Nanoparticles for Catalysis

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

Deadline for manuscript submissions: closed (31 January 2016) | Viewed by 101678

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Special Issue Editors

Departamento de Quimica and Instituto Universitario de Tecnologia Quimica (CSIC-UPV), Universitat Politecnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, Spain
Interests: heterogeneous catalysis; photocatalysis
Special Issues, Collections and Topics in MDPI journals
Department of Chemistry, Universitat Politècnica de València, Valencia, Spain
Interests: heterogeneous catalysis and photocatalysis; green chemistry; energy and environmental applications; fine chemicals; petrochemistry; porous and 2D materials; metal nanoparticles
Special Issues, Collections and Topics in MDPI journals

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

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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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145 KiB  
Editorial
Nanoparticles for Catalysis
by Sergio Navalón and H. García
Nanomaterials 2016, 6(7), 123; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6070123 - 23 Jun 2016
Cited by 57 | Viewed by 5474
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

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3535 KiB  
Article
Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds
by Huishan Shang, Kecheng Pan, Lu Zhang, Bing Zhang and Xu Xiang
Nanomaterials 2016, 6(6), 103; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6060103 - 04 Jun 2016
Cited by 40 | Viewed by 5993
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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3806 KiB  
Article
Synthesis of Ball-Like Ag Nanorod Aggregates for Surface-Enhanced Raman Scattering and Catalytic Reduction
by Wenjing Zhang, Yin Cai, Rui Qian, Bo Zhao and Peizhi Zhu
Nanomaterials 2016, 6(6), 99; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6060099 - 25 May 2016
Cited by 9 | Viewed by 6060
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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3075 KiB  
Article
Mechanochemical Synthesis of TiO2 Nanocomposites as Photocatalysts for Benzyl Alcohol Photo-Oxidation
by Weiyi Ouyang, Ewelina Kuna, Alfonso Yepez, Alina M. Balu, Antonio A. Romero, Juan Carlos Colmenares and Rafael Luque
Nanomaterials 2016, 6(5), 93; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6050093 - 18 May 2016
Cited by 41 | Viewed by 7958
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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11370 KiB  
Article
Nickel Decorated on Phosphorous-Doped Carbon Nitride as an Efficient Photocatalyst for Reduction of Nitrobenzenes
by Anurag Kumar, Pawan Kumar, Chetan Joshi, Manvi Manchanda, Rabah Boukherroub and Suman L. Jain
Nanomaterials 2016, 6(4), 59; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6040059 - 01 Apr 2016
Cited by 116 | Viewed by 11194
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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1829 KiB  
Article
Reduction of Nitroarenes into Aryl Amines and N-Aryl hydroxylamines via Activation of NaBH4 and Ammonia-Borane Complexes by Ag/TiO2 Catalyst
by Dimitrios Andreou, Domna Iordanidou, Ioannis Tamiolakis, Gerasimos S. Armatas and Ioannis N. Lykakis
Nanomaterials 2016, 6(3), 54; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6030054 - 22 Mar 2016
Cited by 37 | Viewed by 8692
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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1179 KiB  
Article
Atomic Layer Deposition of Pt Nanoparticles within the Cages of MIL-101: A Mild and Recyclable Hydrogenation Catalyst
by Karen Leus, Jolien Dendooven, Norini Tahir, Ranjith K. Ramachandran, Maria Meledina, Stuart Turner, Gustaaf Van Tendeloo, Jan L. Goeman, Johan Van der Eycken, Christophe Detavernier and Pascal Van Der Voort
Nanomaterials 2016, 6(3), 45; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6030045 - 09 Mar 2016
Cited by 37 | Viewed by 8178
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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1575 KiB  
Communication
N-doped TiO2 Nanotubes as an Effective Additive to Improve the Catalytic Capability of Methanol Oxidation for Pt/Graphene Nanocomposites
by Xiaohua Wang, Yueming Li, Shimin Liu and Long Zhang
Nanomaterials 2016, 6(3), 40; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6030040 - 26 Feb 2016
Cited by 17 | Viewed by 5009
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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6030 KiB  
Article
Supramolecular Assembly of Gold Nanoparticles on Carbon Nanotubes: Application to the Catalytic Oxidation of Hydroxylamines
by Nimesh Shah, Pallabita Basu, Praveen Prakash, Simon Donck, Edmond Gravel, Irishi N. N. Namboothiri and Eric Doris
Nanomaterials 2016, 6(3), 37; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6030037 - 24 Feb 2016
Cited by 9 | Viewed by 5466
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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5191 KiB  
Article
Coupling of Nanocrystalline Anatase TiO2 to Porous Nanosized LaFeO3 for Efficient Visible-Light Photocatalytic Degradation of Pollutants
by Muhammad Humayun, Zhijun Li, Liqun Sun, Xuliang Zhang, Fazal Raziq, Amir Zada, Yang Qu and Liqiang Jing
Nanomaterials 2016, 6(1), 22; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6010022 - 20 Jan 2016
Cited by 35 | Viewed by 6993
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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2253 KiB  
Article
Investigation of MnO2 and Ordered Mesoporous Carbon Composites as Electrocatalysts for Li-O2 Battery Applications
by Chih-Chun Chin, Hong-Kai Yang and Jenn-Shing Chen
Nanomaterials 2016, 6(1), 21; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6010021 - 18 Jan 2016
Cited by 16 | Viewed by 7961
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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1729 KiB  
Article
The Influence of Carbonaceous Matrices and Electrocatalytic MnO2 Nanopowders on Lithium-Air Battery Performances
by Alessandro Minguzzi, Gianluca Longoni, Giuseppe Cappelletti, Eleonora Pargoletti, Chiara Di Bari, Cristina Locatelli, Marcello Marelli, Sandra Rondinini and Alberto Vertova
Nanomaterials 2016, 6(1), 10; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6010010 - 06 Jan 2016
Cited by 17 | Viewed by 5540
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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1916 KiB  
Article
Hydrothermal Synthesis of Ultrasmall Pt Nanoparticles as Highly Active Electrocatalysts for Methanol Oxidation
by Wenhai Ji, Weihong Qi, Shasha Tang, Hongcheng Peng and Siqi Li
Nanomaterials 2015, 5(4), 2203-2211; https://0-doi-org.brum.beds.ac.uk/10.3390/nano5042203 - 08 Dec 2015
Cited by 33 | Viewed by 7102
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

Jump to: Editorial, Research

5810 KiB  
Review
Biosynthesis of Metal Nanoparticles: Novel Efficient Heterogeneous Nanocatalysts
by Jose M. Palomo and Marco Filice
Nanomaterials 2016, 6(5), 84; https://0-doi-org.brum.beds.ac.uk/10.3390/nano6050084 - 05 May 2016
Cited by 57 | Viewed by 7204
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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