Tailoring the facet distribution on copper with chloride
Mazaira, Pedro (University of Copenhagen. Department of Chemistry)
Madsen, Thor Kongstad (University of Copenhagen. Department of Chemistry)
Plaza-Mayoral, Elena (University of Copenhagen. Department of Chemistry)
Kristoffersen, Henrik H. (University of Copenhagen. Department of Chemistry)
Chorkendorff, Ib (University of Denmark. Department of Physics)
Dalby, Kim Nicole (Topsoe A/S)
van der Stam, War (Utrecht University. Inorganic Chemistry and Catalysis)
Rossmeisl, Jan (University of Copenhagen. Department of Chemistry)
Escudero-Escribano, María (Institut Català de Nanociència i Nanotecnologia)
Sebastián-Pascual, Paula (University of Copenhagen. Department of Chemistry)

Data:	2023
Resum:	Electrocatalytic reactions are sensitive to the catalyst surface structure. Therefore, finding methods to determine active surface sites with different geometry is essential to address the structure-electrocatalytic performance relationships. In this work, we propose a simple methodology to tune and quantify the surface structure on copper catalysts. We tailor the distribution and ratio of facets on copper by electrochemically oxidizing and reducing the surface in chloride-rich aqueous solutions. We then address the formation of new facets with voltammetric lead (Pb) underpotential deposition (UPD). We first record the voltammetric lead UPD on different single facets, which have intense peaks at different potential values. We use this data to decouple each facet peak-contribution in the lead (Pb) UPD curves of the tailored and multifaceted copper surfaces and determine the geometry of the active sites. We combine experiments with density functional theory (DFT) calculations to assess the ligand effect of chloride anions on the copper facet distribution during the surface oxidation/electrodeposition treatment. Our experiments and Wulff constructions suggest that chloride preferentially adsorbs on the (310) facet, reducing the number of (111) sites and inducing the growth of (310) or n(100) × (110) domains. Our work provides a tool to correlate active sites with copper geometries, which is needed to assess the structure-performance relationships in electrocatalysis. We also demonstrate an easy method for selectively tailoring the facet distribution of copper, which is essential to design a well-defined nanostructured catalyst.
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Matèria:	Active site ; Active surface sites ; Catalyst surfaces ; Copper catalyst ; Different geometry ; Electrocatalytic performance ; Electrocatalytic reactions ; Simple++ ; Underpotential deposition ; Voltammetric
Publicat a:	Chemical science, Vol. 15, Issue 5 (February 2023) , p. 1714-1725, ISSN 2041-6539

DOI: 10.1039/d3sc05988j
PMID: 38303937

12 p, 3.2 MB

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