Phosphomolybdic acid supported single-metal-atom catalysis in CO oxidation: first-principles calculations

Ming-an, YU; Feng, Yingxin; Gao, Liye; Lin, Sen

doi:10.1039/c8cp03916j

Cited by 35 publications

(12 citation statements)

References 53 publications

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“…Several groups have used this metal-functionalized POM-SAC model system (where the SAC is located in the 4-H site) for computational studies on reduction/oxidation reactions including alkene epoxidation, [61] N 2 reduction, [62,63] NO x (NO and N 2 O) reduction, [64][65][66] and CO oxidation. [67][68][69][70] In 2019, Sautet, Yan and co-workers investigated how metalsupport interactions affect stability and hydrogenation activity of Class I POM-SACs. To this end, they compared the binding of Pt atoms on four Keggin-anions, [XM 12 O 40 ] n− (X = P (n = 3), Si (n = 4), M = W VI , Mo VI ) using experiment and theory.…”

Section: Noble-metal-functionalized Pom-sacsmentioning

confidence: 99%

“…However, subsequent DFT analyses revealed that an alternative Langmuir-Hinshelwood mechanism could be energetically favoured. [70] To gain insight into this discrepancy, Liu and colleagues performed DFT calculations to show that the oxo ligands bound to the single-atom site are chemically nonequivalent, due to polarization effects of the anchored SAC. When these effects are considered in the mechanistic analysis, [69] theory again predicts that the MvK mechanism is energetically favored for the Rh-functionalized POM-SACs studied.…”

Section: Noble-metal-functionalized Pom-sacsmentioning

confidence: 99%

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Polyoxometalate‐Single Atom Catalysts (POM‐SACs) in Energy Research and Catalysis

Liu

Streb

2021

Advanced Energy Materials

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have only been explored since the early 21st century, mainly because their identification and characterization has been virtually impossible before, due to a lack of high-resolution instrumentation (such as electron or scanning probe microscopies). [1,4] Beyond classical heterogeneous SACs, much research has recently focused on developing molecular SAC model systems. Here, polyoxometalate-single atom catalysts (POM-SACs) are of enormous interest as these molecular metal oxides could form the link between molecularly well-defined prototypes and technologically relevant solid-state SACs. In this Review, we will provide a brief introduction into the current status in SACs chemistry. We then discuss pioneering studies as well as current research challenges in POM-SACs chemistry with an emphasis on sustainable energy research. Finally, we will identify future areas in POM-SAC research and highlight the bottlenecks which need to be overcome to further develop this field. Classical Single Atom Catalysts Common Anchoring Strategies and Applications of SACsSACs offer the ultimate atomic reactivity, as each single atom is interacting with its environment and can act as catalytic site. [7][8][9] The key to the successful preparation of SACs is to stabilize catalytic metal centers as individual atoms by utilizing hosts/supports featuring strong binding motifs (Figure 1). Early model systems included high specific surface area carbons, [10,11] metal oxides, [12,13] as well as materials with uniform pores and regular structures, such as zeolites, [14] metal organic frameworks (MOFs) [5,[14][15][16][17][18][19] and covalent organic frameworks (COFs). [20,21] Stabilization of single-atoms on supports requires a support-surface with specific anchoring sites, such as coordinatively unsaturated surface atoms (e.g., O 2− , OH − ), surface vacancies or heteroatom dopants (e.g., N, P, S, and halogens). The SACs can be stabilized on the support surface by covalent or ionic interactions, or by geometric enclosure in small pores. Each anchoring mode offers several benefits and challenges. For instance, the coordination of a single metal atom to surface oxo ligands makes the single-atom accessible from the outside, e.g., for binding of a substrate. However, it also leads to high surface-energy and destabilization of the single-atom, so that leaching, or agglomeration are possible. In contrast, Single atom catalysts-SACs-have received intense interest in sustainable energy research due to their enormous application potential and broad catalytic scope. In particular, SACs anchored on molecular metal oxides-polyoxometalates (POMs)-offer unrivalled possibilities as models to understand the function of these complex systems on the atomic level. Research questions which are difficult to address for classical heterogeneous SACs can be addressed by experiment and theory using POM-SACs as prototype catalysts. This review reviews the emerging field of POM-SAC research with a focus on fundamental properties and their application in energy conversion...

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Section: Noble-metal-functionalized Pom-sacsmentioning

confidence: 99%

Section: Noble-metal-functionalized Pom-sacsmentioning

confidence: 99%

Polyoxometalate‐Single Atom Catalysts (POM‐SACs) in Energy Research and Catalysis

Liu

Streb

2021

Advanced Energy Materials

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“…The geometries of nanotubes and studied molecules (such as OOH, OH, H 2 O and CO) are optimized by M06-2X/6-311G+ (2d, 2p) in GAMESS package. [59][60][61][62][63][64][65][66][67][68][69][70][71][72] The consistent eld is investigated by 10 À6 Hartree as convergence value. Vibrational frequencies of nanotubes and molecules by M06-2X/6-311G+ (2d, 2p) are calculated.…”

Section: Computational Detailsmentioning

confidence: 99%

“…[83][84][85][86][87] The energy and Gibbs free energy (G ¼ E 0 + ZPE + DH + RT À TS) values of nanotubes are calculated. The E 0 and ZPE are electronic energy and zero-point energy and T is 298.15 K. [59][60][61][62][63][64][65][66][67][68][69][70][71][72] Adoption energy (E doped ) and Gibbs free energy adoption (G doped ) of B atoms in SiNT (7, 0) are calculated: [59][60][61][62][63][64][65][66][67][68][69][70][71][72] and transition state, reaction energy (DE r ) and activation barrier energy (DE a ) are examined by LST/QST method and M06-2X. 64 Activation energy (DE a ¼ E TS À E IS ) is difference of energy between transition (E TS ) and initial (E IS ) studied complexes.…”

Section: Computational Detailsmentioning

confidence: 99%

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Theoretical investigation of the ORR on boron–silicon nanotubes (B–SiNTs) as acceptable catalysts in fuel cells

Razavi

Najafi

2019

RSC Adv.

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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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Phosphomolybdic acid supported single-metal-atom catalysis in CO oxidation: first-principles calculations

Cited by 35 publications

References 53 publications

Polyoxometalate‐Single Atom Catalysts (POM‐SACs) in Energy Research and Catalysis

Polyoxometalate‐Single Atom Catalysts (POM‐SACs) in Energy Research and Catalysis

Theoretical investigation of the ORR on boron–silicon nanotubes (B–SiNTs) as acceptable catalysts in fuel cells

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

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