Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

Wang, Yang‐Gang; Mei, Donghai; Glezakou, Vassiliki Alexandra; Li, Jun; Rousseau, Roger

doi:10.1038/ncomms7511

Cited by 400 publications

(482 citation statements)

References 57 publications

(79 reference statements)

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“…In this section, we discuss the methods and models that are mainly being used in the nanocluster catalysis community, and emphasize why we need to be careful when using some of these models to describe the catalytic properties when the catalytic interface is so dynamic. It is clear that finding the correlation between catalyst morphology and catalytic performance is essential to designing new catalysts with enhanced efficiency . Hence, a major tool is global optimization, already discussed above, to be used for the finding of both the global and the accessible local minima of cluster catalysts.…”

Section: Notes On the Computational Methodsmentioning

confidence: 99%

Surface‐supported cluster catalysis: Ensembles of metastable states run the show

Zandkarimi

Alexandrova

2019

WIREs Comput Mol Sci

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It has recently been shown that the dynamic behavior of surface‐supported nanocluster catalysts in realistic reaction conditions defies conventional models used in catalysis. This opens new doors in catalysis by giving more leverage in catalyst design, but also requires a major revision of the understanding of how dynamic heterogeneous catalytic interfaces operate, as well as of the computational approaches of catalyst modeling, and experimental methods of catalyst characterization. Major aspects of the new paradigm include the collective action of many catalyst states that form a statistical ensemble in reaction conditions, the catalytic activity and selectivity being driven by rare and metastable catalyst states, reaction thermodynamics and kinetics being controlled by different states of the catalyst, broken scaling relationships, non‐Arrhenius behaviors, and catalyst dynamic restructuring being an essential part of the reaction mechanism. For computation, this complexity means the departure from the standard density functional theory calculations of reaction mechanisms on a single catalyst structure. For experiment, it calls for the development of operando characterization tools with the per‐site resolution and the ability to find the minority sites that govern the catalytic activity. For catalyst design, the goal becomes the creation of the catalyst state (geometric and electronic) that might not be present in the as‐prepared catalyst, but would develop in the reaction conditions and would have the desired activity then. While cluster catalysts are the most dramatic in their dynamic fluxionality, other amorphous interfaces also exhibit some of it, and thus are also subject to similar paradigm revision. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis

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Section: Notes On the Computational Methodsmentioning

confidence: 99%

Surface‐supported cluster catalysis: Ensembles of metastable states run the show

Zandkarimi

Alexandrova

2019

WIREs Comput Mol Sci

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“…[49] To develop correlations between the properties and performance of SACs,i ti sn ecessary to improve our knowledge of their evolution under reaction conditions.The potential influence of dynamic effects,such as the generation [66] or aggregation [67] of single-atom active centers during catalysis,aswell as changes in their coordination during the catalytic cycle, [68] is increasingly recognized. [49] To develop correlations between the properties and performance of SACs,i ti sn ecessary to improve our knowledge of their evolution under reaction conditions.The potential influence of dynamic effects,such as the generation [66] or aggregation [67] of single-atom active centers during catalysis,aswell as changes in their coordination during the catalytic cycle, [68] is increasingly recognized.…”

Section: Properties Of Sacsmentioning

confidence: 99%

The Multifaceted Reactivity of Single‐Atom Heterogeneous Catalysts

2018

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Single-atom heterogeneous catalysts (SACs) attached to carefully chosen hosts are attracting considerable interest; principally because they offer maximum utilization per metal atom and are usually readily recyclable. However, diminution of the atomic population of nanoparticles or nanoclusters to single atoms can significantly alter reactivity because of the consequent changes in the active-site structure. By examining various diverse applications, we ascertain whether the performance of SACs is enhanced or suppressed. We also note that SACs generally display unique kinds of catalytic cycles. The choice of host is crucial since it influences both the electronic and steric environment of the metal center. Moreover, it may function as a cocatalyst. All these aspects impact upon the design of new SACs, which exhibit similarities to hetero- and homogeneous predecessors. Additionally, SACs offer a viable replacement of soluble metal complexes in processes that remain difficult to heterogenize.

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“…The climbing image nudged elastic band (CI-NEB) method, 44 which searches to find the saddle point, as well as the minimum energy path for reactions by estimating the tangent to the path at each image, was adopted for the reaction pathway 45,46 shown in Fig. 3, where the end states I to V were obtained by relaxation and I is set as the reference.…”

Section: A Reaction Pathwaymentioning

confidence: 99%

Phonocatalysis. An ab initio simulation experiment

Kim

Kaviany

2016

AIP Advances

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Using simulations, we postulate and show that heterocatalysis on large-bandgap semiconductors can be controlled by substrate phonons, i.e., phonocatalysis. With ab initio calculations, including molecular dynamic simulations, the chemisorbed dissociation of XeF6 on h-BN surface leads to formation of XeF4 and two surface F/h-BN bonds. The reaction pathway and energies are evaluated, and the sorption and reaction emitted/absorbed phonons are identified through spectral analysis of the surface atomic motion. Due to large bandgap, the atomic vibration (phonon) energy transfer channels dominate and among them is the match between the F/h-BN covalent bond stretching and the optical phonons. We show that the chemisorbed dissociation (the pathway activation ascent) requires absorption of large-energy optical phonons. Then using progressively heavier isotopes of B and N atoms, we show that limiting these high-energy optical phonons inhibits the chemisorbed dissociation, i.e., controllable phonocatalysis.

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Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

Cited by 400 publications

References 57 publications

Surface‐supported cluster catalysis: Ensembles of metastable states run the show

Surface‐supported cluster catalysis: Ensembles of metastable states run the show

The Multifaceted Reactivity of Single‐Atom Heterogeneous Catalysts

Phonocatalysis. An ab initio simulation experiment

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