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Metal‐Nanoparticle‐Based Catalysts
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Metal‐Nanoparticle‐Based Catalysts

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (20 April 2022) | Viewed by 7008

Special Issue Editors

Dr. Guangfang Li

E-Mail Website
Guest Editor
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Interests: design and regulation of metal nanostructures; photocatalysis; electrocatalysis
Special Issues, Collections and Topics in MDPI journals
Dr. Fan Tian

E-Mail Website
Guest Editor
School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Xiongchu Avenue, Wuhan 430073, China
Interests: cluster; nanostructures; heterocatalysis

Special Issue Information

Dear Colleagues,

Compared with their monometallic counterparts, multimetallic nanoparticles exhibit remarkably enhanced architectural, optical, and catalytic tunability, endowing nanoparticles with unexpected properties and thereby benefiting from the synergy between multiple constituents. In particular, hybrid nanostructures, created by coupling catalytically active metals with plasmonic materials, have been extensively studied for widespread applications in various chemical or electrochemical reactions. By using light as an energy resource, the plasmonic metallic nanoparticles can efficiently harvest electromagnetic radiation, converting it into localized surface plasmon resonances (LSPR), which may radiatively decay through photon scattering to amplify a local electromagnetic field in the vicinity of plasmonic metal surfaces or through a nonradiative pathway involving Landau damping via photon absorption, resulting in a generation of various energetic carriers that can be transferred to the catalytically active metal and accelerate the corresponding reaction rates.

The plasmon resonances of metallic nanostructures are intimately correlated to their compositions, geometries, and sizes, among other characteristics. Precise control of nanocrystals is the keystone for fine tuning and rational optimization of the plasmonic and catalytic properties of metallic nanoparticles. The aim of this SI is to understand the structure–composition–property relationship of multimetallic nanoparticles and uncover the complex mechanisms underpinning plasmon-derived photocatalysis toward establishing fundamental knowledge for the rational design of hybrid nanocatalysts with highly catalytic activities.

Dr. Guangfang Li
Dr. Fan Tian
Guest Editors

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • plasmon
  • catalysis
  • multimetallic
  • nanoparticles
  • structural control
  • photocatalysis
  • photoelectrocatalysis

Published Papers (4 papers)

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Research

14 pages, 7714 KiB  
Article
Effect of Bimetallic Dimer-Embedded TiO2(101) Surface on CO2 Reduction: The First-Principles Calculation
by Chongyang Li, Cui Shang, Bin Zhao, Gang Zhang, Liangliang Liu, Wentao Yang and Zhiquan Chen
Materials 2022, 15(7), 2538; https://doi.org/10.3390/ma15072538 - 30 Mar 2022
Viewed by 1567
Abstract
The first-principles calculation was used to explore the effect of a bimetallic dimer-embedded anatase TiO2(101) surface on CO2 reduction behaviors. For the dimer-embedded anatase TiO2(101) surface, Zn-Cu, Zn-Pt, and Zn-Pd dimer interstitials could stably stay on the TiO [...] Read more.
The first-principles calculation was used to explore the effect of a bimetallic dimer-embedded anatase TiO2(101) surface on CO2 reduction behaviors. For the dimer-embedded anatase TiO2(101) surface, Zn-Cu, Zn-Pt, and Zn-Pd dimer interstitials could stably stay on the TiO2(101) surface with a binding energy of about −2.36 eV, as well as the electronic states’ results. Meanwhile, the results of adsorption energy, structure parameters, and electronic states indicated that CO2 was first physically and then chemically adsorbed much more stably on these three kinds of dimer-embedded TiO2(101) substrate with a small barrier energy of 0.03 eV, 0.23 eV, and 0.12 eV. Regarding the reduction process, the highest-energy barriers of the CO2 molecule on the Zn-Cu dimer-embedded TiO2(101) substrate was 0.31 eV, which largely benefited the CO2-reduction reaction (CO2RR) activity and was much lower than that of the other two kinds of Zn-Pt and Cu-Pt dimer-TiO2 systems. Simultaneously, the products CO* and *O* of CO2 reduction were firmly adsorbed on the dimer-embedded TiO2(101) surface. Our results indicated that a non-noble Zn-Cu dimer might be a more suitable and economical choice, which might theoretically promote the designation of high CO2RR performance on TiO2 catalysts. Full article
(This article belongs to the Special Issue Metal‐Nanoparticle‐Based Catalysts)
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11 pages, 1777 KiB  
Article
Preparation of Aluminum–Molybdenum Alloy Thin Film Oxide and Study of Molecular CO + NO Conversion on Its Surface
by Tamerlan T. Magkoev, Dzhamilya G. Mustafaeva, Vladislav B. Zaalishvili, Oleg G. Ashkhotov and Zaurbek T. Sozaev
Materials 2022, 15(6), 2245; https://doi.org/10.3390/ma15062245 - 18 Mar 2022
Cited by 2 | Viewed by 1441
Abstract
Adsorption and interaction of carbon monoxide (CO) and nitric oxide (NO) molecules on the surface of bare Al-Mo(110) system and on that obtained by its in situ oxidation have been studied in ultra-high vacuum (base pressure: ca. 10−8 Pa) by means of [...] Read more.
Adsorption and interaction of carbon monoxide (CO) and nitric oxide (NO) molecules on the surface of bare Al-Mo(110) system and on that obtained by its in situ oxidation have been studied in ultra-high vacuum (base pressure: ca. 10−8 Pa) by means of Auger and X-ray photoelectron spectroscopy (AES, XPS), low energy electron diffraction (LEED), reflection–absorption infrared and thermal desorption spectroscopy (RAIRS, TDS), and by the work function measurements. In order to achieve the Al-Mo(110) alloy the thin aluminum film of a few monolayers thick was in situ deposited onto the Mo(110) crystal and then annealed at 800 K. As a result of Al atoms diffusion into the Mo(110) subsurface region and the chemical reaction, the surface alloy of a hexagonal atomic symmetry corresponding to Al2Mo alloy is formed. The feature of thus formed surface alloy regarding molecular adsorption is that, unlike the bare Mo(110) and Al(111) substrates, on which both CO and NO dissociate, adsorption on the alloy surface is non-dissociative. Moreover, adsorption of carbon monoxide dramatically changes the state of pre-adsorbed NO molecules, displacing them to higher-coordinated adsorption sites and simultaneously tilting their molecular axis closer to the surface plane. After annealing of this coadsorbed system up to 320 K the (CO + NO → CO2 + N) reaction takes place resulting in carbon dioxide desorption into the gas phase and nitriding of the substrate. Such an enhancement of catalytic activity of Mo(110) upon alloying with Al is attributed to surface reconstruction resulting in appearance of new adsorption/reaction centers at the Al/Mo interface (steric effect), as well as to the Mo d-band filling upon alloying (electronic effect). Catalytic activity mounts further when the Al-Mo(110) is in situ oxidized. The obtained Al-Mo(110)-O ternary system is a prototype of a metal/oxide model catalysts featuring the metal oxides and the metal/oxide perimeter interfaces as a the most active reaction sites. As such, this type of low-cost metal alloy oxide models precious metal containing catalysts and can be viewed as a potential substitute to them. Full article
(This article belongs to the Special Issue Metal‐Nanoparticle‐Based Catalysts)
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12 pages, 3232 KiB  
Article
Theoretical Mechanism on the Cellulose Regeneration from a Cellulose/EmimOAc Mixture in Anti-Solvents
by Zhaoyang Ju, Yihang Yu, Shaokeng Feng, Tingyu Lei, Minjia Zheng, Liyong Ding and Mengting Yu
Materials 2022, 15(3), 1158; https://doi.org/10.3390/ma15031158 - 02 Feb 2022
Cited by 7 | Viewed by 1856
Abstract
The experiments on cellulose dissolution/regeneration have made some achievements to some extent, but the mechanism of cellulose regeneration in ionic liquids (ILs) and anti-solvent mixtures remains elusive. In this work, the cellulose regeneration mechanism in different anti-solvents, and at different temperatures and concentrations, [...] Read more.
The experiments on cellulose dissolution/regeneration have made some achievements to some extent, but the mechanism of cellulose regeneration in ionic liquids (ILs) and anti-solvent mixtures remains elusive. In this work, the cellulose regeneration mechanism in different anti-solvents, and at different temperatures and concentrations, has been studied with molecular dynamics (MD) simulations. The IL considered is 1-ethyl-3-methylimidazolium acetate (EmimOAc). In addition, to investigate the microcosmic effects of ILs and anti-solvents, EmimOAc-nH2O (n = 0–6) clusters have been optimized by Density Functional Theory (DFT) calculations. It can be found that water is beneficial to the regeneration of cellulose due to its strong polarity. The interactions between ILs and cellulose will become strong with the increase in temperature. The H-bonds of cellulose chains would increase with the rising concentrations of anti-solvents. The interaction energies between cellulose and the anions of ILs are stronger than that of cations. Furthermore, the anti-solvents possess a strong affinity for ILs, cation–anion pairs are dissociated to form H-bonds with anti-solvents, and the H-bonds between cellulose and ILs are destroyed to promote cellulose regeneration. Full article
(This article belongs to the Special Issue Metal‐Nanoparticle‐Based Catalysts)
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12 pages, 2772 KiB  
Communication
An Accessible Integrated Nanoparticle in a Metallic Hole Structure for Efficient Plasmonic Applications
by Vasanthan Devaraj, Jong-Wan Choi, Jong-Min Lee and Jin-Woo Oh
Materials 2022, 15(3), 792; https://doi.org/10.3390/ma15030792 - 21 Jan 2022
Cited by 7 | Viewed by 1585
Abstract
Addressing the severe deterioration of gap mode properties in spherical-shaped nanoparticles (NPs) becomes necessary due to their utilization in a wide range of multi-disciplinary applications. In this work, we report an integrated plasmonic nanostructure based on a spherical-shaped nanoparticle (NP) in a metallic [...] Read more.
Addressing the severe deterioration of gap mode properties in spherical-shaped nanoparticles (NPs) becomes necessary due to their utilization in a wide range of multi-disciplinary applications. In this work, we report an integrated plasmonic nanostructure based on a spherical-shaped nanoparticle (NP) in a metallic hole as an alternative to a NP-only structure. With the help of three-dimensional (3D) electromagnetic simulations, we reveal that when a NP is positioned on the top of a metallic hole, it can exhibit superior gap-mode-based local-field intensity enhancement. The integrated nanostructure displayed a ~22-times increase in near-field enhancement characteristics, similar to cube- or disk-shaped nanostructure’s plasmonic properties. From an experimental perspective, the NP positioning on top of the metallic hole can be realized more easily, facilitating a simple fabrication meriting our design approach. In addition to the above advantages, a good geometrical tolerance (metallic hole-gap size error of ~20 nm) supported by gap mode characteristics enhances flexibility in fabrication. These combined advantages from an integrated plasmonic nanostructure can resolve spherical-shaped NP disadvantages as an individual nanostructure and enhance its utilization in multi-disciplinary applications. Full article
(This article belongs to the Special Issue Metal‐Nanoparticle‐Based Catalysts)
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