Restructuring dynamics of surface species in bimetallic nanoparticles probed by modulation excitation spectroscopy

Prahlad K. Routh; Evgeniy Redekop; Sebastian Prodinger; Jessi E.S. van der Hoeven; Kang Rui Garrick Lim; Joanna Aizenberg; Maarten Nachtegaal; Adam H. Clark; Anatoly I. Frenkel

doi:10.1038/s41467-024-51068-4

Restructuring dynamics of surface species in bimetallic nanoparticles probed by modulation excitation spectroscopy

Prahlad K. Routh, Evgeniy Redekop, Sebastian Prodinger, Jessi E.S. van der Hoeven, Kang Rui Garrick Lim, Joanna Aizenberg, Maarten Nachtegaal, Adam H. Clark, Anatoly I. Frenkel^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Restructuring of metal components on bimetallic nanoparticle surfaces in response to the changes in reactive environment is a ubiquitous phenomenon whose potential for the design of tunable catalysts is underexplored. The main challenge is the lack of knowledge of the structure, composition, and evolution of species on the nanoparticle surfaces during reaction. We apply a modulation excitation approach to the X-ray absorption spectroscopy of the 30 atomic % Pd in Au supported nanocatalysts via the gas (H₂ and O₂) concentration modulation. For interpreting restructuring kinetics, we correlate the phase-sensitive detection with the time-domain analysis aided by a denoising algorithm. Here we show that the surface and near-surface species such as Pd oxides and atomically dispersed Pd restructured periodically, featuring different time delays. We propose a model that Pd oxide formation is preceded by the build-up of Pd regions caused by oxygen-driven segregation of Pd atoms towards the surface. During the H₂ pulse, rapid reduction and dissolution of Pd follows an induction period which we attribute to H₂ dissociation. Periodic perturbations of nanocatalysts by gases can, therefore, enable variations in the stoichiometry of the surface and near-surface oxides and dynamically tune the degree of oxidation/reduction of metals at/near the catalyst surface.

Original language	English
Article number	6736 (2024)
Journal	Nature Communications
Volume	15
Issue number	1
DOIs	https://doi.org/10.1038/s41467-024-51068-4
Publication status	Published - 7 Aug 2024

Bibliographical note

Publisher Copyright:
© The Author(s) 2024.

Funding

This project was primarily supported by Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Award No. DE-SC0012573. SP acknowledges the iCSI (industrial Catalysis Science and Innovation) Centre for Research based Innovation, which receives financial support from the Research Council of Norway under contract no. 237922. KRGL acknowledges financial support from the Agency for Science, Technology and Research (A*STAR) Singapore National Science Scholarship (PhD). The Swiss Light Source is acknowledged for the provision of beamtime at the SuperXAS beamline. JESvdH acknowledges funding from the NWO Veni project with project number VI.Veni.212.046 which is financed by the Dutch Research Council (NWO), and funding for access to the TFS Spectra300 at EM Utrecht from the Netherlands Electron Microscopy Infrastructure (NEMI), project number 184.034.014, part of the National Roadmap and financed by the Dutch Research Council. DAS:The data that support the findings of this study are available from the corresponding author upon request.

Funders	Funder number
Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center - US Department of Energy, Office of Science, Office of Basic Energy Sciences	DE-SC0012573
Research Council of Norway	237922
Agency for Science, Technology and Research (A*STAR) Singapore National Science Scholarship (PhD)
Dutch Research Council (NWO)	VI.Veni.212.046
Netherlands Electron Microscopy Infrastructure (NEMI)	184.034.014
Dutch Research Council

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title = "Restructuring dynamics of surface species in bimetallic nanoparticles probed by modulation excitation spectroscopy",

abstract = "Restructuring of metal components on bimetallic nanoparticle surfaces in response to the changes in reactive environment is a ubiquitous phenomenon whose potential for the design of tunable catalysts is underexplored. The main challenge is the lack of knowledge of the structure, composition, and evolution of species on the nanoparticle surfaces during reaction. We apply a modulation excitation approach to the X-ray absorption spectroscopy of the 30 atomic % Pd in Au supported nanocatalysts via the gas (H2 and O2) concentration modulation. For interpreting restructuring kinetics, we correlate the phase-sensitive detection with the time-domain analysis aided by a denoising algorithm. Here we show that the surface and near-surface species such as Pd oxides and atomically dispersed Pd restructured periodically, featuring different time delays. We propose a model that Pd oxide formation is preceded by the build-up of Pd regions caused by oxygen-driven segregation of Pd atoms towards the surface. During the H2 pulse, rapid reduction and dissolution of Pd follows an induction period which we attribute to H2 dissociation. Periodic perturbations of nanocatalysts by gases can, therefore, enable variations in the stoichiometry of the surface and near-surface oxides and dynamically tune the degree of oxidation/reduction of metals at/near the catalyst surface.",

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Restructuring dynamics of surface species in bimetallic nanoparticles probed by modulation excitation spectroscopy

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