Single Layer of Polymeric Metal–Phthalocyanine: Promising Substrate to Realize Single Pt Atom Catalyst with Uniform Distribution

Chen, X. F.; Yan, Jun‐Min; Jiang, Q.

doi:10.1021/jp411183h

Cited by 25 publications

(22 citation statements)

References 49 publications

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“…As the supported metal species downsize to the single atom, the interaction between active site and support is always uniform, which can be much easier to be characterized by both experiment and theoretical calculation. [ 13 ] With the help of advanced techniques, for instance, X‐ray absorption spectroscopy (XAS), the information about electronic state can be obtained in detail, which pushes the understanding of EMSI much further. [ 14 ] After the development for nine years, the synthesis of SACs with low and high loading amount has been realized by many methods such as, defect engineering, [ 15 ] space confinement, [ 16 ] coordination design, [ 17 ] and so on.…”

Section: Introductionmentioning

confidence: 99%

Electronic Metal–Support Interaction of Single‐Atom Catalysts and Applications in Electrocatalysis

et al. 2020

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between the electronic structure and catalytic efficiency of heterogenous catalysts. Dating back to 1930s, the concept of "electronic factor" was proposed by G. M. Schwab to describe the influence of electronic interaction on catalytic behavior of supported catalyst and divided the interaction into two parts, structural and synergetic ones. [4] Electrons transferring between the metal and the support was first under consideration when it came to the catalysis. After that, S. J. Tauster used the term of "strong metal-support interaction" (SMSI) to describe the chemisorption properties of group VIII elements supported by a metal oxide (e.g. SiO 2 , MgO) in 1978. [5] Later the concept was broadened to interaction between any metallic species and support, based on the experimental phenomena. [6] Till that time, based on the early characterization of surface science, researchers had realized that the active site might change during the process from metallic to an SMSI state, which was indicated to be covered or encapsulated by the support. [7] Among many hypotheses concerning the mechanism of SMSI, electron transfer between the metal and the support has been adapted by many researchers, and was confirmed by Rodriguez based on X-ray crystallography and UV photoemission spectroscopy in 1990s. [8] Then almost at the same time that the term of SACs was formally put forward, C. T. Campbell proposed the concept of "electronic metal-support interaction" (EMSI). As Campbell described, the chemical and catalytic properties might be affected by the electronic perturbations (i.e., shifts in the energy of d-band center) due to the EMSI. [9] In other words, the EMSI gave a much more detailed explanation of the enhanced properties of supported catalysts than SMSI, indicating that the study on catalysis was finally pushed to the electronic scale after so many years. [9b,c,10] Unfortunately, for metal particles or clusters, the accurate identification of electronic state is often difficult or even impossible. [11] The most reliable way to overcome the barrier above is to develop the catalyst based on single-atom metal that avoids intrinsic metal effects, including the electronic quantum size effect as well as structure-sensitivity geometrical effect. [12] Therefore, the rise of SACs provides a nearly perfect model to study the EMSI. As the supported metal species downsize to the single atom, the interaction between active site and support is always uniform, which can be much easier to be characterized by both experiment and theoretical calculation. [13] With the help of advanced techniques, for instance, X-ray absorption spectroscopy (XAS), the information about electronic The electronic metal-support interaction (EMSI), which acts as a bridge between theoretical electronic study and the design of heterogenous catalysts, has attracted much attention. Utilizing the interaction between the metal and the support is one of the most essential strategies to enhance electrocatalytic efficiency due to structural and synergetic promotion. To ...

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Section: Introductionmentioning

confidence: 99%

Electronic Metal–Support Interaction of Single‐Atom Catalysts and Applications in Electrocatalysis

et al. 2020

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“…Nevertheless, single‐atom metallic catalysts limit mass‐application in some ways. For instance, exploiting new alternative supports which can possess extra‐large surface areas and more monovacancy distribution and thus can achieve atom‐scale control of single metallic atoms is of significance, due to the high mobility and their sinter easiness of metallic atoms on support . It likely not only can create appropriate interactions between metallic single‐atoms and supports, but also markedly improve catalytic activity instead of specific activity via increasing the metal loading, retaining a single atomic state.…”

Section: Discussionmentioning

confidence: 99%

Metallic Nanocatalysis: An Accelerating Seamless Integration with Nanotechnology

Dai

Wang

Liu

et al. 2014

Small

101

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Rapidly growing research interests surround heterogeneous nanocatalysis, in which metal nanoparticles (NPs) play a pivotal role as structure-sensitive active centers. With advances in nanotechnology, the morphology of metal NPs can be precisely controlled, which can provide well-defined models of nanocatalysts for understanding and optimizing the structure-reactivity correlations and the catalytic mechanisms. Benefiting from this, further credible evidence can be acquired on well-defined nanocatalysts rather than common multiphase systems, which is of great significance for the design and practical application of active metal nanocatalysts. Numerous studies demonstrate that enhanced structure-sensitive catalytic activity and selectivity are dependent not only on an increased surface-to-volume ratio and special surface atom arrangements, but also on tailored metal-metal and metal-organic-ligand interfaces, which is ascribed to the size, shape, composition, and ligand effects. Size-reactivity relationships and underlying size-dependent metal-oxide interactions are observed in many reactions. For bimetallic nanocatalysts, the composition and nanostructure play critical roles in regulating reactivities. Crystal facets favor individual catalytic selectivity and rates via distinct reaction pathways occurring on diverse atomic arrangements, both to low-index and high-index facets. High-index facets exhibit superior reactivities owing to their high-energy active sites, which facilitate rapid bond-breaking and new bond generation. Additionally, organic ligands may enhance the catalytic activity and selectivity of metal nanocatalysts via changing the adsorption energies of reactants and/or reaction energy barriers. Furthermore, atomically dispersed metals, especially single-atom metallic catalysts, have emerged recently, which can achieve better specific catalytic activity compared to conventional nanostructured metallic catalysts due to the low-coordination environment, stronger interaction with supports, and maximum service efficiency. Here, recent progress in shaped metallic nanocatalysts is examined and several parameters are discussed, as well as finally highlighting single-atom metallic catalysts and some perspectives on nanocatalysis. The integration of nanotechnology and nanocatalysis has been shaping up and, no doubt, the combination of sensitive characterization techniques and quantum calculations will play more important roles in such processes.

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“…Geometry optimizations were performed using DMol 3 (Dassault Systèmes BIOVIA, San Diego, CA, USA) under the following conditions: 1) the spin-polarized general gradient approximation (GGA)-PBE functional [14,15] option, and 2) the DNP basis set, to predict the properties of catalyst and adsorbates (H 2 or CO). GGA-PBE based functions have been extensively used to describe systems including Pt catalysts [16][17][18] and carbon-based materials [19][20][21][22][23][24][25].…”

Section: Methodsmentioning

confidence: 99%

Influence of defective sites in Pt/C catalysts on the anode of direct methanol fuel cell and their role in CO poisoning: a first-principles study

Kwon¹,

Lee²

2015

Carbon letters

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Carbon-supported Pt catalyst systems containing defect adsorption sites on the anode of direct methanol fuel cells were investigated, to elucidate the mechanisms of H 2 dissociation and carbon monoxide (CO) poisoning. Density functional theory calculations were carried out to determine the effect of defect sites located neighboring to or distant from the Pt catalyst on H 2 and CO adsorption properties, based on electronic properties such as adsorption energy and electronic band gap. Interestingly, the presence of neighboring defect sites led to a reduction of H 2 dissociation and CO poisoning due to atomic Pt filling the defect sites. At distant sites, H 2 dissociation was active on Pt, but CO filled the defect sites to form carbon π-π bonds, thus enhancing the oxidation of the carbon surface. It should be noted that defect sites can cause CO poisoning, thereby deactivating the anode gradually.

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Single Layer of Polymeric Metal–Phthalocyanine: Promising Substrate to Realize Single Pt Atom Catalyst with Uniform Distribution

Cited by 25 publications

References 49 publications

Electronic Metal–Support Interaction of Single‐Atom Catalysts and Applications in Electrocatalysis

Electronic Metal–Support Interaction of Single‐Atom Catalysts and Applications in Electrocatalysis

Metallic Nanocatalysis: An Accelerating Seamless Integration with Nanotechnology

Influence of defective sites in Pt/C catalysts on the anode of direct methanol fuel cell and their role in CO poisoning: a first-principles study

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