Spatiotemporal Mapping of Local Heterogeneities during Electrochemical Carbon Dioxide Reduction.

Autor: An H; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands., de Ruiter J; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands., Wu L; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands., Yang S; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands., Meirer F; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands., van der Stam W; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands., Weckhuysen BM; Inorganic Chemistry and Catalysis Group, Institute for Sustainable and Circular Chemistry and Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Jazyk: angličtina
Zdroj: JACS Au [JACS Au] 2023 Jul 06; Vol. 3 (7), pp. 1890-1901. Date of Electronic Publication: 2023 Jul 06 (Print Publication: 2023).
DOI: 10.1021/jacsau.3c00129
Abstrakt: The activity and selectivity of a copper electrocatalyst during the electrochemical CO 2 reduction reaction (eCO 2 RR) are largely dominated by the interplay between local reaction environment, the catalyst surface, and the adsorbed intermediates. In situ characterization studies have revealed many aspects of this intimate relationship between surface reactivity and adsorbed species, but these investigations are often limited by the spatial and temporal resolution of the analytical technique of choice. Here, Raman spectroscopy with both space and time resolution was used to reveal the distribution of adsorbed species and potential reaction intermediates on a copper electrode during eCO 2 RR. Principal component analysis (PCA) of the in situ Raman spectra revealed that a working electrocatalyst exhibits spatial heterogeneities in adsorbed species, and that the electrode surface can be divided into CO-dominant (mainly located at dendrite structures) and C-C dominant regions (mainly located at the roughened electrode surface). Our spectral evaluation further showed that in the CO-dominant regions, linear CO was observed (as characterized by a band at ∼2090 cm -1 ), accompanied by the more classical Cu-CO bending and stretching vibrations located at ∼280 and ∼360 cm -1 , respectively. In contrast, in the C-C directing region, these three Raman bands are suppressed, while at the same time a band at ∼495 cm -1 and a broad Cu-CO band at ∼2050 cm -1 dominate the Raman spectra. Furthermore, PCA revealed that anodization creates more C-C dominant regions, and labeling experiments confirmed that the 495 cm -1 band originates from the presence of a Cu-C intermediate. These results indicate that a copper electrode at work is very dynamic, thereby clearly displaying spatiotemporal heterogeneities, and that in situ micro-spectroscopic techniques are crucial for understanding the eCO 2 RR mechanism of working electrocatalyst materials.
Competing Interests: The authors declare no competing financial interest.
(© 2023 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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