Reactivity of Atomic Gold Anions toward Oxygen and the Oxidation of CO:  Experiment and Theory

Ml, Kimble; Aw, Castleman; Mitrić, Roland; Bürgel, Christian; Bonacić-Koutecký,

doi:10.1021/ja030544b

Cited by 199 publications

(190 citation statements)

References 28 publications

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“…Prior to the experimental investigations of Haruta [58], gold was considered to be inert. In recent years, numerous experimental and theoretical studies have revealed the contrary, prompting extensive work to elucidate the mechanisms involved [59][60][61][62][63][64][65][66][67]. Important remaining questions included: Do small gold clusters contribute to the presence of O-atoms sufficient to promote oxidation of CO; and what is the influence of charge accumulation or deficiency on the reactivity?…”

Section: Elucidating Mechanisms Of Catalytic Reactionsmentioning

confidence: 99%

Cluster Structure and Reactions: Gaining Insights into Catalytic Processes

Castleman

2011

Catal Lett

157

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To many researchers outside the field of cluster science it may come as a surprise that much can be learned of its relevance to catalysis, even restricting the discussion to ionized systems. This perspective is largely focused on catalytic oxidation reactions in which oxygen radical centers on transition metal oxides play a dominant role. The objective is to present how fundamental insights into reaction mechanisms can be gained through employing alternative approaches that complement rather than supersede more conventional methods in t he field of catalysis. In view of the well acknowledged role of defect centers in effecting reactivity, and the preponderance of recent papers presenting evidence of the importance of charged sites, the need/desire to conduct repetitive experiments is clear. Presented herein are approaches using clusters to accomplish this in order to unravel fundamental catalytic reaction mechanisms, and to use identified superatoms and the concepts of element mimics to tailor catalysts with desired functionality.

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Section: Elucidating Mechanisms Of Catalytic Reactionsmentioning

confidence: 99%

Cluster Structure and Reactions: Gaining Insights into Catalytic Processes

Castleman

2011

Catal Lett

157

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“…2 Typical catalysts for CO oxidation consist of noble metals, such as Pt, [3][4][5][6][7][8] Pd, 5,6,[9][10][11][12] Ru 13 and Au, [14][15][16][17] and they have been widely investigated for decades. To further increase the catalytic performance and reduce the cost, recent research attention has turned to ''single atom catalysts'' (SACs) 18,19 by downsizing the catalyst to the atomic scale, which provides a platform for the establishment of new fundamental science as well as the design of excellent catalysts.…”

Section: Introductionmentioning

confidence: 99%

A promising single atom catalyst for CO oxidation: Ag on boron vacancies of h-BN sheets

Yang

et al. 2017

Phys. Chem. Chem. Phys.

103

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Single atom catalysts (SACs) have attracted broad research interest in recent years due to their importance in various fields, such as environmental protection and energy conversion. Here, we discuss the mechanisms of CO oxidation to CO 2 over single Ag atoms supported on hexagonal boron-nitride sheets (Ag 1 /BN) through systematic van der Waals inclusive density functional theory (DFT-D)calculations. The Ag adatom can be anchored onto a boron defect (V B ), as suggested by the large energy barrier of 3.12 eV for Ag diffusion away from the V B site. Three possible mechanisms (i.e., Eley-Rideal, Langmuir-Hinshelwood, and termolecular Eley-Rideal) of CO oxidation over Ag 1 /BN are investigated. Due to ''CO-Promoted O 2 Activation'', the termolecular Eley-Rideal (TER) mechanism is the most relevant one for CO oxidation over Ag 1 /BN and the rate-limiting reaction barrier is only 0.33 eV. More importantly, the first principles molecular dynamics simulations confirm that CO oxidation via the TER mechanism may easily occur at room temperature. Analyses with the inclusion of temperature and entropy effects further indicate that the CO oxidation via the TER mechanism over Ag 1 /BN is thermodynamically favorable in a broad range of temperatures.

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“…41 CO oxidation on anionic gold clusters occurs via the EleyRideal mechanism, 38, 51, 52 while CO oxidation on cationic gold atoms can occur via both Eley-Rideal and LangmuirHinshelwood mechanisms. 52 Therefore, the charge state of gold particles (which can be controlled by the support) can considerably influence their reactivity and define the reaction mechanism. 47,48,53 On the other hand it is commonly accepted that the inert supports, such as SiO 2 or hexagonal boron nitride (h-BN), do not affect the electronic and geometric structure of the supported clusters.…”

Section: Introductionmentioning

confidence: 99%

CO oxidation on h-BN supported Au atom

Gao

Lyalin

Taketsugu

2013

The Journal of Chemical Physics

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The mechanism of CO oxidation by O 2 on Au atoms supported on the pristine and defected hexagonal boron nitride (h-BN) surface has been studied theoretically using density functional theory. It is found that O 2 binds stronger than CO on an Au atom supported on the defect free h-BN surface and h-BN surface with nitrogen vacancy (V N @h-BN), but weaker than CO on a free Au atom or Au trapped by a boron vacancy (V B @h-BN). The excess of the positive or negative charge on Au can considerably change its catalytic properties and enhance activation of the adsorbed O 2 . Coadsorption of CO and O 2 on Au, Au/V N @h-BN, and Au/V B @h-BN results in additional charge transfer to O 2 . Various pathways of the CO oxidation reaction by molecular oxygen are studied. We found two different pathways for CO oxidation: a two-step pathway where two CO 2 molecules are formed independently, and a self-promotion pathway where oxidation of the first CO molecule is promoted by the second CO molecule. Interaction of Au with the defect-free and defected h-BN surface considerably affects the CO oxidation reaction pathways and barriers. Therefore, Au supported on the h-BN surface (pristine or defected) cannot be considered as pseudo-free atom and support effects have to be taken into account, even when the interaction of Au with the support is weak.

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Reactivity of Atomic Gold Anions toward Oxygen and the Oxidation of CO: Experiment and Theory

Cited by 199 publications

References 28 publications

Cluster Structure and Reactions: Gaining Insights into Catalytic Processes

Cluster Structure and Reactions: Gaining Insights into Catalytic Processes

A promising single atom catalyst for CO oxidation: Ag on boron vacancies of h-BN sheets

CO oxidation on h-BN supported Au atom

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