An oxidized magnetic Au single atom on doped TiO<sub>2</sub>(110) becomes a high performance CO oxidation catalyst due to the charge effect

Shi, Jinlei; Zhao, Xingju; Zhang, Li Ying; Xue, Xiangfei; Guo, Zhengxiao; Gao, Yanfei; Li, S. F.

doi:10.1039/c7ta05483a

Cited by 52 publications

(38 citation statements)

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“…However, most experimental evidence points toward al ower activity of SAs compared to metal clusters. [58] In contrast, as tudy of B-and N-doped carbon supports indicated that anionic Au species formed in the presence of boron were more active because CO was less strongly adsorbed than it would otherwise be on Au cations. [51] Au 1 /CeO 2 was later shown to be stable for the preferential oxidation of CO in H 2 -rich streams.…”

Section: Methodsmentioning

confidence: 95%

“…As ac onsequence of the known activity in this reaction, Au-based systems have attracted significant attention. [58,62,92] Maximizing the degree of oxidation by doping with as econd transition metal was predicted to yield the highest activity for Au 1 /TiO 2 systems. [87][88][89][90] On the other hand, Qiao et al highlighted ap otential advantage of SAs for demonstrating increased resistance to sintering of Au 1 /FeO x compared to larger Au nanostructures.…”

Section: Methodsmentioning

confidence: 99%

“…[91] Thec hallenge of developing an active SACh as inspired various ab initio studies,w hich aim to elucidate the optimal charge state and geometry of Au species. [58,62,92] Maximizing the degree of oxidation by doping with as econd transition metal was predicted to yield the highest activity for Au 1 /TiO 2 systems. [58] In contrast, as tudy of B-and N-doped carbon supports indicated that anionic Au species formed in the presence of boron were more active because CO was less strongly adsorbed than it would otherwise be on Au cations.…”

Section: Methodsmentioning

confidence: 99%

“…[58,62,92] Maximizing the degree of oxidation by doping with as econd transition metal was predicted to yield the highest activity for Au 1 /TiO 2 systems. [58] In contrast, as tudy of B-and N-doped carbon supports indicated that anionic Au species formed in the presence of boron were more active because CO was less strongly adsorbed than it would otherwise be on Au cations. [62] This resembles the mechanistic path proposed for Au/CeO 2 , in which the oxidation state of Au is initially negative and becomes positively charged upon O 2 dissociation;t hus,C O can adsorb and readily reacts with as urface oxygen to form CO 2 .…”

Section: Methodsmentioning

confidence: 99%

“…Quantum-size effects,a rising from electron confinement in the absence of neighboring atoms with similar energy orbitals (most nonmetals), are accompanied by as hift from continuous energy bands to discrete atomic orbitals. [43] Additionally,t he strong interaction with the host required for stabilization of single atoms (SAs) often results in bond polarization, which can lead to extensive charge transfer from or to the metal, thereby originating cationic or anionic species.Asurvey of the predicted electronic state of Au,Pt, and Pd atoms on distinct hosts, [44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61][62] quantified based on the robust method for charge analysis introduced by Bader, [63] emphasizes the significant potential changes in the degree of electron transfer ( Figure 3). As expected, am uch narrower range of charge states is anticipated for SAAs than for SACs based on oxide-or carbon-based materials.Inthe latter hosts,noteworthy differences are also observed for inequivalent sites on the same materials.F or example,t he calculated values for gold atoms bonded to axial or pyridine sites in N-doped single-wall carbon nanotubes were 0.9 and 0.41 e À ,r espectively.…”

Section: Properties Of Sacsmentioning

confidence: 99%

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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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Section: Methodsmentioning

confidence: 95%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Properties Of Sacsmentioning

confidence: 99%

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The Multifaceted Reactivity of Single‐Atom Heterogeneous Catalysts

2018

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Supported Metal Single‐Atom Thermocatalysts for Oxidation Reactions

Piccolo

Loridant

Christopher

2022

Supported Metal Single Atom Catalysis

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The interest in single-metal-atom dispersion in heterogeneous catalysis has existed since the 1950s with spectroscopic investigations of rhodium "single-site" catalysts supported on alumina, and more recently with oxometallate monomers for selective oxidation reactions. A decade ago, advances in electron microscopy intensified the interest of the catalysis community in controlling the dispersion of supported metals down to the single-atom active site level and revealing their intrinsic catalytic properties. Pioneering works in the ever-growing field of single-atom catalysis investigated late transition metals (group 8 to 11) supported on transition metal oxides for the CO oxidation and water-gas shift reactions. Since then, various single-atom catalysts, most often supported on oxides, have been evaluated in a broad panel of thermal oxidation reactions, and have often shown remarkable performances. Besides CO oxidation over oxidesupported noble metals, which represents the major part of the literature, this chapter reviews the main classes of oxidation reactions, including total and selective oxidations of hydrocarbons and oxygenates, on 2 oxide-or carbon-supported catalysts. Throughout the chapter, we emphasize several aspects that we consider important, such as the coordination environment and stability of single metal atoms, as well as their compared performance with supported nanoparticles. Figure 3. a) Aberration-corrected STEM image of Pt atoms (identified by yellow circles) on ca. 5 nm diameter anatase TiO2 particles. Adapted with permission from [72], Copyright 2017 ACS. b) CO probemolecule FTIR spectra of a Pt/TiO2 SAC as a function of temperature during a TPD measurement. c) DFT-calculated structure of CO bound to PtO2 adsorbed at a TiO2(145) step edge. b and c adapted with permission from [73], Copyright 2018 Elsevier. d) Schematic showing the structural transformation of isolated Pt species as a function of environmental conditions. Adapted with permission from [74],Copyright 2019 Springer Nature. e) DFT-calculated reaction pathway for CO oxidation on a Pd/TiO2 SAC that was supported by spectroscopic and kinetic analyses. Adapted with permission from [75],

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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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An oxidized magnetic Au single atom on doped TiO₂(110) becomes a high performance CO oxidation catalyst due to the charge effect

Cited by 52 publications

References 61 publications

The Multifaceted Reactivity of Single‐Atom Heterogeneous Catalysts

The Multifaceted Reactivity of Single‐Atom Heterogeneous Catalysts

Supported Metal Single‐Atom Thermocatalysts for Oxidation Reactions

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

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An oxidized magnetic Au single atom on doped TiO2(110) becomes a high performance CO oxidation catalyst due to the charge effect

Cited by 52 publications

References 61 publications

The Multifaceted Reactivity of Single‐Atom Heterogeneous Catalysts

The Multifaceted Reactivity of Single‐Atom Heterogeneous Catalysts

Supported Metal Single‐Atom Thermocatalysts for Oxidation Reactions

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

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An oxidized magnetic Au single atom on doped TiO₂(110) becomes a high performance CO oxidation catalyst due to the charge effect