Size-dependent effects of Cu° nanoparticles on electronic properties and ethanol dehydrogenation catalysis via Cu+-O-Cu+ species

Osmari, Taynara A., Petrolini, Davi D., Lopez-Castillo, Alejandro, Henrique de Morais, Leonardo, Zanchet, Daniela, Sainna, Mala A., Willock, David ORCID: https://orcid.org/0000-0002-8893-1090, Gallo, Jean Marcel R., dos Santos, João B.O. and Bueno, José Maria C. 2024. Size-dependent effects of Cu° nanoparticles on electronic properties and ethanol dehydrogenation catalysis via Cu+-O-Cu+ species. Materials Today Chemistry 41 , 102318. 10.1016/j.mtchem.2024.102318 Item availability restricted.

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Abstract

Copper (Cu) nanoparticles, widely utilized as catalysts in industrial applications, exhibit intriguing behavior in structure-sensitive reactions like ethanol dehydrogenation. Contrary to expectations, the catalytic activity does not consistently increase as the size of Cu nanoparticles decreases. In Cu catalysts, the particle size significantly effects the Cu0/Cu+ ratio on the nanoparticle surface. Decreasing the size of Cu nanoparticles promotes their oxidation, leading to the formation of Cu+ and O2− species. This alteration subsequently influences the structural and electronic properties of the catalytic Cu sites. Through Cu nanoparticle calculations, the presence of an O ad-atom was identified to modify the electron density at the Cu site, thereby altering the ethanol adsorption energy and impacting the overall catalytic activity. The increase in O coverage, due to size effects, resulted in a notable decrease in the heat of adsorption on Cu nanoparticles (by approximately 20 kJ mol− 1). The observed high ΔEads indicates that more ethanol molecules could reach the transition state for the reaction, subsequently augmenting turnover rates (TOF) and reducing the apparent activation energy (Eaap) concerning Cu particle size.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Publisher:	Elsevier
ISSN:	2468-5194
Funders:	EPSRC
Date of First Compliant Deposit:	20 December 2024
Date of Acceptance:	18 September 2024
Last Modified:	13 Jan 2025 10:00
URI:	https://orca.cardiff.ac.uk/id/eprint/174882

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