; Peter Strasser

doi:10.1038/s41565-019-0551-6

Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2-CO co-feeds on Cu and Cu-tandem electrocatalysts

Xingli Wang, Jorge Ferreira de Araujo, Wen Ju, Alexander Bagger, Henrike Schmies, Stefanie Kuhl, Jan Rossmeisl, Peter Strasser

Department of Chemistry

70 Citations (Scopus)

Abstract

Unlike energy efficiency and selectivity challenges, the kinetic effects of impure or intentionally mixed CO₂ feeds on the catalytic reactivity of the direct electrochemical CO₂ reduction reaction (CO2RR) have been poorly studied. Given that industrial CO₂ feeds are often contaminated with CO, a closer investigation of the CO2RR under CO₂/CO co-feed conditions is warranted. Here, we report mechanistic insights into the CO2RR reactivity of CO₂/CO co-feeds on Cu-based nanocatalysts. Kinetic isotope-labelling experiments—performed in an operando differential electrochemical mass spectrometry capillary flow cell with millisecond time resolution—showed an unexpected enhanced production of C₂H₄, with a yield increase of almost 50%, from a cross-coupled ¹²CO₂–¹³CO reactive pathway. The results suggest the absence of site competition between CO₂ and CO molecules on the reactive surface at the reactant-specific sites. The practical significance of sustained local interfacial CO partial pressures under CO₂ depletion is demonstrated by metallic/non-metallic Cu/Ni–N-doped carbon tandem catalysts. Our findings show the mechanistic origin of improved C₂ product formation under co-feeding, but also highlight technological opportunities of impure CO₂/CO process feeds for H₂O/CO₂ co-electrolysers.

Original language	English
Journal	Nature Nanotechnology
Volume	14
Issue number	11
Pages (from-to)	1063–1070
ISSN	1748-3387
DOIs	https://doi.org/10.1038/s41565-019-0551-6
Publication status	Published - 1 Nov 2019

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title = "Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2-CO co-feeds on Cu and Cu-tandem electrocatalysts",

abstract = "Unlike energy efficiency and selectivity challenges, the kinetic effects of impure or intentionally mixed CO2 feeds on the catalytic reactivity of the direct electrochemical CO2 reduction reaction (CO2RR) have been poorly studied. Given that industrial CO2 feeds are often contaminated with CO, a closer investigation of the CO2RR under CO2/CO co-feed conditions is warranted. Here, we report mechanistic insights into the CO2RR reactivity of CO2/CO co-feeds on Cu-based nanocatalysts. Kinetic isotope-labelling experiments—performed in an operando differential electrochemical mass spectrometry capillary flow cell with millisecond time resolution—showed an unexpected enhanced production of C2H4, with a yield increase of almost 50%, from a cross-coupled 12CO2–13CO reactive pathway. The results suggest the absence of site competition between CO2 and CO molecules on the reactive surface at the reactant-specific sites. The practical significance of sustained local interfacial CO partial pressures under CO2 depletion is demonstrated by metallic/non-metallic Cu/Ni–N-doped carbon tandem catalysts. Our findings show the mechanistic origin of improved C2 product formation under co-feeding, but also highlight technological opportunities of impure CO2/CO process feeds for H2O/CO2 co-electrolysers.",

author = "Xingli Wang and {de Araujo}, {Jorge Ferreira} and Wen Ju and Alexander Bagger and Henrike Schmies and Stefanie Kuhl and Jan Rossmeisl and Peter Strasser",

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T1 - Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2-CO co-feeds on Cu and Cu-tandem electrocatalysts

AU - Wang, Xingli

AU - de Araujo, Jorge Ferreira

AU - Ju, Wen

AU - Bagger, Alexander

AU - Schmies, Henrike

AU - Kuhl, Stefanie

AU - Rossmeisl, Jan

AU - Strasser, Peter

PY - 2019/11/1

Y1 - 2019/11/1

N2 - Unlike energy efficiency and selectivity challenges, the kinetic effects of impure or intentionally mixed CO2 feeds on the catalytic reactivity of the direct electrochemical CO2 reduction reaction (CO2RR) have been poorly studied. Given that industrial CO2 feeds are often contaminated with CO, a closer investigation of the CO2RR under CO2/CO co-feed conditions is warranted. Here, we report mechanistic insights into the CO2RR reactivity of CO2/CO co-feeds on Cu-based nanocatalysts. Kinetic isotope-labelling experiments—performed in an operando differential electrochemical mass spectrometry capillary flow cell with millisecond time resolution—showed an unexpected enhanced production of C2H4, with a yield increase of almost 50%, from a cross-coupled 12CO2–13CO reactive pathway. The results suggest the absence of site competition between CO2 and CO molecules on the reactive surface at the reactant-specific sites. The practical significance of sustained local interfacial CO partial pressures under CO2 depletion is demonstrated by metallic/non-metallic Cu/Ni–N-doped carbon tandem catalysts. Our findings show the mechanistic origin of improved C2 product formation under co-feeding, but also highlight technological opportunities of impure CO2/CO process feeds for H2O/CO2 co-electrolysers.

AB - Unlike energy efficiency and selectivity challenges, the kinetic effects of impure or intentionally mixed CO2 feeds on the catalytic reactivity of the direct electrochemical CO2 reduction reaction (CO2RR) have been poorly studied. Given that industrial CO2 feeds are often contaminated with CO, a closer investigation of the CO2RR under CO2/CO co-feed conditions is warranted. Here, we report mechanistic insights into the CO2RR reactivity of CO2/CO co-feeds on Cu-based nanocatalysts. Kinetic isotope-labelling experiments—performed in an operando differential electrochemical mass spectrometry capillary flow cell with millisecond time resolution—showed an unexpected enhanced production of C2H4, with a yield increase of almost 50%, from a cross-coupled 12CO2–13CO reactive pathway. The results suggest the absence of site competition between CO2 and CO molecules on the reactive surface at the reactant-specific sites. The practical significance of sustained local interfacial CO partial pressures under CO2 depletion is demonstrated by metallic/non-metallic Cu/Ni–N-doped carbon tandem catalysts. Our findings show the mechanistic origin of improved C2 product formation under co-feeding, but also highlight technological opportunities of impure CO2/CO process feeds for H2O/CO2 co-electrolysers.

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DO - 10.1038/s41565-019-0551-6

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C2 - 31591526

SN - 1748-3387

VL - 14

SP - 1063

EP - 1070

JO - Nature Nanotechnology

JF - Nature Nanotechnology

IS - 11

ER -

Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2-CO co-feeds on Cu and Cu-tandem electrocatalysts

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