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

Deadline for manuscript submissions: closed (31 January 2016) | Viewed by 110044

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Prof. Dr. Hermenegildo García

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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
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Prof. Dr. Sergio Navalon

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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

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Published Papers (14 papers)

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Editorial

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145 KiB

Open AccessEditorial

Nanoparticles for Catalysis

by Sergio Navalón and H. García

Nanomaterials 2016, 6(7), 123; https://doi.org/10.3390/nano6070123 - 23 Jun 2016

Cited by 62 | Viewed by 5981

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

Open AccessArticle

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://doi.org/10.3390/nano6060103 - 4 Jun 2016

Cited by 44 | Viewed by 6584

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 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 (K_a) 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

Open AccessArticle

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://doi.org/10.3390/nano6060099 - 25 May 2016

Cited by 9 | Viewed by 6436

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 (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

Open AccessArticle

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://doi.org/10.3390/nano6050093 - 18 May 2016

Cited by 45 | Viewed by 8536

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 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

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11370 KiB

Open AccessArticle

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://doi.org/10.3390/nano6040059 - 1 Apr 2016

Cited by 137 | Viewed by 11880

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 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

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1829 KiB

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

by Dimitrios Andreou, Domna Iordanidou, Ioannis Tamiolakis, Gerasimos S. Armatas and Ioannis N. Lykakis

Nanomaterials 2016, 6(3), 54; https://doi.org/10.3390/nano6030054 - 22 Mar 2016

Cited by 38 | Viewed by 9432

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) 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

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1179 KiB

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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://doi.org/10.3390/nano6030045 - 9 Mar 2016

Cited by 38 | Viewed by 8759

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 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

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1575 KiB

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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://doi.org/10.3390/nano6030040 - 26 Feb 2016

Cited by 18 | Viewed by 5333

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

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6030 KiB

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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://doi.org/10.3390/nano6030037 - 24 Feb 2016

Cited by 9 | Viewed by 5957

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.

(This article belongs to the Special Issue Nanoparticles for Catalysis)

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5191 KiB

Open AccessArticle

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://doi.org/10.3390/nano6010022 - 20 Jan 2016

Cited by 37 | Viewed by 7422

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 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

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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://doi.org/10.3390/nano6010021 - 18 Jan 2016

Cited by 16 | Viewed by 8671

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 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 (D_O₂andD_{_O⁻₂}), the rate constant (k_f) for producing O_₂^•−_, 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 k_f and k for MnO_₂/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

Open AccessFeature PaperArticle

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://doi.org/10.3390/nano6010010 - 6 Jan 2016

Cited by 17 | Viewed by 5933

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 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

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1916 KiB

Open AccessArticle

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://doi.org/10.3390/nano5042203 - 8 Dec 2015

Cited by 42 | Viewed by 7739

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 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

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Review

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5810 KiB

Open AccessReview

Biosynthesis of Metal Nanoparticles: Novel Efficient Heterogeneous Nanocatalysts

by Jose M. Palomo and Marco Filice

Nanomaterials 2016, 6(5), 84; https://doi.org/10.3390/nano6050084 - 5 May 2016

Cited by 58 | Viewed by 7835

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 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

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