Learning from the Heterogeneity at Electrochemical Interfaces

Ryu, C. Hyun; Lee, Hyein; Lee, Heekwon; Ren, Haixia

doi:10.1021/acs.jpclett.2c02009

Cited by 22 publications

(21 citation statements)

References 89 publications

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“…Intra- and interparticle communication between different catalytic sites was probed by statistical analysis of single molecule fluorescence microscopy measurements. , Pd nanorods, Au nanorods, and Au nanoplates were examined as nanocatalysts for various probe reactions. Intraparticle sites communication was observed by pairing catalytic event in region i of the catalyst to subsequent event in region j (Figure b).…”

Section: Inter- and Intraparticle Diffusionmentioning

confidence: 99%

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Mechanistic Insights Gained by High Spatial Resolution Reactivity Mapping of Homogeneous and Heterogeneous (Electro)Catalysts

et al. 2023

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The recent development of high spatial resolution microscopy and spectroscopy tools enabled reactivity analysis of homogeneous and heterogeneous (electro)catalysts at previously unattainable resolution and sensitivity. These techniques revealed that catalytic entities are more heterogeneous than expected and local variations in reaction mechanism due to divergences in the nature of active sites, such as their atomic properties, distribution, and accessibility, occur both in homogeneous and heterogeneous (electro)catalysts. In this review, we highlight recent insights in catalysis research that were attained by conducting high spatial resolution studies. The discussed case studies range from reactivity detection of single particles or single molecular catalysts, inter- and intraparticle communication analysis, and probing the influence of catalysts distribution and accessibility on the resulting reactivity. It is demonstrated that multiparticle and multisite reactivity analyses provide unique knowledge about reaction mechanism that could not have been attained by conducting ensemble-based, averaging, spectroscopy measurements. It is highlighted that the integration of spectroscopy and microscopy measurements under realistic reaction conditions will be essential to bridge the gap between model-system studies and real-world high spatial resolution reactivity analysis.

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Section: Inter- and Intraparticle Diffusionmentioning

confidence: 99%

Section: Inter- and Intraparticle Diffusionmentioning

confidence: 99%

Mechanistic Insights Gained by High Spatial Resolution Reactivity Mapping of Homogeneous and Heterogeneous (Electro)Catalysts

et al. 2023

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“…One effective method to study the electrochemical activity at the grain boundaries, which eliminates the ambiguity from ensemble averaging, is single-entity electrochemistry: to study the electrochemistry of the entity, e.g., single particle, single cell, and single molecule, one at a time. − If one can study one grain boundary at a time, interpreting the activity results will be greatly simplified. Scanning electrochemical cell microscopy (SECCM) is a versatile technique that allows the study of local electrochemistry at the nanoscale and single-entity level, − which is suitable for local electrochemical measurement at single grain boundaries.…”

Section: Introductionmentioning

confidence: 99%

Interfacial Structure and Energy Determine the Heterogeneity in the Electrochemical Metal Dissolution Activity at Grain Boundary

Wang

Ren

2023

Chem. Mater.

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Grain boundaries are defects present in polycrystalline materials that often possess unique electrochemical activity, including in metal dissolution reactions. The structural origin of the enhanced activity at some grain boundaries is often experimentally elusive because of the ambiguity in attributing the activity to a specific grain boundary due to ensemble averaging. Herein, we experimentally elucidate the structural and energetic effect of grain boundary on metal dissolution reaction by colocalized scanning electrochemical cell microscopy (SECCM) and electron microscopy assisted by focused ion beam (FIB). The local dissolution activity at isolated locations containing only single grain boundaries is measured from SECCM. The structure and orientation of the same grain boundary planes are characterized by electron backscatter diffraction and FIB, which is confirmed by transmission electron microscopy (TEM). The relative interfacial energy of these grain boundaries is also measured via the thermal grooving method. Using anodic dissolution at Ag grain boundaries as a model system, we found that the dissolution rate increases with grain boundary energy and the density of broken bonds at the grain boundary plane. The results explain the heterogeneity in the activity of metal dissolution at different grain boundaries, elucidating the initiation sites of metal dissolution. The method developed here is generally applicable to revealing the structure− activity correlation of electrochemical reactions at grain boundaries.

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“…[6][7][8][9] To succeed in this task, it is mandatory a deep understanding of the relation between the catalyst composition and structure with its performance (activity, selectivity and durability), i.e., the so-called structure-activity relationship. Unfortunately, except for some model systems, [10][11][12][13] it is tricky to succeed in this task due to the multiple factors playing a relevant and simultaneous role in (electro-)catalytic processes. [14] It is worth pointing out that there is an intrinsic complexity introduced by the word "structure" in this field: depending on the system/material of interest, it can refer to the shape, and/or size, and/or facet crystallographic orientation, and/or crystallographic structure, etc.…”

Section: Introductionmentioning

confidence: 99%

Development of electrochemical cells for spatially resolved analysis using a multi-technique approach: from conventional experiments to X-ray nanoprobe beamlines

Vicente

Raju

Gomes

et al. 2023

Preprint

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Real (electro-)catalysts are often heterogeneous, and their activity and selectivity depend on the properties of specific active sites. Therefore, unveiling the so-called structure-activity relationship is essential for a rational search for better materials and, consequently, for the development of the field of (electro-)catalysts. Thus, spatially resolved techniques are powerful tools as they allow us to characterize and/or measure the activity and selectivity of different regions of heterogeneous catalysts. To take full advantage of that, we have developed spectroelectrochemical cells (SEC) to perform spatially resolved analysis using X-ray nanoprobe synchrotron beamlines, and conventional pieces of equipment. Here, we describe the techniques available at the Carnaúba beamline at Sirius-LNLS storage ring, then we show how our SECs enable obtaining X-ray (XRF, XRD, XAS, etc.) and vibrational spectroscopy (FTIR and Raman) contrast images. Through some proof-of-concept experiments, we demonstrate how using a multi-technique approach could render a complete and detailed analysis of an (electro-)catalyst overall performance.

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Learning from the Heterogeneity at Electrochemical Interfaces

Cited by 22 publications

References 89 publications

Mechanistic Insights Gained by High Spatial Resolution Reactivity Mapping of Homogeneous and Heterogeneous (Electro)Catalysts

Mechanistic Insights Gained by High Spatial Resolution Reactivity Mapping of Homogeneous and Heterogeneous (Electro)Catalysts

Interfacial Structure and Energy Determine the Heterogeneity in the Electrochemical Metal Dissolution Activity at Grain Boundary

Development of electrochemical cells for spatially resolved analysis using a multi-technique approach: from conventional experiments to X-ray nanoprobe beamlines

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