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Metal Nanocatalysts in Green Synthesis and Energy Applications

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (30 August 2016) | Viewed by 60294

Special Issue Editors


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Guest Editor
Chemistry Department, University of Bari “Aldo Moro”, 4 via Orabona, 70126 Bari, Italy
Interests: surface science; nanoantimicrobials; (nano)catalysts; chem- & bio-sensors; spectroscopy for chemical analysis
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Guest Editor
Dipartimento di Chimica, Università degli Studi di Bari Aldo Moro, 4 Via Orabona, I-70126 Bari, Italy
Interests: catalysts for green chemistry; C-C and C-X bond coupling; MALDI mass spectrometry; fuel cells, CO2 and CO chemical fixation
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The number of studies and patents dealing with traditional metal nanoparticles and non-conventional nanocatalysts is increasing tremendously in the fields of catalysis and energy.

Nano-catalysis is expected to be a fruitful area for Green Chemistry, and the increasing ability to design in the nano-state may offer expanding catalytic developments. Nanotechnologies can help to redraw old industrial processes under a “greener” approach, re-evaluating, at a small scale, the synthesis of fine chemicals or drugs for the pharmaceutical industry. By finely tuning the scalability of the process, waste minimization and the saving of energy could be important goals easily reached by modern industry.

However, to provide the maximum benefit for society and the environment, nanocatalyst recycling is mandatory and it still represents an open challenge for chemists. To this end, supported catalysts, in combination with eco-friendly solvents (viz. ionic liquids, supercritical fluids, fluorous phases, water, etc.), can represent a valid and green alternative to homogeneous catalysis in classic solvents.

The need for energy is increasing worldwide, while, at the same time, fossil resources are decreasing tremendously. Industrial economies, as well as emerging countries, need to produce, transport, store, and use energy with increased efficiency.

In recent years, there have been tremendous efforts focusing on the development of new and cost-effective electrochemical technologies and materials. Novel nanophases, electrodes, and electrolyte materials are extensively investigated, as well as electrode and device configurations, to improve energy production, storage, and conversion technologies, employing electrochemical methods. In particular, electrodeposition is well known for depositing metals and metallic alloys at the industrial level, with a wide range of applications, from large area surface treatments to most advanced electronic industries. The electrodeposition of materials represents a new challenge, not only from an academic point of view, but also from an economic one, as this method presents interesting characteristics for large areas, such as low cost, and generally low temperature and soft processing of materials. The great interest in nanometer-scale materials systems arises from the fact that their optical, electrical, magnetic, or mechanical properties are often very different from the same materials in the bulk phase, and, more importantly, they can be tuned by changing the physical dimensions of the material. The procedure can be extended to the deposition of metals with the aim of limiting the amount of precious metals in electrocatalysis.

This Special Issue of Molecules focuses on the use of nanocatalysts and nanotechnologies in a wide range of catalytic organic reactions, electro-catalysis, and energy applications.

Suitable topics include, just to cite a few:

  • Traditional carbon-carbon or carbon-heteroatom bond forming reactions (e.g., Heck, Suzuki, Stille, Sonogashira, Ullmann, Glodberg, and so on);
  • Synthetic approaches, based on the green chemistry principles: atom-economy, dematerialization, energy saving, raw material diversification, green solvents, etc.;
  • Detoxification of PCBs, fixation and chemical valorization of CO2, and so on;
  • Nano-metal catalyzed processes and technologies for recycle/conversion of plastics, biomasses and wastes;
  • Development, characterization, device technology and performance of nano-metals and non-conventional nanocatalysts in: fuel cells, batteries, supercapacitors,    electrocatalysis, etc.;
  • Surfaces modified for Energy Devices

Truly multidisciplinary studies providing a bird’s-eye-view of nanocatalyst features, including its development/synthesis and its analytical chemical and morphological characterization, as well as applications and structure-performance level correlations, are strongly encouraged.

Dr. Nicola Cioffi
Dr. Antonio Monopoli
Prof. Dr. Massimo Innocenti
Guest Editors

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Published Papers (8 papers)

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Research

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2730 KiB  
Communication
Preparation of Cu@Cu2O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol
by Seongwan Jang, Chohye Yoon, Jae Myung Lee, Sungkyun Park and Kang Hyun Park
Molecules 2016, 21(11), 1467; https://doi.org/10.3390/molecules21111467 - 2 Nov 2016
Cited by 8 | Viewed by 6867
Abstract
HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe3O4@HKUST-1 by layer-by layer assembly strategy and Cu@Cu [...] Read more.
HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe3O4@HKUST-1 by layer-by layer assembly strategy and Cu@Cu2O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu2O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di-tert-butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity. Full article
(This article belongs to the Special Issue Metal Nanocatalysts in Green Synthesis and Energy Applications)
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1371 KiB  
Article
Spectroelectrochemical Study of Carbon Monoxide and Ethanol Oxidation on Pt/C, PtSn(3:1)/C and PtSn(1:1)/C Catalysts
by Rubén Rizo, María Jesús Lázaro, Elena Pastor and Gonzalo García
Molecules 2016, 21(9), 1225; https://doi.org/10.3390/molecules21091225 - 12 Sep 2016
Cited by 25 | Viewed by 7569
Abstract
PtSn-based catalysts are one of the most active materials toward that contribute ethanol oxidation reaction (EOR). In order to gain a better understanding of the Sn influence on the carbon monoxide (principal catalyst poison) and ethanol oxidation reactions in acidic media, a systematic [...] Read more.
PtSn-based catalysts are one of the most active materials toward that contribute ethanol oxidation reaction (EOR). In order to gain a better understanding of the Sn influence on the carbon monoxide (principal catalyst poison) and ethanol oxidation reactions in acidic media, a systematic spectroelectrochemical study was carried out. With this end, carbon-supported PtSnx (x = 0, 1/3 and 1) materials were synthesized and employed as anodic catalysts for both reactions. In situ Fourier transform infrared spectroscopy (FTIRS) and differential electrochemical mass spectrometry (DEMS) indicate that Sn diminishes the amount of bridge bonded CO (COB) and greatly improves the CO tolerance of Pt-based catalysts. Regarding the effect of Sn loading on the EOR, it enhances the catalytic activity and decreases the onset potential. FTIRS and DEMS analysis indicate that the C-C bond scission occurs at low overpotentials and at the same potential values regardless of the Sn loading, although the amount of C-C bond breaking decreases with the rise of Sn in the catalytic material. Therefore, the elevated catalytic activity toward the EOR at PtSn-based electrodes is mainly associated with the improved CO tolerance and the incomplete oxidation of ethanol to form acetic acid and acetaldehyde species, causing the formation of a higher amount of both C2 products with the rise of Sn loading. Full article
(This article belongs to the Special Issue Metal Nanocatalysts in Green Synthesis and Energy Applications)
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2054 KiB  
Article
An Integrated Experimental/Theoretical Study of Structurally Related Poly-Thiophenes Used in Photovoltaic Systems
by Davide Vanossi, Luigi Cigarini, Andrea Giaccherini, Enrico Da Como and Claudio Fontanesi
Molecules 2016, 21(1), 110; https://doi.org/10.3390/molecules21010110 - 19 Jan 2016
Cited by 12 | Viewed by 5680
Abstract
In this work, a series of eight thiophene-based polymers (exploited as “donors” in bulk heterojunction photovoltaics cells), whose structures were designed to be suitably tuned with the electronic characteristics of the [6,6]-Phenyl C61 butyric acid methyl ester (PCBM), is considered,. The electronic properties [...] Read more.
In this work, a series of eight thiophene-based polymers (exploited as “donors” in bulk heterojunction photovoltaics cells), whose structures were designed to be suitably tuned with the electronic characteristics of the [6,6]-Phenyl C61 butyric acid methyl ester (PCBM), is considered,. The electronic properties of the mono-, di-, trimeric oligomers are reckoned (at the Hartree-Fock and DFT level of the theory) and compared to experimental spectroscopic and electrochemical results. Indeed, electrochemical and spectroscopic results show a systematic difference whose physical nature is assessed and related to the exciton (electron-hole) binding energy ( J e , h ). The critical comparison of the experimental and theoretical band gaps, i.e., the HOMO-LUMO energy difference, suggests that electrochemical and DFT values are the most suited to being used in the design of a polythiophene-based p-n junction for photovoltaics. Full article
(This article belongs to the Special Issue Metal Nanocatalysts in Green Synthesis and Energy Applications)
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5212 KiB  
Communication
An Efficient and Recyclable Nanoparticle-Supported Cobalt Catalyst for Quinoxaline Synthesis
by Fatemeh Rajabi, Diego Alves and Rafael Luque
Molecules 2015, 20(11), 20709-20718; https://doi.org/10.3390/molecules201119731 - 19 Nov 2015
Cited by 17 | Viewed by 6538
Abstract
The syntheses of quinoxalines derived from 1,2-diamine and 1,2-dicarbonyl compounds under mild reaction conditions was carried out using a nanoparticle-supported cobalt catalyst. The supported nanocatalyst exhibited excellent activity and stability and it could be reused for at least ten times without any loss [...] Read more.
The syntheses of quinoxalines derived from 1,2-diamine and 1,2-dicarbonyl compounds under mild reaction conditions was carried out using a nanoparticle-supported cobalt catalyst. The supported nanocatalyst exhibited excellent activity and stability and it could be reused for at least ten times without any loss of activity. No cobalt contamination could be detected in the products by AAS measurements, pointing to the excellent activity and stability of the Co nanomaterial. Full article
(This article belongs to the Special Issue Metal Nanocatalysts in Green Synthesis and Energy Applications)
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12768 KiB  
Article
Resin-Immobilized Palladium Nanoparticle Catalysts for Organic Reactions in Aqueous Media: Morphological Aspects
by Piero Mastrorilli, Maria M. Dell’Anna, Antonino Rizzuti, Matilda Mali, Mauro Zapparoli and Cristina Leonelli
Molecules 2015, 20(10), 18661-18684; https://doi.org/10.3390/molecules201018661 - 14 Oct 2015
Cited by 20 | Viewed by 7162
Abstract
An insight into the nano- and micro-structural morphology of a polymer supported Pd catalyst employed in different catalytic reactions under green conditions is reported. The pre-catalyst was obtained by copolymerization of the metal-containing monomer Pd(AAEMA)2 [AAEMA = deprotonated form of 2-(acetoacetoxy) [...] Read more.
An insight into the nano- and micro-structural morphology of a polymer supported Pd catalyst employed in different catalytic reactions under green conditions is reported. The pre-catalyst was obtained by copolymerization of the metal-containing monomer Pd(AAEMA)2 [AAEMA = deprotonated form of 2-(acetoacetoxy) ethyl methacrylate] with ethyl methacrylate as co-monomer, and ethylene glycol dimethacrylate as cross-linker. This material was used in water for the Suzuki-Miyaura cross-coupling of aryl bromides, and for the reduction of nitroarenes and quinolines using NaBH4 or H2, as reductants. TEM analyses showed that in all cases the pristine Pd(II) species were reduced in situ to Pd(0), which formed metal nanoparticles (NPs, the real active species). The dependence of their average size (2–10 nm) and morphology on different parameters (temperature, reducing agent, presence of a phase transfer agent) is discussed. TEM and micro-IR analyses showed that the polymeric support retained its porosity and stability for several catalytic cycles in all reactions and Pd NPs did not aggregate after reuse. The metal nanoparticle distribution throughout the polymer matrix after several recycles provided precious information about the catalytic mechanism, which was truly heterogeneous in the hydrogenation reactions and of the so-called “release and catch” type in the Suzuki coupling. Full article
(This article belongs to the Special Issue Metal Nanocatalysts in Green Synthesis and Energy Applications)
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729 KiB  
Communication
Transfer Hydrogenation Employing Ethylene Diamine Bisborane in Water and Pd- and Ru-Nanoparticles in Ionic Liquids
by Sebastian Sahler, Martin Scott, Christian Gedig and Martin H. G. Prechtl
Molecules 2015, 20(9), 17058-17069; https://doi.org/10.3390/molecules200917058 - 17 Sep 2015
Cited by 8 | Viewed by 6258
Abstract
Herein we demonstrate the use of ethylenediamine bisborane (EDAB) as a suitable hydrogen source for transfer hydrogenation reactions on C-C double bonds mediated by metal nanoparticles. Moreover, EDAB also acts as a reducing agent for carbonyl functionalities in water under metal-free conditions. Full article
(This article belongs to the Special Issue Metal Nanocatalysts in Green Synthesis and Energy Applications)
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3671 KiB  
Article
Synergy of Cobalt and Silver Microparticles Electrodeposited on Glassy Carbon for the Electrocatalysis of the Oxygen Reduction Reaction: An Electrochemical Investigation
by Claudio Zafferoni, Giacomo Cioncoloni, Maria Luisa Foresti, Luigi Dei, Emiliano Carretti, Francesco Vizza, Alessandro Lavacchi and Massimo Innocenti
Molecules 2015, 20(8), 14386-14401; https://doi.org/10.3390/molecules200814386 - 7 Aug 2015
Cited by 11 | Viewed by 6476
Abstract
The combination of two different metals, each of them acting on different steps of the oxygen reduction reaction (ORR), yields synergic catalytic effects. In this respect, the electrocatalytic effect of silver is enhanced by the addition of cobalt, which is able to break [...] Read more.
The combination of two different metals, each of them acting on different steps of the oxygen reduction reaction (ORR), yields synergic catalytic effects. In this respect, the electrocatalytic effect of silver is enhanced by the addition of cobalt, which is able to break the O–O bond of molecular oxygen, thus accelerating the first step of the reduction mechanism. At the same time, research is to further reduce the catalyst’s cost, reducing the amount of Ag, which, even though being much less expensive than Pt, is still a noble metal. From this point of view, using a small amount of Ag together with an inexpensive material, such as graphite, represents a good compromise. The aim of this work was to verify if the synergic effects are still operating when very small amounts of cobalt (2–10 μg·cm−2) are added to the microparticles of silver electrodeposited on glassy carbon, described in a preceding paper from us. To better stress the different behaviour observed when cobalt and silver are contemporarily present in the deposit, the catalytic properties of cobalt alone were investigated. The analysis was completed by the Levich plots to evaluate the number of electrons involved and by Tafel plots to show the effects on the reaction mechanism. Full article
(This article belongs to the Special Issue Metal Nanocatalysts in Green Synthesis and Energy Applications)
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Review

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3013 KiB  
Review
Novel Metal Nanomaterials and Their Catalytic Applications
by Jiaqing Wang and Hongwei Gu
Molecules 2015, 20(9), 17070-17092; https://doi.org/10.3390/molecules200917070 - 17 Sep 2015
Cited by 99 | Viewed by 11450
Abstract
In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe [...] Read more.
In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts) and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis. Full article
(This article belongs to the Special Issue Metal Nanocatalysts in Green Synthesis and Energy Applications)
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