Interplay of surface and subsurface contributions in electrocatalysis

Vitale-Sullivan, Molly E.; Stoerzinger, Kelsey A.

doi:10.1016/j.coelec.2023.101252

Cited by 4 publications

(4 citation statements)

References 58 publications

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“…Akbashev et al reported SrTiO 3 with sublayer SrRuO 3 catalyst, in which the subsurface of SrRuO 3 efficiently activates the top layer of SrTiO 3. Regarding the few unit cell thin films of LaFeO 3 and LaFeO 3 /LaNiO 3 system, we regard the near surface region as relevant for OER activity, in agreement with Vitale-Sullivan’s view …”

Section: Introductionsupporting

confidence: 86%

“…25 The bilayer thin films in many cases exhibit special properties and 26 Regarding the few unit cell thin films of LaFeO 3 and LaFeO 3 /LaNiO 3 system, we regard the near surface region as relevant for OER activity, in agreement with Vitale-Sullivan's view. 27 In the investigation of complex transition-metal systems, in situ X-ray absorption spectroscopy (XAS) plays an important role in probing the electronic structure (valence, spin states, covalence, and charge transfer) under working conditions regardless of long-range or short-range order. 28 We used fluorescence yield (FY) XAS, which is a bulk-sensitive technique.…”

Section: ■ Introductionmentioning

confidence: 99%

“… 26 Regarding the few unit cell thin films of LaFeO 3 and LaFeO 3 /LaNiO 3 system, we regard the near surface region as relevant for OER activity, in agreement with Vitale-Sullivan’s view. 27 …”

Section: Introductionmentioning

confidence: 99%

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In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction

Che,

van den Bosch,

et al. 2024

J. Phys. Chem. C

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We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO 3 and LaFeO 3 /LaNiO 3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La 0.67 Sr 0.33 MnO 3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca 2 Nb 3 O 10 nanosheet-buffered 100 nm SiN x membranes. The in situ Fe and Ni Kedges XAS spectra were measured from the backside of the SiN x membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO 3 film.

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Section: Introductionsupporting

confidence: 86%

Section: ■ Introductionmentioning

confidence: 99%

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In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction

Che,

van den Bosch,

et al. 2024

J. Phys. Chem. C

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“…4a, Methods), showing Pd@Pt<1L>Pd@Pt2L>Pd@Pt5L>Pd@Pt8L. It is been reported that the effective distance for subsurface to impact on catalysis is within the first three atomic layers 40,41 . Using the fourth valley of pair distribution function (PDF) as threshold, we identify all LCHs in the distance within the first three atomic layers, where we define a heterogeneous center as a Pt/Pd atom whose surrounding is a chemically mixed coordination shell composed of both Pt and Pd (Fig.…”

Section: Local Chemical Heterogeneity On the Surfacementioning

confidence: 89%

Revealing the interface-driven atomic local chemical heterogeneity in bimetallic catalysts in three dimensions

Zhou,

Xie,

Xie

et al. 2024

Preprint

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Subsurface atomic configurations exert a profound influence on the surface electronic structures, thereby playing a critical role in electrocatalysis. However, an in-depth understanding of intricate three-dimensional surface/subsurface structures in catalysts remain limited due to the weak interfacial signal and the inherent complexity in local structural and compositional nuances. Here, by determining the entirety of surface and subsurface atomic structures in Pd@Pt model catalysts through atomic-resolution electron tomography, our investigation reveals the pivotal role of atomic-scale local chemical heterogeneity, driven by atomic interfacial diffusion at the core-shell interface, in modulating the electronic structures and consequently tuning the catalytic behaviors in electrocatalytic ethanol oxidation reaction. Density functional theory calculations further elucidate that the atomically interfacial diffusion notably enhances OH adsorption energy at Pt sites while decreases CO adsorption energy at Pd sites on the surface by shifting the d-band center. These results broaden the existing paradigm of atomic interplay between surface and subsurface realms in bimetallic catalysts at fundamental level, offering valuable information for efficient catalyst design.

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Modifications in Subsurface of Catalysts: Impact of Bringing in Electrophilicity on Catalytic Applications

Khan,

2024

ChemistrySelect

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Surface, interface, and subsurface in catalysts are broadly perceived as independent units in materials, relying on diverse bonding environments and are recurrently studied discretely because of experimental challenges in distinguishing the surface and subsurface effects. Metal crystals, isolated atoms, or metal nanoparticles in supported catalysts induce an electrophilic nature in subsurface, enhancing the catalysis efficiency. In this review, the influence of modification in subsurface of catalysts and their specific catalytic outputs are discussed. Key approaches and techniques for insertion of subsurface modifications and impact of electrophilicity upon catalysis upgradation are observed. A compilation of frequently used chemical reactions catalyzed by subsurface‐modified catalysts have been structured and thoroughly illustrated.

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Interplay of surface and subsurface contributions in electrocatalysis

Cited by 4 publications

References 58 publications

In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction

In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction

Revealing the interface-driven atomic local chemical heterogeneity in bimetallic catalysts in three dimensions

Modifications in Subsurface of Catalysts: Impact of Bringing in Electrophilicity on Catalytic Applications

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Interplay of surface and subsurface contributions in electrocatalysis

Cited by 4 publications

References 58 publications

In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction

In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction

Revealing the interface-driven atomic local chemical heterogeneity in bimetallic catalysts in three dimensions

Modifications in Subsurface of Catalysts: Impact of Bringing in Electrophilicity on Catalytic Applications

Contact Info

Product

Resources

About

In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction

In Situ X-ray Absorption Spectroscopy of LaFeO₃ and LaFeO₃/LaNiO₃ Thin Films in the Electrocatalytic Oxygen Evolution Reaction