Partial PdAu nanoparticle embedding into TiO 2 support accentuates catalytic contributions from the Au/TiO 2 interface

Lim, Kang Rui Garrick; Kaiser, Selina K.; Herring, Connor J.; Kim, Taek-Seung; Perich, Marta Perxés; Garg, Sadhya; O’Connor, Christopher R.; Aizenberg, Michael; van der Hoeven, Jessi E. S.; Reece, Christian; Montemore, Matthew M.; Aizenberg, Joanna

doi:10.1073/pnas.2422628122

Partial PdAu nanoparticle embedding into TiO ₂ support accentuates catalytic contributions from the Au/TiO ₂ interface

Journal Article · Wed Jan 08 23:00:00 EST 2025 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2422628122· OSTI ID:2497867

; Kaiser, Selina K.; Herring, Connor J.; Kim, Taek-Seung; Perich, Marta Perxés; Garg, Sadhya; ; Aizenberg, Michael; van der Hoeven, Jessi E. S.; Reece, Christian; Montemore, Matthew M.;

Despite the broad catalytic relevance of metal–support interfaces, controlling their chemical nature, the interfacial contact perimeter (exposed to reactants), and consequently, their contributions to overall catalytic reactivity, remains challenging, as the nanoparticle and support characteristics are interdependent when catalysts are prepared by impregnation. Here, we decoupled both characteristics by using a raspberry-colloid-templating strategy that yields partially embedded PdAu nanoparticles within well-defined SiO ₂ or TiO ₂ supports, thereby increasing the metal–support interfacial contact compared to nonembedded catalysts that we prepared by attaching the same nanoparticles onto support surfaces. Between nonembedded PdAu/SiO ₂ and PdAu/TiO ₂ , we identified a support effect resulting in a 1.4-fold higher activity of PdAu/TiO ₂ than PdAu/SiO ₂ for benzaldehyde hydrogenation. Notably, partial nanoparticle embedding in the TiO ₂ raspberry-colloid-templated support increased the metal–support interfacial perimeter and consequently, the number of Au/TiO ₂ interfacial sites by 5.4-fold, which further enhanced the activity of PdAu/TiO ₂ by an additional 4.1-fold. Theoretical calculations and in situ surface-sensitive desorption analyses reveal facile benzaldehyde binding at the Au/TiO ₂ interface and at Pd ensembles on the nanoparticle surface, explaining the connection between the number of Au/TiO ₂ interfacial sites (via the metal–support interfacial perimeter) and catalytic activity. Our results demonstrate partial nanoparticle embedding as a synthetic strategy to produce thermocatalytically stable catalysts and increase the number of catalytically active Au/TiO ₂ interfacial sites to augment catalytic contributions arising from metal–support interfaces.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0012573

OSTI ID:: 2497867

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 2 Vol. 122; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Partial PdAu nanoparticle embedding into TiO ₂ support accentuates catalytic contributions from the Au/TiO ₂ interface