Lonely Atoms with Special Gifts: Breaking Linear Scaling Relationships in Heterogeneous Catalysis with Single-Atom Alloys

Darby, Matthew T.; Stamatakis, Michail; Michaelides, Angelos; Sykes, E. Charles H.

doi:10.1021/acs.jpclett.8b01888

Cited by 252 publications

(288 citation statements)

References 98 publications

(283 reference statements)

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“…H2 dissociation) are activated on the highly active PGM dopant atom, and after spillover the catalysis occurs on the relatively inert coinage metal. 10 This has been verified by density functional theory (DFT) as well as surface science studies. [10][11][12] In addition SAAs exhibit superior activity compared to their monometallic hosts 13 in conjunction with exceptional selectivity unrivalled by pure PGMs.…”

Section: Introductionmentioning

confidence: 76%

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CO-Induced Aggregation and Segregation of Highly Dilute Alloys: A Density Functional Theory Study

2019

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Highly dilute binary alloys composed of an active platinum group metal (PGM) and a more inert coinage metal are important in the field of catalysis, as they function as active and selective catalysts. Their catalytic properties depend on the surface "ensemble" of PGM atoms, whose size may be altered under reactive conditions. We use density functional theory and investigate the interaction of CO, a molecule common in numerous industrially important chemistries, with alloys that are composed of a PGM (Pt, Pd, Rh, Ir, Ni) doped in coinage metal hosts (Cu, Au, Ag). We study the adsorption of CO on the (211) step and (100) facet and compare our results to those previously obtained on the (111) facet. We determine strong correlations between the adsorption energies of CO across the facets and highlight the corresponding thermochemical scaling relations. Finally, we study the stability of isolated surface dopant atoms with respect to aggregation into clusters and segregation into the bulk, both in the presence and absence of CO. We find that strong COdopant interactions significantly influence the morphology of the catalyst surface, suggesting that it may be possible to establish control over the ensemble size of the dopant by tuning PCO.

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Section: Introductionmentioning

confidence: 76%

“…7,8 A new class of bimetallic catalysts, that has recently drawn a lot of attention, is single atom alloys (SAAs). 9,10 These catalysts are composed of isolated platinum group metal (PGM) atoms (i.e. Ni, Pt, Ir, Rh and Pd) that reside on the surface layer of a coinage metal host (i.e.…”

Section: Introductionmentioning

confidence: 99%

CO-Induced Aggregation and Segregation of Highly Dilute Alloys: A Density Functional Theory Study

2019

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“…Liu and Corma have published an insightful summary of the potential applications in a variety of reactions [55], and highlight water–gas shift, selective hydrogenations, photocatalysis and electrocatalytic reactions as attractive targets. Isolated atom geometries are known to be useful for hydrogenation reactions in closely related, so-called single atom alloys (SAA) [56], where incorporated Pt and Pd atoms, for example, dissociate H 2 leading to spillover onto a more inert host metal where further chemistry takes place [57, 58]. Zhang and coworkers have shown that this concept extends to metal oxide supports, and specifically that Pt 1 /FeO x and Ir 1 /FeO x can catalyse the selective hydrogenation of nitroarenes [59].…”

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confidence: 99%

Single-Atom Catalysis: How Structure Influences Catalytic Performance

Parkinson

2019

Catal Lett

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“…Due to the heterolytic dissociation of H 2 at single atom metal sites, the catalytic mechanism for the hydrogenation reactions over SACs could be quite different from that over NPs. From a conceptual standpoint, the Sabatier principle captured by “volcano”‐shaped plots shows that the optimum catalyst requires a compromise between strong and weak bindings ( Figure a) . The Brønsted–Evans–Polanyi (BEP) relationship further underpins this behavior by relating the activation energy to reaction energy (Figure b).…”

Section: Applicationsmentioning

confidence: 98%

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

et al. 2019

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metal atoms are highly desirable for supported noble-metal (NM) catalysts. [2] Single-atom catalyst (SAC), defined as a catalyst composing only isolated singleatom active sites on supports, was first introduced by Zhang and co-workers in 2011. [3] Owing to the single-atom feature of active sites, SACs provide great advantages in minimizing the usage of precious metal with a 100% atom-utilization efficiency, which thus result in an improved catalytic reactivity, and have aroused extensive attention in the field of catalysis over the past few years. [4] Meanwhile, since the electronic properties of active sites greatly depend on the size and shape of metal particles, which then governs the performance of a catalyst, [5] downsizing metal nanoparticles (NPs) to single atom with the decreased low coordination and the quantized orbital of active sites, is recognized as the other important factor in tuning the catalytic performance of SACs. [5,6] However, due to the tendency of aggregation of single atoms during preactivation and under reaction procedures, utilization of metal/support interactions to immobilize single atom on supports plays a crucial role on the stability of SACs, and the development of effective synthesis strategies is indispensable to realize the distribution and chemical bonding of active sites on supports for the further applications of SACs.In particular, high density of active sites with well-defined local coordination structure to give appreciable catalytic activity/ selectivity and long-term stability are the ultimate goals in catalysis. [7] Thus, long-standing interest exists in fabricating heterogeneous catalysts that feature atomically dispersed metal atoms as active sites for catalytic processes. Even though, considerable efforts have been devoted to, and many advances have been achieved in supported NM-SACs for various heterogeneous catalytic applications, inclusive of CO oxidation, selective hydrogenation, water-gas shift, CO 2 reduction, electrocatalysis, and etc. [2b,7b,8] The achievements from recent studies have greatly contributed to the fast development of single-atom catalysis and paves the way for the rational design of efficient SACs in much broader catalytic systems.In this review, we will focus on this new kind of material, with great attention on the geometric and electronic structure of the single atom active sites, as well as its stability on supports. The recently developed strategies for synthesizing SACs with high metal loading and precise structure are also Single-atom catalysts (SACs), with atomically distributed active metal sites on supports, serve as a newly advanced material in catalysis, and open broad prospects for a wide variety of catalytic processes owing to their unique catalytic behaviors. To construct SACs with precise structures and high density of accessible single-atom sites, while preventing aggregation to large nanoparticles, various strategies for their chemical synthesis have been recently developed by improving the distribution and chemical bondi...

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Lonely Atoms with Special Gifts: Breaking Linear Scaling Relationships in Heterogeneous Catalysis with Single-Atom Alloys

Cited by 252 publications

References 98 publications

CO-Induced Aggregation and Segregation of Highly Dilute Alloys: A Density Functional Theory Study

CO-Induced Aggregation and Segregation of Highly Dilute Alloys: A Density Functional Theory Study

Single-Atom Catalysis: How Structure Influences Catalytic Performance

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

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