Factors in Gold Nanocatalysis: Oxidation of CO in the Non‐Scalable Size Regime

Landman, Uzi; Yoon, Bokwon; Zhang, Chun; Arenz, Matthias

doi:10.1002/chin.200745202

Cited by 31 publications

(54 citation statements)

References 34 publications

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“…(16) implies that reducible supports, which lower the Fermi level, contribute to the adsorption of molecules while oxidizing supports, which raise the Fermi level, improve the desorption of the products. This agrees well with the experimental results on reducible supports [11,14,16].…”

Section: The Size Dependence Of the Reaction Ratesupporting

confidence: 92%

“…conditions than traditional catalysts [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. CO oxidation is one of the important oxidation reactions catalyzed by gold NPs, where non-monotonic size effects were experimentally observed in the range of 1-5 nm [3][4][5][6][7][8][9][10][11][12].…”

mentioning

confidence: 99%

“…CO oxidation is one of the important oxidation reactions catalyzed by gold NPs, where non-monotonic size effects were experimentally observed in the range of 1-5 nm [3][4][5][6][7][8][9][10][11][12]. Other factors established experimentally that contribute to the reaction activity of gold NPs include the nature of the support [5,6,10,11], low coordinated gold atoms [8][9][10], defects presented at the interfaces [14,15], a non-metallic nature of gold clusters [5] and photon-induced or injected hot electrons [17,18]. In spite of intense research in this field, the origin of the size effects has not been completely established yet although many important aspects of the reaction were theoretically investigated [8-10, 14,15,19,20].…”

mentioning

confidence: 99%

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Wolkenstein’s Model of Size Effects in CO Oxidation by Gold Nanoparticles

Turaeva

Krueger

2020

Catalysts

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The theoretical model of a volcano-type size dependence of extraordinary catalytic activity of gold nanoparticles in CO oxidation is proposed based on the electronic theory of catalysis, the jellium model of metal clusters and the d-band model of formation bonds in transition metals. The kinetics of the general mechanism of CO oxidation reaction catalyzed by gold nanoparticles through dissociative adsorption of oxygen molecules and interaction with CO molecules from the gas-phase is considered by introducing electronic steps into 3-step mechanism of the reaction, corresponding to transitions between weak and strong chemisorbed states of intermediates. By introducing the exponential dependences of the fractions of weak and strong chemisorbed intermediates (O, CO2) on the size dependent Fermi level of the metal cluster with respect to antibonding energy levels of the intermediates, a volcano-type dependence of reaction rate on the size of gold nanoparticles is obtained. The dependence of the reaction rate upon the supports is taken into account by introducing the additional energy term into the Fermi level of the metal catalyst.

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Section: The Size Dependence Of the Reaction Ratesupporting

confidence: 92%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Wolkenstein’s Model of Size Effects in CO Oxidation by Gold Nanoparticles

Turaeva

Krueger

2020

Catalysts

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“…Understanding and potential utilization of the size-dependent evolution of the physical and chemical properties of materials aggregates, from the molecular and cluster regime to the condensed matter phase are outstanding challenges of modern materials science, with investigations starting in the late 1990's on size-selected supported nanometer-scale metal cluster catalysts heralding the emergence of nanocatalysis as a promising direction in heterogeneous catalysis [1,3,29].…”

Section: Reactions Catalyzed By Supported Nanoclustersmentioning

confidence: 99%

Assessing the concept of structure sensitivity or insensitivity for sub-nanometer catalyst materials

et al. 2016

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The nature of the nano-catalyzed hydrogenation of ethylene, yielding benchmark information pertaining to the concept of structure sensitivity/insensitivity and its applicability at the bottom of the catalyst particle size-range, is explored with experiments on size-selected Ptn (n=7-40) clusters softlanded on MgO, in conjunction with first-principles simulations. As in the case of larger particles both the direct ethylene hydrogenation channel and the parallel hydrogenation-dehydrogenation ethylidyne-producing route must be considered, with the fundamental uncovering that at the <1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to the structure insensitivity found for larger particles. In this size-regime, the chemical properties can be modulated and tuned by a single atom, reflected by the onset of low temperature hydrogenation at T >150 K catalyzed by Pt n (n≥10) clusters, with maximum room temperature reactivity observed for Pt 13 using a pulsed molecular beam technique. Structure insensitive behavior, inherent for specific cluster sizes at ambient temperatures, can be induced in the more active sizes, e.g. Pt 13 , by a temperature increase, up to 400 K, which opens dehydrogenation channels leading to ethylidyne formation. This reaction channel was, however found to be attenuated on Pt 20 , as catalyst activity remained elevated after the 400 K step. Pt 30 displayed behavior which can be understood from extrapolating bulk properties to this size range; in particular the calculated d-band center. In the non-scalable subnanometer size regime, however, precise control of particle size may be used for atom-by-atom tuning and manipulation of catalyzed hydrogenation activity and selectivity.

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“…This is largely because supported metal clusters provide us with relatively easily computable and well-defined model systems for studying quantum size effects in catalysis. [112][113][114] Furthermore, their size-dependent reactivity and selectivity can be utilized to control the performance of the system by tuning the exact cluster size and the electronic structure of the system. [114][115][116][117][118]…”

Section: Induced Chiralitymentioning

confidence: 99%

Spectroscopy for model heterogeneous asymmetric catalysis

Kartouzian¹

2019

Chirality

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Heterogeneous catalysis has vastly benefited from investigations performed on model systems under well‐controlled conditions. The application of most of the techniques utilized for such studies is not feasible for asymmetric reactions as enantiomers possess identical physical and chemical properties unless while interacting with polarized light and other chiral entities. A thorough investigation of a heterogeneous asymmetric catalytic process should include probing the catalyst prior to, during, and after the reaction as well as the analysis of reaction products to evaluate the achieved enantiomeric excess. I present recent studies that demonstrate the strength of chiroptical spectroscopic methods to tackle the challenges in investigating model heterogeneous asymmetric catalysis covering all the abovementioned aspects.

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Factors in Gold Nanocatalysis: Oxidation of CO in the Non‐Scalable Size Regime

Cited by 31 publications

References 34 publications

Wolkenstein’s Model of Size Effects in CO Oxidation by Gold Nanoparticles

Wolkenstein’s Model of Size Effects in CO Oxidation by Gold Nanoparticles

Assessing the concept of structure sensitivity or insensitivity for sub-nanometer catalyst materials

Spectroscopy for model heterogeneous asymmetric catalysis

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