Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases

Ren, Zhibo; Liu, Ning; Chen, Biaohua; Li, Jianwei; Mei, Donghai

doi:10.1021/acs.jpcc.7b10208

Cited by 27 publications

(42 citation statements)

References 41 publications

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“…However, it is known since 1970s that clusters majorly change shapes in the presence of the support—a concept of strong metal–support interaction (SMSI), and also the adsorbates . For instance, it has been shown that Pt 13 cluster shape will significantly change when deposited on CeO 2 . Even different surface cuts could lead to different stable cluster structures: Ab initio molecular dynamics (AIMD) simulations revealed that the CeO 2 (110) surface provides the most stability for the Pt 13 nanocluster (Figure ).…”

Section: The Global Minimum Structure Of the Cluster Catalyst: Not Trmentioning

confidence: 99%

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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: The Global Minimum Structure Of the Cluster Catalyst: Not Trmentioning

confidence: 99%

Section: The Global Minimum Structure Of the Cluster Catalyst: Not Trmentioning

confidence: 99%

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

Zandkarimi

Alexandrova

2019

WIREs Comput Mol Sci

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“…Several methods have been proposed to characterize the electron transfer around the interfacial area, e.g., work function (Liu et al, 2016 ), Bader charge analysis (Lim and Wilcox, 2011 ; Ewing et al, 2015 ), and charge density difference (Wang Y. et al, 2017 ; Ren et al, 2018 ). Basically, the work function can be defined as ϕ = E vac − E F , where E F is the Fermi energy and E vac denotes the electrostatic potential of the vacuum level.…”

Section: Resultsmentioning

confidence: 99%

“…Several methods have been proposed to characterize the electron transfer around the interfacial area, e.g., work function (Liu et al, 2016), Bader charge analysis (Lim and Wilcox, 2011;Ewing et al, 2015), and charge density difference (Wang Y. et al, 2017;Ren et al, 2018). Basically, the work function can be defined as φ = E vac − E F , where E F is the Fermi energy and E vac denotes the FIGURE 3 | The calculated total density of states (TDOS) for (A) the icosahedron Pt 13 cluster, (B) the clean 20%-MIL-125-(SCH 3 ) 2 (001) surface, and (C) the optimized Pt 13 /20%-MIL-125-(SCH 3 ) 2 system (the Pt 13 cluster is spin-polarized).…”

Section: Electron Transfer Properties Across the Pt13/20%-mil-125-(scmentioning

confidence: 99%

A Ti-MOF Decorated With a Pt Nanoparticle Cocatalyst for Efficient Photocatalytic H2 Evolution: A Theoretical Study

Zhong

Wang

et al. 2020

Front. Chem.

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Pt nanoparticles (NPs) are often used as cocatalysts to enhance the photocatalytic hydrogen production catalyzed by the metal organic framework (MOF) materials. The catalytic efficiency of many Pt/MOF systems can be greatly improved when Pt NPs are used as cocatalysts. In this work, the Pt/20%-MIL-125-(SCH 3) 2 was chosen as the template material to understand the functional role of a Pt metal cocatalyst in the catalytic process. Experimentally, the catalytic activity of Pt/20%-MIL-125-(SCH 3) 2 is more than 100 times that of the system without the help of Pt NPs. Firstly, we proposed a searching algorithm, which is based on the combined Monte Carlo (MC) method and principal component analysis (PCA) algorithm, to find that the most probable adsorption site of the Pt 13 nanocluster loaded on the (001) surface of 20%-MIL-125-(SCH 3) 2. Next, by using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, we revealed that the accumulation of some positive charges on the Pt 13 cluster and proton adsorbed on the Pt 13 cluster, which can promote the separation of photogenerated electrons and holes, thus improving the photocatalytic efficiency. This work not only provides a method to obtain the adsorption configuration of metal clusters on various MOFs but also provides a new insight into increasing photocatalytic efficiency for H 2 production in Pt/MOF systems.

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“…For example, it is reported that the supported Pt 13 nanocluster has the tendency to wet the CeO 2 surface in the gas phase (CO) due to the strong MSI. Notably, this MSI is clearly enhanced with the presence of the aqueous phase …”

Section: The Thermal Stability Of Supported Metal Nanoparticlesmentioning

confidence: 99%

Multiscale simulation on thermal stability of supported metal nanocatalysts

Deng

Qiu

Yao

et al. 2019

WIREs Comput Mol Sci

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The main goal of computer simulation here is the rapid and accurate description or prediction of catalyst structures and their thermal stabilities, which is sometimes difficult to achieve via simulation methods at a single length or time scale. For example, an Au NP with a diameter of only 5 nm owns around 4,000 atoms, it is enormously too large for first principle-based DFT calculations. Therefore, it is expected to use different simulation method to solve the problem at the corresponding scale, and sometimes the multiscale simulation strategies are necessary which bridge the models and simulation techniques across a broad range of length and time scales. 18,19 Based on the study of supported metal nanocatalysts, we mainly introduce here the catalysis application of three widely used simulation methods: the DFT calculation, MD simulation, and ML strategy. | DFT-based first principle calculation for heterogeneous catalysisDFT is a computational quantum-mechanical modeling method used in chemistry, physics, and materials science to study the electronic structure (principally the ground state) of atoms, molecules, many-body systems, and the condensed phases. 20 The properties can be determined by using functionals of the electron density. Currently, DFT has become an essential complement in catalysis science. As for the research of supported metal nanocatalysts, it can provide insights into the geometric and FIGURE 1 Interaction energies for the density functional theory (DFT) calculations and the fitted Morse potential curve of the structure of (a) weak metalsupport interaction (MSI) and (b) strong MSI DENG ET AL.

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Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases

Cited by 27 publications

References 41 publications

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

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

A Ti-MOF Decorated With a Pt Nanoparticle Cocatalyst for Efficient Photocatalytic H2 Evolution: A Theoretical Study

Multiscale simulation on thermal stability of supported metal nanocatalysts

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