Effect of crystal facets in plasmonic catalysis

• Published in: Nature communications Vol. 15; no. 1; pp. 3923 - 13
• Main Authors: Kang, Yicui, João, Simão M., Lin, Rui, Liu, Kang, Zhu, Li, Fu, Junwei, Cheong, Weng-Chon (Max), Lee, Seunghoon, Frank, Kilian, Nickel, Bert, Liu, Min, Lischner, Johannes, Cortés, Emiliano
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 09.05.2024; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 147/135; 147/143; 639/638/439; 639/638/440/949; 639/925/357/354; Carbon dioxide; Catalysis; Crystals; Electric fields; Energy conversion; Gold; Humanities and Social Sciences; Hydrogen evolution; multidisciplinary; Nanoparticles; Neutralization; Plasmonics; Plasmons; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-47994-y

While the role of crystal facets is well known in traditional heterogeneous catalysis, this effect has not yet been thoroughly studied in plasmon-assisted catalysis, where attention has primarily focused on plasmon-derived mechanisms. Here, we investigate plasmon-assisted electrocatalytic CO 2 reduction using different shapes of plasmonic Au nanoparticles - nanocube (NC), rhombic dodecahedron (RD), and octahedron (OC) - exposing {100}, {110}, and {111} facets, respectively. Upon plasmon excitation, Au OCs doubled CO Faradaic efficiency (FE CO ) and tripled CO partial current density (j CO ) compared to a dark condition, with NCs also improving under illumination. In contrast, Au RDs maintained consistent performance irrespective of light exposure, suggesting minimal influence of light on the reaction. Temperature experiments ruled out heat as the main factor to explain such differences. Atomistic simulations and electromagnetic modeling revealed higher hot carrier abundance and electric field enhancement on Au OCs and NCs than RDs. These effects now dominate the reaction landscape over the crystal facets, thus shifting the reaction sites when comparing dark and plasmon-activated processes. Plasmon-assisted H 2 evolution reaction experiments also support these findings. The dominance of low-coordinated sites over facets in plasmonic catalysis suggests key insights for designing efficient photocatalysts for energy conversion and carbon neutralization. Crystal facets are known to be important in traditional heterogeneous catalysis, yet this effect has not been studied in plasmon-assisted catalysis. Here, the authors investigate the impact facets have on CO 2 reduction using plasmonic Au NPs.