Metallic Nanoparticles and Metal-Mediated Synthesis in Catalysis

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Nanostructured Catalysts".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 9538

Special Issue Editors


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Departamento de Engenharia Química, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, 1959-007 Lisboa, Portugal
Interests: sustainable homogeneous and supported catalysis; oxidation catalysis; green synthesis of metallic nanoparticles; mechanochemistry (synthesis and catalysis); molecular electrochemistry
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REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Porto, Portugal
Interests: heterogeneous catalysis; catalytic process; biomass valorization; carbon-based material; biofuels; CO2 valorization; renewable energy
Special Issues, Collections and Topics in MDPI journals

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1. Área Departamental de Engenharia Química, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, 1500-310 Lisboa, Portugal
2. Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, 1500-310 Lisboa, Portugal
Interests: eco-sustainable catalysis; mechanochemistry; sustainable preparation methods; nanomaterials functionalization

Special Issue Information

Dear Colleagues,

The application of nanotechnology in catalysis and in particular in organic synthesis involving CO and H2 oxidation, hydrocarbons functionalization, nitroarenes and NO reduction or C-C coupling among others, has made important advances in order to achieve the highest catalytic activity and selectivity while maintaining high stability. For this purpose, metallic and bimetallic nanoparticles as well as various types of core-shell nanostructures with specific functions have been developed through various synthetic protocols. Catalytic studies have demonstrated a relationship between size and shape and increasing rates of conversion and selectivity. In addition, bimetallic nanocatalysts have shown a synergistic effect relative to the individual properties of each metal.

For these reasons, we propose as the theme of this Special Issue the development of new metal-based nanocatalysts (with special emphasis on non-noble-metal (Fe, Cu, Ni, Co, etc.)-based nanoparticle catalysts prepared from green synthesis approaches) capable of, in suspension or supported, catalyzing several important reactions including the synthesis of organic compounds, degradation of pollutants and biomass valorization, in an efficient and sustainable way.

Prof. Dr. Elisabete C.B.A. Alegria
Dr. Andreia F. Peixoto
Dr. Mohamed M. A. Soliman
Guest Editors

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Keywords

  • Metal Nanoparticles
  • Nanocatalysis
  • Core-shell Nanoparticles
  • Metal-mediated Organic Synthesis
  • Catalytic Biomass Valorization

Published Papers (4 papers)

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Research

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22 pages, 4394 KiB  
Article
C-H versus C-O Addition: A DFT Study of the Catalytic Cleavage of the β-O-4 Ether Linkage in Lignin by Iridium and Cobalt Pincer Complexes
by Mary Mensah, Richard Tia, Evans Adei and Nora H. de Leeuw
Catalysts 2023, 13(4), 757; https://doi.org/10.3390/catal13040757 - 15 Apr 2023
Viewed by 1596
Abstract
The potential energy surfaces of the reactions involved in the catalytic cleavage of 2-phenoxy-1-phenylethanol, a model of the β-O-4 linkage in lignin, by (iprPCP)-Ir, (iprPCOP)-Ir, (iprPCP)-Co and (iprPCOP)-Co complexes have been studied [...] Read more.
The potential energy surfaces of the reactions involved in the catalytic cleavage of 2-phenoxy-1-phenylethanol, a model of the β-O-4 linkage in lignin, by (iprPCP)-Ir, (iprPCOP)-Ir, (iprPCP)-Co and (iprPCOP)-Co complexes have been studied using the M06/6-311G**/LANL2TZ level of theory. Both iridium and cobalt are found to be active towards the cleavage of the β-O-4 linkage, with rate constants of 44.7 s−1 and 5.1 × 106 s−1, respectively. The iridium catalysts prefer the ‘initial C-H addition’ pathway, showing a kinetic preference of 16.8 kcal mol−1 over the ‘direct C-O insertion’ pathway, while the cobalt catalysts prefer the ‘direct C-O insertion’ route which is kinetically favored by 15.7 kcal mol−1 over the ‘initial C-H addition’ pathway. A two-state reactivity occurs along the preferred pathway for the cobalt-catalyzed reaction. Full article
(This article belongs to the Special Issue Metallic Nanoparticles and Metal-Mediated Synthesis in Catalysis)
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21 pages, 20087 KiB  
Article
Glycerol Valorization over ZrO2-Supported Copper Nanoparticles Catalysts Prepared by Chemical Reduction Method
by Juan Garcés, Ramón Arrué, Néstor Novoa, Andreia F. Peixoto and Ricardo J. Chimentão
Catalysts 2021, 11(9), 1040; https://doi.org/10.3390/catal11091040 - 28 Aug 2021
Cited by 7 | Viewed by 2570
Abstract
Copper nanoparticles (NPs) and ZrO2-supported copper NPs (Cu NPs/ZrO2) were synthesized via a chemical reduction method applying different pH (4, 7 and 9) and evaluated in a glycerol dehydration reaction. Copper NPs were characterized with transmission electron microscopy (TEM) [...] Read more.
Copper nanoparticles (NPs) and ZrO2-supported copper NPs (Cu NPs/ZrO2) were synthesized via a chemical reduction method applying different pH (4, 7 and 9) and evaluated in a glycerol dehydration reaction. Copper NPs were characterized with transmission electron microscopy (TEM) and UV–vis spectroscopy. Transmission electron microcopy (TEM) results revealed a homogeneous distribution of copper NPs. A hypsochromic shift was identified with UV–vis spectroscopy as the pH of the synthesis increased from pH = 4 to pH = 9. Zirconia-supported copper NPs catalysts were characterized using N2 physisorption, X-ray diffraction (XRD), TEM, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), temperature-programmed desorption of ammonia (NH3-TPD) and N2O chemisorption. The presence of ZrO2 in the chemical reduction method confirmed the dispersion of the copper nanoparticles. X-ray diffraction indicated only the presence of tetragonal zirconia patterns in the catalysts. XPS identified the Cu/Zr surface atomic ratio of the catalysts. TPR patterns showed two main peaks for the Cu NPS/ZrO2 pH = 9 catalyst; the first peak between 125 and 180 °C (region I) was ascribed to more dispersed copper species, and the second one between 180 and 250 °C (region II) was assigned to bulk CuO. The catalysts prepared at pH = 4 and pH = 7 only revealed reduction at lower temperatures (region I). Copper dispersion was determined by N2O chemisorption. With NH3-TPD it was found that Cu NPs/ZrO2 pH = 9 exhibited the highest total quantity of acidic sites and the highest apparent kinetic constant, with a value of 0.004 min−1. The different pH applied to the synthesis media of the copper nanoparticles determined the resultant copper dispersion on the ZrO2 support, providing active domains for glycerol conversion. Full article
(This article belongs to the Special Issue Metallic Nanoparticles and Metal-Mediated Synthesis in Catalysis)
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Review

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27 pages, 44211 KiB  
Review
Core–Shell Catalysts for Conventional Oxidation of Alcohols: A Brief Review
by Luís M. M. Correia, Maxim L. Kuznetsov and Elisabete C. B. A. Alegria
Catalysts 2023, 13(7), 1137; https://doi.org/10.3390/catal13071137 - 21 Jul 2023
Cited by 1 | Viewed by 1256
Abstract
This review highlights recent research on the application of core–shell structured materials as catalysts in the oxidation of alcohols to value-added products, such as benzaldehyde, acetophenone, benzophenone, cinnamaldehyde, and vanillin, among others. While the application of various unconventional energy inputs (such as microwave [...] Read more.
This review highlights recent research on the application of core–shell structured materials as catalysts in the oxidation of alcohols to value-added products, such as benzaldehyde, acetophenone, benzophenone, cinnamaldehyde, and vanillin, among others. While the application of various unconventional energy inputs (such as microwave and ultrasound irradiation) was reported, this paper focuses on conventional heating. The oxidation of homocyclic aromatic, heterocyclic aromatic, aliphatic, and alicyclic alcohols catalyzed by core–shell composite catalysts is addressed. This work also highlights some unique advantages of core–shell nanomaterial catalysis, namely the flexibility of combining individual functions for specific purposes as well as the effect of various parameters on the catalytic performance of these materials. Full article
(This article belongs to the Special Issue Metallic Nanoparticles and Metal-Mediated Synthesis in Catalysis)
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28 pages, 3070 KiB  
Review
Carbon Dioxide Conversion on Supported Metal Nanoparticles: A Brief Review
by Sergio Posada-Pérez, Miquel Solà and Albert Poater
Catalysts 2023, 13(2), 305; https://doi.org/10.3390/catal13020305 - 30 Jan 2023
Cited by 11 | Viewed by 2720
Abstract
The increasing concentration of anthropogenic CO2 in the air is one of the main causes of global warming. The Paris Agreement at COP 21 aims to reach the global peak of greenhouse gas emissions in the second half of this century, with [...] Read more.
The increasing concentration of anthropogenic CO2 in the air is one of the main causes of global warming. The Paris Agreement at COP 21 aims to reach the global peak of greenhouse gas emissions in the second half of this century, with CO2 conversion towards valuable added compounds being one of the main strategies, especially in the field of heterogeneous catalysis. In the current search for new catalysts, the deposition of metallic nanoparticles (NPs) supported on metal oxides and metal carbide surfaces paves the way to new catalytic solutions. This review provides a comprehensive description and analysis of the relevant literature on the utilization of metal-supported NPs as catalysts for CO2 conversion to useful chemicals and propose that the next catalysts generation can be led by single-metal-atom deposition, since in general, small metal particles enhance the catalytic activity. Among the range of potential indicators of catalytic activity and selectivity, the relevance of NPs’ size, the strong metal–support interactions, and the formation of vacancies on the support are exhaustively discussed from experimental and computational perspective. Full article
(This article belongs to the Special Issue Metallic Nanoparticles and Metal-Mediated Synthesis in Catalysis)
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