Observation and Characterization of Dicarbonyls on a RhCu Single-Atom Alloy

Wang, Yicheng; Schumann, Julia; Happel, Elizabeth E; Çınar, Volkan; Sykes, E. Charles H.; Stamatakis, Michail; Michaelides, Angelos; Hannagan, Ryan T.

doi:10.1021/acs.jpclett.2c01596

Cited by 6 publications

(4 citation statements)

References 40 publications

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“…by performing rigorous control experiments on the monometallic samples. 187 It should be noted that due to the low stability of metal nanoclusters, the activation conditions used before the chemisorption measurements should be carefully selected to avoid sintering or other types of structural transformation of the nanoclusters. Nevertheless, when the probe molecules interact with binuclear bimetallic sites and bimetallic nanoclusters, the adsorption configuration of the probe molecules could be different to the classic metal nanoparticles.…”

Section: Characterization Of Surface Propertiesmentioning

confidence: 99%

“… Therefore, the precise measurements of the metal sites in bimetallic nanoparticles relies on the identification of the adsorption configuration (mono- or dicarbonyl configuration) of the probe molecule at the measurement conditions (temperature, partial pressure of the probe molecule etc.) by performing rigorous control experiments on the monometallic samples …”

Section: Characterization Of Bimetallic Sitesmentioning

confidence: 99%

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Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

2023

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Heterogeneous bimetallic catalysts have broad applications in industrial processes, but achieving a fundamental understanding on the nature of the active sites in bimetallic catalysts at the atomic and molecular level is very challenging due to the structural complexity of the bimetallic catalysts. Comparing the structural features and the catalytic performances of different bimetallic entities will favor the formation of a unified understanding of the structure−reactivity relationships in heterogeneous bimetallic catalysts and thereby facilitate the upgrading of the current bimetallic catalysts. In this review, we will discuss the geometric and electronic structures of three representative types of bimetallic catalysts (bimetallic binuclear sites, bimetallic nanoclusters, and nanoparticles) and then summarize the synthesis methodologies and characterization techniques for different bimetallic entities, with emphasis on the recent progress made in the past decade. The catalytic applications of supported bimetallic binuclear sites, bimetallic nanoclusters, and nanoparticles for a series of important reactions are discussed. Finally, we will discuss the future research directions of catalysis based on supported bimetallic catalysts and, more generally, the prospective developments of heterogeneous catalysis in both fundamental research and practical applications.

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Section: Characterization Of Surface Propertiesmentioning

confidence: 99%

Section: Characterization Of Bimetallic Sitesmentioning

confidence: 99%

Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

2023

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“…[7][8][9][10][11][12] Oxidation of CO is a fundamental reaction that plays a critical role in many technologically important systems such as the water gas shift reaction, [13][14][15][16][17][18] catalytic converters, [19][20][21] and for the purification of hydrogen used in proton-exchange membrane fuel cells, [22][23][24][25] In addition, CO is an excellent probe molecule for the characterization of surfaces. [26][27][28][29][30] As a result, the adsorption of CO and its oxidation have been extensively studied in the SAC field. For example, DeRita et al demonstrated that isolated Pt atom active sites can dynamically change under reaction conditions when supported on TiO 2 .…”

Section: Introductionmentioning

confidence: 99%

Effect of Surface Temperature on the Distribution and Reactivity of Rh Active Sites for CO Oxidation

Çınar,

Dannar,

Hunt

et al. 2023

ChemCatChem

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Single‐atom catalysts are a fast‐emerging area in which late‐transition metal atoms are supported on oxides, metals, and carbonaceous supports. They show great promise for selective chemical reactions due to their well‐defined active sites, and significantly reduce precious metal loading. However, oxide‐supported single‐atom catalysts have drawbacks such as deactivation due to sintering, and there are on‐going debates about the exact nature of the active sites. Herein we report a model system where the surface temperature during Rh deposition on a copper oxide support dictates the Rh size distribution. Our temperature‐programmed desorption experiments reveal that Rh clusters perform CO oxidation at lower temperature than single atoms, and isotopic labelling demonstrates differences in the mechanism in that the C−O bond is broken and reformed on clusters, as opposed to a pure Mars van Krevelen mechanism for CO oxidation at the single‐atom Rh sites. We further examine the cluster size distributions with scanning tunneling microscopy and X‐ray photoelectron spectroscopy which confirm the presence of both clusters and single atoms for the lower temperature deposition and only single atoms for the higher temperature deposition. Together, these results provide a fundamental understanding of the differences in the CO oxidation mechanism on Rh atoms and clusters.

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“…There are, however, some indications that more than one CO molecule can adsorb on a transition metal substitution atom on a copper surface. Adsorption of two CO molecules has been experimentally observed for Cu surfaces doped with either Co or with Rh, and this has been supported by DFT calculations. This indicates that in order to apply the Sabatier principle correctly and assess the catalytic performance, one needs to consider the adsorption of whatever number of CO molecules is expected to be present under reaction conditions, not just the adsorption of the first CO.…”

mentioning

confidence: 99%

Single-Atom Substituents in Copper Surfaces May Adsorb Multiple CO Molecules

Christiansen,

Peña-Torres,

Jónsson

et al. 2024

J. Phys. Chem. Lett.

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Copper is a good CO 2 electroreduction catalyst as products beyond CO form, but efficiency and selectivity is low. Experiments have shown that an admixture of other elements can help, and computational screening studies have pointed out various promising candidates based on the adsorption of a single CO molecule as a descriptor. Our calculations of CO adsorption on surfaces where a first row transition metal atom replaces a Cu atom show that multiple CO molecules, not just one, bind to the substitutional atom. For Fe, Co, and Ni atoms, a decrease in binding energy is found, but the reverse trend, namely, increasing bond strength, is found for V, Cr, and Mn and the first three CO molecules. Magnetic moment, charge, and position of the substitutional atom are also strongly affected by the CO adsorption in most cases. Magnetic moment is stepwise reduced to zero, and the outward displacement of the substitutional atom increased.

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Observation and Characterization of Dicarbonyls on a RhCu Single-Atom Alloy

Cited by 6 publications

References 40 publications

Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

Effect of Surface Temperature on the Distribution and Reactivity of Rh Active Sites for CO Oxidation

Single-Atom Substituents in Copper Surfaces May Adsorb Multiple CO Molecules

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