Special Issue "Catalysis for Low Temperature Fuel Cells"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: closed (30 June 2016)

Special Issue Editors

Guest Editor
Dr. Vincenzo Baglio

CNR-ITAE Institute for Advanced Energy Technologies “N. Giordano”, Via Salita S. Lucia sopra Contesse 5, Messina 98126, Italy
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Interests: direct alcohol fuel cells; electrocatalysis; polymer electrolyte fuel cells; water electrolysis; metal–air batteries; dye-sensitized solar cells; photo-electrolysis; carbon dioxide electro-reduction
Guest Editor
Dr. David Sebastián

Institute for Advanced Energy Technologies “Nicola Giordano” (ITAE-CNR), Messina, Italy
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Special Issue Information

Dear Colleagues,

Today, the development of active and stable catalysts still represents a challenge to be overcome in the research field of low temperature fuel cells. Operation at low temperatures demands the utilization of highly active catalysts to reduce the activation energy of the electrochemical reactions involved in the electrodes, and thus obtain practical performances and high efficiencies. At present, the most practical catalysts in low temperature fuel cells are highly dispersed Pt nanoparticles. However, these present several drawbacks, such as high cost, limited earth resources, sensitivity to contaminants, no tolerance to the presence of alcohols and instability due to carbon support corrosion and Pt dissolution. In the search for alternative catalysts, researchers have looked at several strategies: increase of the utilization of Pt catalysts by means of novel structures (metal/support); alloying with transition metals; new carbon and non-carbon supports; cheaper platinum-group-metals like Pd; non-platinum-group metals catalysts (Fe-N-C, Co-N-C, etc.); among others. This Special Issue is intended to cover the most recent progress in advanced electro-catalysts, from the synthesis and characterization to the evaluation of activity and degradation mechanisms, in order to gain insights towards the development of high-performing fuel cells.

Dr. Vincenzo Baglio
Dr. David Sebastián
Guest Editors

Manuscript Submission Information

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Keywords

  • proton/anion exchange membrane fuel cells
  • direct alcohol fuel cells
  • oxygen electro-reduction
  • alcohol electro-oxidation
  • electro-oxidation of other organic fuels (formic acid, glycols, etc.)
  • hydrogen electro-oxidation
  • electrode structure
  • catalyst degradation analysis and mechanisms
  • pt-group-metal (Pt, Pd, Ir, Rh, Os, Ru) catalysts
  • non Pt-group-metal catalysts

Published Papers (11 papers)

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Editorial

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Open AccessEditorial Catalysis for Low-Temperature Fuel Cells
Catalysts 2017, 7(12), 370; doi:10.3390/catal7120370
Received: 23 November 2017 / Revised: 28 November 2017 / Accepted: 28 November 2017 / Published: 1 December 2017
PDF Full-text (187 KB) | HTML Full-text | XML Full-text
Abstract
Today, the development of active and stable catalysts still represents a challenge to be overcome in the research field of low-temperature fuel cells.[...] Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)

Research

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Open AccessArticle Pulsed Laser Deposition of Platinum Nanoparticles as a Catalyst for High-Performance PEM Fuel Cells
Catalysts 2016, 6(11), 180; doi:10.3390/catal6110180
Received: 29 September 2016 / Revised: 7 November 2016 / Accepted: 17 November 2016 / Published: 22 November 2016
Cited by 1 | PDF Full-text (2083 KB) | HTML Full-text | XML Full-text
Abstract
The catalyst layers for polymer-electrolyte-membrane (PEM) fuel cells were fabricated by deposition of platinum directly onto the gas diffusion layer using pulsed laser deposition (PLD). This technique reduced the number of steps required to synthesize the catalyst layers and the amount of Pt
[...] Read more.
The catalyst layers for polymer-electrolyte-membrane (PEM) fuel cells were fabricated by deposition of platinum directly onto the gas diffusion layer using pulsed laser deposition (PLD). This technique reduced the number of steps required to synthesize the catalyst layers and the amount of Pt loading required. PEM fuel cells with various Pt loadings for the cathode were investigated. With a cathode Pt loading of 100 μ g·cm 2 , the current density of a single cell reached 1205 mA·cm 2 at 0.6 V, which was close to that of a single cell using an E-TEK (trademark) Pt/C electrode with a cathode Pt loading of 400 μ g·cm 2 . Furthermore, for a PEM fuel cell with both electrodes prepared by PLD and a total anode and cathode Pt loading of 117 μ g·cm 2 , the overall Pt mass-specific power density at 0.6 V reached 7.43 kW·g 1 , which was five times that of a fuel cell with E-TEK Pt/C electrodes. The high mass-specific power density was due to that a very thin nanoporous Pt layer was deposited directly onto the gas diffusion layer, which made good contact with the Nafion membrane and thus resulted in a low-resistance membrane electrode assembly. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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Open AccessArticle One Pot Synthesis of Pt/Graphene Composite Using Polyamidoamine/Chitosan as a Template and Its Electrocatalysis for Methanol Oxidation
Catalysts 2016, 6(10), 165; doi:10.3390/catal6100165
Received: 17 August 2016 / Revised: 18 October 2016 / Accepted: 19 October 2016 / Published: 24 October 2016
Cited by 2 | PDF Full-text (3150 KB) | HTML Full-text | XML Full-text
Abstract
A one-pot hydrothermal strategy was used to synthesize Pt/GNs (PAMAM) & Pt/GNs (CS) composites. Pt nanoparticles are deposited onto graphene sheets (GNs) via synchronous reduction of K2PtCl4 and graphene oxide (GO) under hydrothermal conditons without additional reducing agent. During the
[...] Read more.
A one-pot hydrothermal strategy was used to synthesize Pt/GNs (PAMAM) & Pt/GNs (CS) composites. Pt nanoparticles are deposited onto graphene sheets (GNs) via synchronous reduction of K2PtCl4 and graphene oxide (GO) under hydrothermal conditons without additional reducing agent. During the synthesis process, polyamidoamine (PAMAM) or chitosan (CS) was used as a template respectively to obtain shape controlled Pt particles on the surface of GNs, leading to the formation of flower-like Pt nanoclusters for Pt/GNs (PAMAM) and uniform spherical Pt nanoparticles for Pt/GNs (CS). PAMAM and CS are simultaneously served as intrinsic reducing agents to accelerate reduction process; ensuring excellent electrical conductivity of the composites. Electrochemical tests show that Pt/GNs (PAMAM) and Pt/GNs (CS) have much higher electrocatalytic activity and better stability toward methanol oxidation reaction (MOR) in comparison with counterpart Pt/GNs and the commercially available 20% Pt/C catalyst (Pt/C) due to their better dispersion of Pt particles, stronger interaction between Pt and substrate materials, and better electron transfer capability. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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Open AccessArticle Facile Synthesis of Bimetallic Pt-Ag/Graphene Composite and Its Electro-Photo-Synergistic Catalytic Properties for Methanol Oxidation
Catalysts 2016, 6(9), 144; doi:10.3390/catal6090144
Received: 25 July 2016 / Revised: 7 September 2016 / Accepted: 9 September 2016 / Published: 16 September 2016
Cited by 1 | PDF Full-text (7284 KB) | HTML Full-text | XML Full-text
Abstract
A Pt-Ag/graphene composite (Pt-Ag/GNs) was synthesized by the facile aqueous solution method, in which Ag+ was first transformed into Ag2O under UV light irradiation, and then Ag2O, Pt2+, and graphene oxide (GO) were simultaneously reduced by
[...] Read more.
A Pt-Ag/graphene composite (Pt-Ag/GNs) was synthesized by the facile aqueous solution method, in which Ag+ was first transformed into Ag2O under UV light irradiation, and then Ag2O, Pt2+, and graphene oxide (GO) were simultaneously reduced by formic acid. It was found that Pt-Ag bimetallic nanoparticles were highly dispersed on the surface of graphene, and their size distribution was narrow with an average diameter of 3.3 nm. Electrocatalytic properties of the Pt-Ag/GNs composite were investigated by cyclic voltammograms (CVs), chronoamperometry (CA), CO-stripping voltammograms, and electrochemical impedance spectrum (EIS) techniques. It was shown that the Pt-Ag/GNs composite has much higher catalytic activity and stability for the methanol oxidation reaction (MOR) and better tolerance toward CO poisoning when compared with Pt/GNs and the commercially available Johnson Matthey 20% Pt/C catalyst (Pt/C-JM). Furthermore, the Pt-Ag/GNs composite showed efficient electro-photo-synergistic catalysis for MOR under UV or visible light irradiation. Particularly in the presence of UV irradiation, the Pt-Ag/GNs composite exhibited an ultrahigh mass activity of 1842.4 mA·mg−1, nearly 2.0 times higher than that without light irradiation (838.3 mA·mg−1). Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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Open AccessArticle Effects of the Electrodeposition Time in the Synthesis of Carbon-Supported Pt(Cu) and Pt-Ru(Cu) Core-Shell Electrocatalysts for Polymer Electrolye Fuel Cells
Catalysts 2016, 6(8), 125; doi:10.3390/catal6080125
Received: 22 June 2016 / Revised: 29 July 2016 / Accepted: 10 August 2016 / Published: 18 August 2016
Cited by 1 | PDF Full-text (4102 KB) | HTML Full-text | XML Full-text
Abstract
Pt(Cu)/C and Pt-Ru(Cu)/C electrocatalysts with core-shell structure supported on Vulcan Carbon XC72R have been synthesized by potentiostatic deposition of Cu nanoparticles on the support, galvanic exchange with Pt and spontaneous deposition of Ru species. The duration of the electrodeposition time of the different
[...] Read more.
Pt(Cu)/C and Pt-Ru(Cu)/C electrocatalysts with core-shell structure supported on Vulcan Carbon XC72R have been synthesized by potentiostatic deposition of Cu nanoparticles on the support, galvanic exchange with Pt and spontaneous deposition of Ru species. The duration of the electrodeposition time of the different species has been modified and the obtained electrocatalysts have been characterized using electrochemical and structural techniques. The High Resolution Transmission Electron Microscopy (HRTEM), Fast Fourier Transform (FFT) and Energy Dispersive X-ray (EDX) microanalyses allowed the determining of the effects of the electrodeposition time on the nanoparticle size and composition. The best conditions identified from Cyclic Voltammetry (CV) corresponded to onset potentials for CO and methanol oxidation on Pt-Ru(Cu)/C of 0.41 and 0.32 V vs. the Reversible Hydrogen Electrode (RHE), respectively, which were smaller by about 0.05 V than those determined for Ru-decorated commercial Pt/C. The CO oxidation peak potentials were about 0.1 V smaller when compared to commercial Pt/C and Pt-Ru/C. The positive effect of Cu was related to its electronic effect on the Pt shells and also to the generation of new active sites for CO oxidation. The synthesis conditions to obtain the best performance for CO and methanol oxidation on the core-shell Pt-Ru(Cu)/C electrocatalysts were identified. When compared to previous results in literature for methanol, ethanol and formic acid oxidation on Pt(Cu)/C catalysts, the present results suggest an additional positive effect of the deposited Ru species due to the introduction of the bifunctional mechanism for CO oxidation. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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Open AccessArticle Hydrothermal Method Using DMF as a Reducing Agent for the Fabrication of PdAg Nanochain Catalysts towards Ethanol Electrooxidation
Catalysts 2016, 6(7), 103; doi:10.3390/catal6070103
Received: 21 June 2016 / Revised: 5 July 2016 / Accepted: 12 July 2016 / Published: 15 July 2016
Cited by 3 | PDF Full-text (2100 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In this article, we developed a facile one-step hydrothermal method using dimethyl formamide (DMF) as a reducing agent for the fabrication of PdAg catalyst. The scanning electron microscope (SEM) and transmission electron microscopy (TEM) images have shown that the as-synthesized PdAg catalyst had
[...] Read more.
In this article, we developed a facile one-step hydrothermal method using dimethyl formamide (DMF) as a reducing agent for the fabrication of PdAg catalyst. The scanning electron microscope (SEM) and transmission electron microscopy (TEM) images have shown that the as-synthesized PdAg catalyst had a nanochain structure. The energy-dispersive X-ray analyzer (EDX) spectrum presented the actual molar ratio of Pd and Ag in the PdAg alloy. Traditional electrochemical measurements, such as cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectrometry (EIS), were performed using a CHI 760D electrochemical analyzer to characterize the electrochemical properties of the as-synthesized catalyst. The results have shown that the PdAg catalyst with a nanochain structure displays higher catalytic activity and stability than pure Pd and commercial Pd/C catalysts. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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Open AccessArticle Oxygen Reduction Electrocatalysts Based on Coupled Iron Nitride Nanoparticles with Nitrogen-Doped Carbon
Catalysts 2016, 6(6), 86; doi:10.3390/catal6060086
Received: 14 April 2016 / Revised: 26 May 2016 / Accepted: 6 June 2016 / Published: 15 June 2016
Cited by 6 | PDF Full-text (6093 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Aimed at developing a highly active and stable non-precious metal electrocatalyst for oxygen reduction reaction (ORR), a novel FexNy/NC nanocomposite—that is composed of highly dispersed iron nitride nanoparticles supported on nitrogen-doped carbon (NC)—was prepared by pyrolyzing carbon black with
[...] Read more.
Aimed at developing a highly active and stable non-precious metal electrocatalyst for oxygen reduction reaction (ORR), a novel FexNy/NC nanocomposite—that is composed of highly dispersed iron nitride nanoparticles supported on nitrogen-doped carbon (NC)—was prepared by pyrolyzing carbon black with an iron-containing precursor in an NH3 atmosphere. The influence of the various synthetic parameters such as the Fe precursor, Fe content, pyrolysis temperature and pyrolysis time on ORR performance of the prepared iron nitride nanoparticles was investigated. The formed phases were determined by experimental and simulated X-ray diffraction (XRD) of numerous iron nitride species. We found that Fe3N phase creates superactive non-metallic catalytic sites for ORR that are more active than those of the constituents. The optimized Fe3N/NC nanocomposite exhibited excellent ORR activity and a direct four-electron pathway in alkaline solution. Furthermore, the hybrid material showed outstanding catalytic durability in alkaline electrolyte, even after 4,000 potential cycles. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)

Review

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Open AccessReview Proton Exchange Membrane Fuel Cell Reversal: A Review
Catalysts 2016, 6(12), 197; doi:10.3390/catal6120197
Received: 19 July 2016 / Revised: 9 September 2016 / Accepted: 10 September 2016 / Published: 8 December 2016
Cited by 3 | PDF Full-text (2385 KB) | HTML Full-text | XML Full-text
Abstract
The H2/air-fed proton exchange membrane fuel cell (PEMFC) has two major problems: cost and durability, which obstruct its pathway to commercialization. Cell reversal, which would create irreversible damage to the fuel cell and shorten its lifespan, is caused by reactant starvation,
[...] Read more.
The H2/air-fed proton exchange membrane fuel cell (PEMFC) has two major problems: cost and durability, which obstruct its pathway to commercialization. Cell reversal, which would create irreversible damage to the fuel cell and shorten its lifespan, is caused by reactant starvation, load change, low catalyst performance, and so on. This paper will summarize the causes, consequences, and mitigation strategies of cell reversal of PEMFC in detail. A description of potential change in the anode and cathode and the differences between local starvation and overall starvation are reviewed, which gives a framework for comprehending the origins of cell reversal. According to the root factor of cell starvation, i.e., fuel cells do not satisfy the requirements of electrons and protons of normal anode and cathode chemical reactions, we will introduce specific methods to mitigate or prevent fuel cell damage caused by cell reversal in the view of system management strategies and component material modifications. Based on a comprehensive understanding of cell reversal, it is beneficial to operate a fuel cell stack and extend its lifetime. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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Open AccessFeature PaperReview Non-Precious Electrocatalysts for Oxygen Reduction Reaction in Alkaline Media: Latest Achievements on Novel Carbon Materials
Catalysts 2016, 6(10), 159; doi:10.3390/catal6100159
Received: 1 August 2016 / Revised: 16 September 2016 / Accepted: 26 September 2016 / Published: 19 October 2016
Cited by 11 | PDF Full-text (1691 KB) | HTML Full-text | XML Full-text
Abstract
Low temperature fuel cells (LTFCs) are considered as clean energy conversion systems and expected to help address our society energy and environmental problems. Up-to-date, oxygen reduction reaction (ORR) is one of the main hindering factors for the commercialization of LTFCs, because of its
[...] Read more.
Low temperature fuel cells (LTFCs) are considered as clean energy conversion systems and expected to help address our society energy and environmental problems. Up-to-date, oxygen reduction reaction (ORR) is one of the main hindering factors for the commercialization of LTFCs, because of its slow kinetics and high overpotential, causing major voltage loss and short-term stability. To provide enhanced activity and minimize loss, precious metal catalysts (containing expensive and scarcely available platinum) are used in abundance as cathode materials. Moreover, research is devoted to reduce the cost associated with Pt based cathode catalysts, by identifying and developing Pt-free alternatives. However, so far none of them has provided acceptable performance and durability with respect to Pt electrocatalysts. By adopting new preparation strategies and by enhancing and exploiting synergetic and multifunctional effects, some elements such as transition metals supported on highly porous carbons have exhibited reasonable electrocatalytic activity. This review mainly focuses on the very recent progress of novel carbon based materials for ORR, including: (i) development of three-dimensional structures; (ii) synthesis of novel hybrid (metal oxide-nitrogen-carbon) electrocatalysts; (iii) use of alternative raw precursors characterized from three-dimensional structure; and (iv) the co-doping methods adoption for novel metal-nitrogen-doped-carbon electrocatalysts. Among the examined materials, reduced graphene oxide-based hybrid electrocatalysts exhibit both excellent activity and long term stability. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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Open AccessFeature PaperReview What Can We Learn in Electrocatalysis, from Nanoparticulated Precious and/or Non-Precious Catalytic Centers Interacting with Their Support?
Catalysts 2016, 6(9), 145; doi:10.3390/catal6090145
Received: 12 July 2016 / Revised: 6 September 2016 / Accepted: 9 September 2016 / Published: 21 September 2016
Cited by 2 | PDF Full-text (24563 KB) | HTML Full-text | XML Full-text
Abstract
This review is devoted to discussing the state of the art in the relevant aspects of the synthesis of novel precious and non-precious electrocatalysts. It covers the production of Pt- and Pd-based electrocatalysts synthesized by the carbonyl chemical route, the synthesis description for
[...] Read more.
This review is devoted to discussing the state of the art in the relevant aspects of the synthesis of novel precious and non-precious electrocatalysts. It covers the production of Pt- and Pd-based electrocatalysts synthesized by the carbonyl chemical route, the synthesis description for the preparation of the most catalytically active transition metal chalcogenides, then the employment of free-surfactants synthesis routes to produce non-precious electrocatalysts. A compilation of the best precious electrocatalysts to perform the hydrogen oxidation reaction (HOR) is described; a section is devoted to the synthesis and electrocatalytic evaluation of non-precious materials which can be used to perform the HOR in alkaline medium. Apropos the oxygen reduction reaction (ORR), the synthesis and modification of the supports is also discussed as well, aiming at describing the state of the art to improve kinetics of low temperature fuel cell reactions via the hybridization process of the catalytic center with a variety of carbon-based, and ceramic-carbon supports. Last, but not least, the review covers the experimental half-cells results in a micro-fuel cell platform obtained in our laboratory, and by other workers, analyzing the history of the first micro-fuel cell systems and their tailoring throughout the time bestowing to the design and operating conditions. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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Open AccessReview Palladium-Based Catalysts as Electrodes for Direct Methanol Fuel Cells: A Last Ten Years Review
Catalysts 2016, 6(9), 130; doi:10.3390/catal6090130
Received: 14 July 2016 / Revised: 18 August 2016 / Accepted: 22 August 2016 / Published: 27 August 2016
Cited by 12 | PDF Full-text (442 KB) | HTML Full-text | XML Full-text
Abstract
Platinum-based materials are accepted as the suitable electrocatalysts for anodes and cathodes in direct methanol fuel cells (DMFCs). Nonetheless, the increased demand and scarce world reserves of Pt, as well as some technical problems associated with its use, have motivated a wide research
[...] Read more.
Platinum-based materials are accepted as the suitable electrocatalysts for anodes and cathodes in direct methanol fuel cells (DMFCs). Nonetheless, the increased demand and scarce world reserves of Pt, as well as some technical problems associated with its use, have motivated a wide research focused to design Pd-based catalysts, considering the similar properties between this metal and Pt. In this review, we present the most recent advancements about Pd-based catalysts, considering Pd, Pd alloys with different transition metals and non-carbon supported nanoparticles, as possible electrodes in DMFCs. In the case of the anode, different reported works have highlighted the capacity of these new materials for overcoming the CO poisoning and promote the oxidation of other intermediates generated during the methanol oxidation. Regarding the cathode, the studies have showed more positive onset potentials, as fundamental parameter for determining the mechanism of the oxygen reduction reaction (ORR) and thus, making them able for achieving high efficiencies, with less production of hydrogen peroxide as collateral product. This revision suggests that it is possible to replace the conventional Pt catalysts by Pd-based materials, although several efforts must be made in order to improve their performance in DMFCs. Full article
(This article belongs to the Special Issue Catalysis for Low Temperature Fuel Cells)
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