Special Issue "Nanoparticles for Catalysis"

A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (31 January 2016)

Special Issue Editors

Guest Editor
Prof. Dr. Hermenegildo García

Instituto Universitario de Tecnología Química CSIC‐UPV, Universidad Politécnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, Spain
Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, Saudi Arabia
Website | E-Mail
Fax: +34 96 387 7809
Interests: catalysis; solar fuels; graphene
Guest Editor
Dr. Sergio Navalón

Deparment of Chemistry, Universidad Politécnica de Valencia, C/Camino de Vera, s/n, 46022, Valencia, Spain
E-Mail
Interests: catalysis; photocatalysis; nanoparticles; nanomaterials; green chemistry

Special Issue Information

Dear Colleagues,

One of the clearest examples of the role of nanoscale on the properties of a material is the catalytic activity of metal nanoparticles. As consequence of the large external surface and higher dispersion on the surface, the catalytic activity of metal nanoparticles is usually much higher for smaller nanoparticles and this property can even disappear for particles above 20 nm. In this type of catalysts, one of the major issues is to avoid agglomeration of the nanoparticles and how to stabilize them against growth. This can be achieved by supporting these nanoparticles on large surface area solids and, as a consequence, the interaction and the support of the nanoparticles is a crucial factor that determines the overall catalytic activity.

The present Special Issue of Nanomaterials is aimed at presenting the current state-of-the-art in the use of nanoparticles in catalysis, a field that has blossomed since the 1980s, with seminal discoveries on gold nanoparticles as a selective catalyst, and that matured two decades ago. Nanoparticles present the transition between molecules and clusters to solid materials and, therefore, they can bridge both homogeneous and heterogeneous catalysis, depending on how nanoparticles are formed. In the present Special Issue, we have invited contributions from leading groups in the field with the aim of giving a balanced view of the current state-of-the-art in this discipline.

Prof. Dr. Hermenegildo Garcia
Dr. Sergio Navalón
Guest Editors

Manuscript Submission Information

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Keywords

  • metal nanoparticles
  • heterogeneous catalysis
  • clusters as catalysts
  • gold nanoparticles as catalyst palladium
  • nanoparticles as catalyst
  • noble metals as catalysts

Published Papers (14 papers)

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Editorial

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Open AccessEditorial Nanoparticles for Catalysis
Nanomaterials 2016, 6(7), 123; doi:10.3390/nano6070123
Received: 20 June 2016 / Revised: 20 June 2016 / Accepted: 21 June 2016 / Published: 23 June 2016
Cited by 2 | PDF Full-text (145 KB) | HTML Full-text | XML Full-text
Abstract
Nanoscience emerged in the last decades of the 20th century with the general aim to determine those properties that appear when small particles of nanometric dimensions are prepared and stabilized.[...] Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)

Research

Jump to: Editorial, Review

Open AccessArticle Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds
Nanomaterials 2016, 6(6), 103; doi:10.3390/nano6060103
Received: 22 April 2016 / Revised: 11 May 2016 / Accepted: 13 May 2016 / Published: 4 June 2016
Cited by 5 | PDF Full-text (3535 KB) | HTML Full-text | XML Full-text
Abstract
To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni) and nickel-platinum (NiPt) nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts
[...] Read more.
To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni) and nickel-platinum (NiPt) nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts were characterized and the role of Pt was analysed using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS) techniques. The Ni2+ was reduced to metallic Ni0 via a self-reduction way utilizing the carbon as a reducing agent. The average sizes of the Ni particles in the NiPt catalysts were smaller than that in the supported Ni catalyst. The electronic structure of Ni was affected by the incorporation of Pt. The optimal NiPt catalysts exhibited remarkably improved activity toward the reduction of nitrophenol, which has an apparent rate constant (Ka) of 18.82 × 10−3 s−1, 6.2 times larger than that of Ni catalyst and also larger than most of the reported values of noble-metal and bimetallic catalysts. The enhanced activity could be ascribed to the modification to the electronic structure of Ni by Pt and the effect of exposed crystal planes. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessArticle Synthesis of Ball-Like Ag Nanorod Aggregates for Surface-Enhanced Raman Scattering and Catalytic Reduction
Nanomaterials 2016, 6(6), 99; doi:10.3390/nano6060099
Received: 30 March 2016 / Revised: 18 May 2016 / Accepted: 18 May 2016 / Published: 25 May 2016
Cited by 3 | PDF Full-text (3806 KB) | HTML Full-text | XML Full-text
Abstract
In this work, ball-like Ag nanorod aggregates have been synthesized via a simple seed-mediated method. These Ag mesostructures were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-Vis), and X-ray diffraction (XRD). Adding a certain amount of polyvinyl pyrrolidone
[...] Read more.
In this work, ball-like Ag nanorod aggregates have been synthesized via a simple seed-mediated method. These Ag mesostructures were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-Vis), and X-ray diffraction (XRD). Adding a certain amount of polyvinyl pyrrolidone (PVP) can prolong its coagulation time. These Ag nanorod aggregates exhibit effective SERS effect, evaluated by Rhodamine 6G (R6G) and doxorubicin (DOX) as probe molecules. The limit of detection (LOD) for R6G and DOX are as low as 5 × 10−9 M and 5 × 10−6 M, respectively. Moreover, these Ag nanorod aggregates were found to be potential catalysts for the reduction of 4-nitrophenol (4-NP) in the presence of NaBH4. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessArticle Mechanochemical Synthesis of TiO2 Nanocomposites as Photocatalysts for Benzyl Alcohol Photo-Oxidation
Nanomaterials 2016, 6(5), 93; doi:10.3390/nano6050093
Received: 3 March 2016 / Revised: 4 May 2016 / Accepted: 7 May 2016 / Published: 18 May 2016
Cited by 5 | PDF Full-text (3075 KB) | HTML Full-text | XML Full-text
Abstract
TiO2 (anatase phase) has excellent photocatalytic performance and different methods have been reported to overcome its main limitation of high band gap energy. In this work, TiO2-magnetically-separable nanocomposites (MAGSNC) photocatalysts with different TiO2 loading were synthesized using a simple
[...] Read more.
TiO2 (anatase phase) has excellent photocatalytic performance and different methods have been reported to overcome its main limitation of high band gap energy. In this work, TiO2-magnetically-separable nanocomposites (MAGSNC) photocatalysts with different TiO2 loading were synthesized using a simple one-pot mechanochemical method. Photocatalysts were characterized by a number of techniques and their photocatalytic activity was tested in the selective oxidation of benzyl alcohol to benzaldehyde. Extension of light absorption into the visible region was achieved upon titania incorporation. Results indicated that the photocatalytic activity increased with TiO2 loading on the catalysts, with moderate conversion (20%) at high benzaldehyde selectivity (84%) achieved for 5% TiO2-MAGSNC. These findings pointed out a potential strategy for the valorization of lignocellulosic-based biomass under visible light irradiation using designer photocatalytic nanomaterials. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessArticle Nickel Decorated on Phosphorous-Doped Carbon Nitride as an Efficient Photocatalyst for Reduction of Nitrobenzenes
Nanomaterials 2016, 6(4), 59; doi:10.3390/nano6040059
Received: 3 February 2016 / Revised: 12 March 2016 / Accepted: 21 March 2016 / Published: 1 April 2016
Cited by 8 | PDF Full-text (11370 KB) | HTML Full-text | XML Full-text
Abstract
Nickel nanoparticle-decorated phosphorous-doped graphitic carbon nitride (Ni@g-PC3N4) was synthesized and used as an efficient photoactive catalyst for the reduction of various nitrobenzenes under visible light irradiation. Hydrazine monohydrate was used as the source of protons and electrons for the
[...] Read more.
Nickel nanoparticle-decorated phosphorous-doped graphitic carbon nitride (Ni@g-PC3N4) was synthesized and used as an efficient photoactive catalyst for the reduction of various nitrobenzenes under visible light irradiation. Hydrazine monohydrate was used as the source of protons and electrons for the intended reaction. The developed photocatalyst was found to be highly active and afforded excellent product yields under mild experimental conditions. In addition, the photocatalyst could easily be recovered and reused for several runs without any detectable leaching during the reaction. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessFeature PaperArticle Reduction of Nitroarenes into Aryl Amines and N-Aryl hydroxylamines via Activation of NaBH4 and Ammonia-Borane Complexes by Ag/TiO2 Catalyst
Nanomaterials 2016, 6(3), 54; doi:10.3390/nano6030054
Received: 10 February 2016 / Revised: 9 March 2016 / Accepted: 10 March 2016 / Published: 22 March 2016
Cited by 7 | PDF Full-text (1829 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In this study, we report the fabrication of mesoporous assemblies of silver and TiO2 nanoparticles (Ag/MTA) and demonstrate their catalytic efficiency for the selective reduction of nitroarenes. The Ag/TiO2 assemblies, which show large surface areas (119–128 m2·g−1)
[...] Read more.
In this study, we report the fabrication of mesoporous assemblies of silver and TiO2 nanoparticles (Ag/MTA) and demonstrate their catalytic efficiency for the selective reduction of nitroarenes. The Ag/TiO2 assemblies, which show large surface areas (119–128 m2·g−1) and narrow-sized mesopores (ca. 7.1–7.4 nm), perform as highly active catalysts for the reduction of nitroarenes, giving the corresponding aryl amines and N-aryl hydroxylamines with NaBH4 and ammonia-borane (NH3BH3), respectively, in moderate to high yields, even in large scale reactions (up to 5 mmol). Kinetic studies indicate that nitroarenes substituted with electron-withdrawing groups reduced faster than those with electron-donating groups. The measured positive ρ values from the formal Hammett-type kinetic analysis of X-substituted nitroarenes are consistent with the proposed mechanism that include the formation of possible [Ag]-H hybrid species, which are responsible for the reduction process. Because of the high observed chemo selectivities and the clean reaction processes, the present catalytic systems, i.e., Ag/MTA-NaBH4 and Ag/MTA-NH3BH3, show promise for the efficient synthesis of aryl amines and N-aryl hydroxylamines at industrial levels. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessArticle Atomic Layer Deposition of Pt Nanoparticles within the Cages of MIL-101: A Mild and Recyclable Hydrogenation Catalyst
Nanomaterials 2016, 6(3), 45; doi:10.3390/nano6030045
Received: 1 February 2016 / Revised: 29 February 2016 / Accepted: 2 March 2016 / Published: 9 March 2016
Cited by 6 | PDF Full-text (1179 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
We present the in situ synthesis of Pt nanoparticles within MIL-101-Cr (MIL = Materials Institute Lavoisier) by means of atomic layer deposition (ALD). The obtained Pt@MIL-101 materials were characterized by means of N2 adsorption and X-ray powder diffraction (XRPD) measurements, showing that
[...] Read more.
We present the in situ synthesis of Pt nanoparticles within MIL-101-Cr (MIL = Materials Institute Lavoisier) by means of atomic layer deposition (ALD). The obtained Pt@MIL-101 materials were characterized by means of N2 adsorption and X-ray powder diffraction (XRPD) measurements, showing that the structure of the metal organic framework was well preserved during the ALD deposition. X-ray fluorescence (XRF) and transmission electron microscopy (TEM) analysis confirmed the deposition of highly dispersed Pt nanoparticles with sizes determined by the MIL-101-Cr pore sizes and with an increased Pt loading for an increasing number of ALD cycles. The Pt@MIL-101 material was examined as catalyst in the hydrogenation of different linear and cyclic olefins at room temperature, showing full conversion for each substrate. Moreover, even under solvent free conditions, full conversion of the substrate was observed. A high concentration test has been performed showing that the Pt@MIL-101 is stable for a long reaction time without loss of activity, crystallinity and with very low Pt leaching. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessCommunication N-doped TiO2 Nanotubes as an Effective Additive to Improve the Catalytic Capability of Methanol Oxidation for Pt/Graphene Nanocomposites
Nanomaterials 2016, 6(3), 40; doi:10.3390/nano6030040
Received: 11 December 2015 / Revised: 27 January 2016 / Accepted: 16 February 2016 / Published: 26 February 2016
Cited by 8 | PDF Full-text (1575 KB) | HTML Full-text | XML Full-text
Abstract
N-doped TiO2 nanotubes have been prepared as additives to improve the catalytic capability of Pt/graphene composites in methanol oxidation reactions. Electrochemical experiments show that the catalytic performance of Pt/graphene composites has been greatly improved by the introduction of N-doped TiO2 nanotubes. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessFeature PaperArticle Supramolecular Assembly of Gold Nanoparticles on Carbon Nanotubes: Application to the Catalytic Oxidation of Hydroxylamines
Nanomaterials 2016, 6(3), 37; doi:10.3390/nano6030037
Received: 19 January 2016 / Revised: 11 February 2016 / Accepted: 16 February 2016 / Published: 24 February 2016
Cited by 3 | PDF Full-text (6030 KB) | HTML Full-text | XML Full-text
Abstract
A supramolecular heterogeneous catalyst was developed by assembly and stabilization of gold nanoparticles on the surface of carbon nanotubes. A layer-by-layer assembly strategy was used and the resulting nanohybrid was involved in the catalytic oxidation of hydroxylamines under mild conditions. The nanohybrid demonstrated
[...] Read more.
A supramolecular heterogeneous catalyst was developed by assembly and stabilization of gold nanoparticles on the surface of carbon nanotubes. A layer-by-layer assembly strategy was used and the resulting nanohybrid was involved in the catalytic oxidation of hydroxylamines under mild conditions. The nanohybrid demonstrated high efficiency and selectivity on hydroxylamine substrates. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessArticle Coupling of Nanocrystalline Anatase TiO2 to Porous Nanosized LaFeO3 for Efficient Visible-Light Photocatalytic Degradation of Pollutants
Nanomaterials 2016, 6(1), 22; doi:10.3390/nano6010022
Received: 26 November 2015 / Revised: 26 November 2015 / Accepted: 15 December 2015 / Published: 20 January 2016
Cited by 8 | PDF Full-text (5191 KB) | HTML Full-text | XML Full-text
Abstract
In this work we have successfully fabricated nanocrystalline anatase TiO2/perovskite-type porous nanosized LaFeO3 (T/P-LFO) nanocomposites using a simple wet chemical method. It is clearly demonstrated by means of atmosphere-controlled steady-state surface photovoltage spectroscopy (SPS) responses, photoluminescence spectra, and fluorescence spectra
[...] Read more.
In this work we have successfully fabricated nanocrystalline anatase TiO2/perovskite-type porous nanosized LaFeO3 (T/P-LFO) nanocomposites using a simple wet chemical method. It is clearly demonstrated by means of atmosphere-controlled steady-state surface photovoltage spectroscopy (SPS) responses, photoluminescence spectra, and fluorescence spectra related to the formed OH radical amount that the photogenerated charge carriers in the resultant T/P-LFO nanocomposites with a proper mole ratio percentage of TiO2 display much higher separation in comparison to the P-LFO alone. This is highly responsible for the improved visible-light activities of T/P-LFO nanocomposites for photocatalytic degradation of gas-phase acetaldehyde and liquid-phase phenol. This work will provide a feasible route to synthesize visible-light responsive nano-photocatalysts for efficient solar energy utilization. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessArticle Investigation of MnO2 and Ordered Mesoporous Carbon Composites as Electrocatalysts for Li-O2 Battery Applications
Nanomaterials 2016, 6(1), 21; doi:10.3390/nano6010021
Received: 9 November 2015 / Revised: 14 December 2015 / Accepted: 12 January 2016 / Published: 18 January 2016
Cited by 1 | PDF Full-text (2253 KB) | HTML Full-text | XML Full-text
Abstract
The electrocatalytic activities of the MnO2/C composites are examined in Li-O2 cells as the cathode catalysts. Hierarchically mesoporous carbon-supported manganese oxide (MnO2/C) composites are prepared using a combination of soft template and hydrothermal methods. The composites are characterized
[...] Read more.
The electrocatalytic activities of the MnO2/C composites are examined in Li-O2 cells as the cathode catalysts. Hierarchically mesoporous carbon-supported manganese oxide (MnO2/C) composites are prepared using a combination of soft template and hydrothermal methods. The composites are characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, small angle X-ray scattering, The Brunauer–Emmett–Teller (BET) measurements, galvanostatic charge-discharge methods, and rotating ring-disk electrode (RRDE) measurements. The electrochemical tests indicate that the MnO2/C composites have excellent catalytic activity towards oxygen reduction reactions (ORRs) due to the larger surface area of ordered mesoporous carbon and higher catalytic activity of MnO2. The O2 solubility, diffusion rates of O2 and O2•− coefficients (DO2 and DO2), the rate constant (kf) for producing O2•−, and the propylene carbonate (PC)-electrolyte
decomposition rate constant (k) of the MnO2/C material were measured by RRDE experiments in the 0.1 M TBAPF6/PC electrolyte. The values of kf and k for MnO2/C are 4.29 × 10−2 cm·s−1 and 2.6 s−1, respectively. The results indicate that the MnO2/C cathode catalyst has higher electrocatalytic activity for the first step of ORR to produce O2•− and achieves a faster PC-electrolyte decomposition rate. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessFeature PaperArticle The Influence of Carbonaceous Matrices and Electrocatalytic MnO2 Nanopowders on Lithium-Air Battery Performances
Nanomaterials 2016, 6(1), 10; doi:10.3390/nano6010010
Received: 1 December 2015 / Revised: 28 December 2015 / Accepted: 31 December 2015 / Published: 6 January 2016
Cited by 1 | PDF Full-text (1729 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Here, we report new gas diffusion electrodes (GDEs) prepared by mixing two different pore size carbonaceous matrices and pure and silver-doped manganese dioxide nanopowders, used as electrode supports and electrocatalytic materials, respectively. MnO2 nanoparticles are finely characterized in terms of structural (X-ray
[...] Read more.
Here, we report new gas diffusion electrodes (GDEs) prepared by mixing two different pore size carbonaceous matrices and pure and silver-doped manganese dioxide nanopowders, used as electrode supports and electrocatalytic materials, respectively. MnO2 nanoparticles are finely characterized in terms of structural (X-ray powder diffraction (XRPD), energy dispersive X-ray (EDX)), morphological (SEM, high-angle annular dark field (HAADF)-scanning transmission electron microscopy (STEM)/TEM), surface (Brunauer Emmet Teller (BET)-Barrett Joyner Halenda (BJH) method) and electrochemical properties. Two mesoporous carbons, showing diverse surface areas and pore volume distributions, have been employed. The GDE performances are evaluated by chronopotentiometric measurements to highlight the effects induced by the adopted materials. The best combination, hollow core mesoporous shell carbon (HCMSC) with 1.0% Ag-doped hydrothermal MnO2 (M_hydro_1.0%Ag) allows reaching very high specific capacity close to 1400 mAh·g−1. Considerably high charge retention through cycles is also observed, due to the presence of silver as a dopant for the electrocatalytic MnO2 nanoparticles. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Open AccessArticle Hydrothermal Synthesis of Ultrasmall Pt Nanoparticles as Highly Active Electrocatalysts for Methanol Oxidation
Nanomaterials 2015, 5(4), 2203-2211; doi:10.3390/nano5042203
Received: 31 October 2015 / Revised: 20 November 2015 / Accepted: 25 November 2015 / Published: 8 December 2015
Cited by 6 | PDF Full-text (1916 KB) | HTML Full-text | XML Full-text
Abstract
Ultrasmall nanoparticles, with sizes in the 1–3 nm range, exhibit unique properties distinct from those of free molecules and larger-sized nanoparticles. Demonstrating that the hydrothermal method can serve as a facile method for the synthesis of platinum nanoparticles, we successfully synthesized ultrasmall Pt
[...] Read more.
Ultrasmall nanoparticles, with sizes in the 1–3 nm range, exhibit unique properties distinct from those of free molecules and larger-sized nanoparticles. Demonstrating that the hydrothermal method can serve as a facile method for the synthesis of platinum nanoparticles, we successfully synthesized ultrasmall Pt nanoparticles with an average size of 2.45 nm, with the aid of poly(vinyl pyrrolidone) (PVP) as reducing agents and capping agents. Because of the size effect, these ultrasmall Pt nanoparticles exhibit a high activity toward the methanol oxidation reaction. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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Review

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Open AccessReview Biosynthesis of Metal Nanoparticles: Novel Efficient Heterogeneous Nanocatalysts
Nanomaterials 2016, 6(5), 84; doi:10.3390/nano6050084
Received: 17 February 2016 / Revised: 19 April 2016 / Accepted: 26 April 2016 / Published: 5 May 2016
Cited by 3 | PDF Full-text (5810 KB) | HTML Full-text | XML Full-text
Abstract
This review compiles the most recent advances described in literature on the preparation of noble metal nanoparticles induced by biological entities. The use of different free or substituted carbohydrates, peptides, proteins, microorganisms or plants have been successfully applied as a new green concept
[...] Read more.
This review compiles the most recent advances described in literature on the preparation of noble metal nanoparticles induced by biological entities. The use of different free or substituted carbohydrates, peptides, proteins, microorganisms or plants have been successfully applied as a new green concept in the development of innovative strategies to prepare these nanoparticles as different nanostructures with different forms and sizes. As a second part of this review, the application of their synthetic ability as new heterogonous catalysts has been described in C–C bond-forming reactions (as Suzuki, Heck, cycloaddition or multicomponent), oxidations and dynamic kinetic resolutions. Full article
(This article belongs to the Special Issue Nanoparticles for Catalysis)
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