Atom-by-atom assembly reveals structure–performance control in PdCu catalysts for CO 2 hydrogenation to methanol

Smith, Louise R., Kohlrausch, Emerson C., Aggett, Kieran J., Samperi, Mario, Ghaderzadeh, Sadegh, Weilhard, Andreas, Norman, Luke T., Gow, Isla E., Chen, Yifan, Bonura, Giuseppe, Cannilla, Catia, Besley, Elena, Morgan, David J. ORCID: https://orcid.org/0000-0002-6571-5731, Slater, Thomas J. A. ORCID: https://orcid.org/0000-0003-0372-1551, Khlobystov, Andrei N., Alves Fernandes, Jesum and Hutchings, Graham J. ORCID: https://orcid.org/0000-0001-8885-1560 2025. Atom-by-atom assembly reveals structure–performance control in PdCu catalysts for CO 2 hydrogenation to methanol. Chemical Science 10.1039/d5sc06681f

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Abstract

The catalytic conversion of CO2 to methanol using bimetallic materials presents a promising pathway for sustainable chemical production. A major challenge is the lack of atomic-level control over the catalyst structure and composition, which hinders the understanding of each metal's role in activity and selectivity. Here, we present a solvent-free on-surface assembly of PdCu bimetallic particles, directly from atoms, on ZnO with precise control of the order and quantity of metal atoms added. This atomic-defined interface reveals when atoms are added simultaneously, the metal with stronger ZnO binding governs particle size, but when introduced sequentially the first metal determines particle size. The simultaneously deposited PdCu exhibits the highest reported methanol productivity for PdCu-systems, achieving 8.2 mol h−1 molmetal−1 at 270 °C and 20 bar. In this catalyst, Cu enhances CO2 adsorption, suppresses Zn incorporation into the PdCu structure and modulates Pd binding strength to reaction intermediates. This enhances methanol selectivity while maintaining high Pd-driven CO2 conversion.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Schools > Chemistry Research Institutes & Centres > Cardiff Catalysis Institute (CCI)
Additional Information:	License information from Publisher: LICENSE 1: URL: https://creativecommons.org/licenses/by/3.0/, Start Date: 2025-10-20
Publisher:	Royal Society of Chemistry
ISSN:	2041-6520
Date of First Compliant Deposit:	3 November 2025
Date of Acceptance:	20 October 2025
Last Modified:	04 Nov 2025 02:30
URI:	https://orca.cardiff.ac.uk/id/eprint/182081

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