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ABSTRACT: Pd nanoparticles have been generated by performing an electroless procedure on a mixed ceria (CeO(2))/carbon black (Vulcan XC-72) support. The resulting material, Pd-CeO(2)/C, has been characterized by means of transmission electron microscopy (TEM), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray diffraction (XRD) techniques. Electrodes coated with Pd-CeO(2)/C have been scrutinized for the oxidation of ethanol in alkaline media in half cells as well as in passive and active direct ethanol fuel cells (DEFCs). Membrane electrode assemblies have been fabricated using Pd-CeO(2)/C anodes, proprietary Fe-Co cathodes, and Tokuyama anion-exchange membranes. The monoplanar passive and active DEFCs have been fed with aqueous solutions of 10 wt% ethanol and 2 M KOH, supplying power densities as high as 66 mW cm(-2) at 25 °C and 140 mW cm(-2) at 80 °C. A comparison with a standard anode electrocatalyst containing Pd nanoparticles (Pd/C) has shown that, at even metal loading and experimental conditions, the energy released by the cells with the Pd-CeO(2)/C electrocatalyst is twice as much as that supplied by the cells with the Pd/C electrocatalyst. A cyclic voltammetry study has shown that the co-support ceria contributes to the remarkable decrease of the onset oxidation potential of ethanol. It is proposed that ceria promotes the formation at low potentials of species adsorbed on Pd, Pd(I)-OH(ads), that are responsible for ethanol oxidation.
ChemSusChem 04/2012; 5(7):1266-73. · 6.83 Impact Factor
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Valentina Bambagioni,
Claudio Bianchini,
Jonathan Filippi,
Alessandro Lavacchi,
Werner Oberhauser,
Andrea Marchionni,
Simonetta Moneti,
Francesco Vizza,
Rinaldo Psaro,
Vladimiro Dal Santo,
Alessandro Gallo,
Sandro Recchia,
Laura Sordelli
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ABSTRACT: The impregnation of Ketjen Black (C) with iron and cobalt phthalocyanines (MPc) taken one by one or as a 1:1 stoichiometric mixture, followed by heat treatment at 600 °C under inert atmosphere, gave materials containing arrays of single metal ions coordinated by four nitrogen atoms (M-N4 units). Increasing the pyrolysis temperature to 800° resulted in the formation of carbon-supported, nanosized metal particles. A key role of the carbon support in determining the material structure at either temperature investigated was demonstrated by TPD, EXAFS, XANES and XRPD studies. These also showed that a Fe–Co alloy is obtained at 800 °C when the impregnation of Ketjen Black involves a mixture of FePc and CoPc. Electrodes coated with the different Fe, Co and Fe–Co materials, containing ca. 3 wt% metal loadings, were scrutinized for the oxygen reduction reaction (ORR) in alkaline media by linear sweep voltammetry. For comparative purposes, two Pt electrocatalysts containing 3 and 20 wt% metal were investigated. The electrochemical activity of all materials was analyzed by Tafel and Koutecky–Levich plots as well as chronopotentiometry. The Fe-containing electrocatalysts have been found to be highly active for the ORR in alkaline media with convective limiting currents as high as 600 A g Fe−1 at room temperature and onset potentials as high as 1.02 V vs. RHE. It has been found that (i) the ORR mass activity of the Pc-derived electrocatalysts is superior to that of the Pt catalysts investigated; (ii) the activity of FePc and FePc–CoPc/C, heat treated at either 600 or 800 °C, is superior to that of the corresponding Co materials; (iii) the electrocatalysts obtained at 600 °C are fairly more active than those obtained at 800 °C.Research highlights▶ Effective cobalt(II)–iron(II) single site electrocatalysts for the ORR. ▶ Nanosized Co–Fe alloy catalyzes efficiently the ORR. ▶ EXAFS study of pyrolized Fe and Co phthalocyanines supported on Ketjen Black. ▶ Highly stable non-noble metal electrocatalysts for the ORR.
Journal of Power Sources 01/2011; 196(5):2519-2529. · 4.95 Impact Factor
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Angewandte Chemie International Edition 09/2010; 49(40):7229-33. · 13.45 Impact Factor
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ABSTRACT: The selective and simultaneous production of hydrogen and chemicals from renewable alcohols, such as ethanol, glycerol, and ethylene glycol, can be accomplished by means of electrolyzers in which the anode electrocatalyst is appropriately designed to promote the partial and selective oxidation of the alcohol. In the electrolyzers described herein, the production of 1 kg of hydrogen from aqueous ethanol occurs with one-third the amount of energy required by a traditional H(2)/O(2) electrolyzer, by virtue of the much lower oxidation potential of ethanol to acetate vs. water to oxygen in alkaline media (E(0)=0.10 V vs. 1.23 V). The self-sustainability of H(2) production is ensured by the simultaneous production of 25 kg of potassium acetate for every kg of H(2), if the promoting co-electrolyte is KOH.
ChemSusChem 07/2010; 3(7):851-5. · 6.83 Impact Factor
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ABSTRACT: The effect of adding small quantities (0.1–1 wt.%) of sodium borohydride (NaBH4) to the anolyte solution of direct ethanol fuel cells (DEFCs) with membrane-electrode assemblies constituted by nanosized Pd/C anode, Fe–Co cathode and anion-exchange membrane (Tokuyama A006) was investigated by means of various techniques. These include cyclic voltammetry, in situ FTIR spectroelectrochemistry, a study of the performance of monoplanar fuel cells and an analysis of the ethanol oxidation products. A comparison with fuel cells fed with aqueous solutions of ethanol proved unambiguously the existence of a promoting effect of NaBH4 on the ethanol oxidation. Indeed, the potentiodynamic curves of the ethanol–NaBH4 mixtures showed higher power and current densities, accompanied by a remarkable increase in the fuel consumption at comparable working time of the cell. A 13C and 11B {1H}NMR analysis of the cell exhausts and an in situ FTIR spectroelectrochemical study showed that ethanol is converted selectively to acetate while the oxidation product of NaBH4 is sodium metaborate (NaBO2). The enhancement of the overall cell performance has been explained in terms of the ability of NaBH4 to reduce the PdO layer on the catalyst surface.
Journal of Power Sources 01/2010; 195:8036-8043. · 4.95 Impact Factor
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ABSTRACT: Ni-Zn and Ni-Zn-P alloys supported on Vulcan XC-72 are effective materials for the spontaneous deposition of palladium through redox transmetalation with Pd(IV) salts. The materials obtained, Pd-(Ni-Zn)/C and Pd-(Ni-Zn-P)/C, have been characterized by a variety of techniques. The analytical and spectroscopic data show that the surface of Pd-(Ni-Zn)/C and Pd-(Ni-Zn-P)/C contain very small, highly dispersed, and highly crystalline palladium clusters as well as single palladium sites, likely stabilized by interaction with oxygen atoms from Ni--O moieties. As a reference material, a nanostructured Pd/C material was prepared by reduction of an aqueous solution of PdCl(2)/HCl with ethylene glycol in the presence of Vulcan XC-72. In Pd/C, the Pd particles are larger, less dispersed, and much less crystalline. Glassy carbon electrodes coated with the Pd-(Ni-Zn)/C and Pd-(Ni-Zn-P)/C materials, containing very low Pd loadings (22-25 microg cm(-2)), were studied for the oxidation of ethanol in alkaline media in half cells and provided excellent results in terms of both specific current (as high as 3600 A g(Pd)(-1) at room temperature) and onset potential (as low as -0.6 V vs Ag/AgCl/KCl(sat)).
ChemSusChem 01/2009; 2(1):99-112. · 6.83 Impact Factor
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Valentina Bambagioni,
Daniele Bani,
Andrea Bencini,
Tarita Biver,
Miriam Cantore,
Riccardo Chelli,
Lorenzo Cinci,
Paola Failli,
Lisa Ghezzi,
Claudia Giorgi,
Silvia Nappini,
Fernando Secco,
Maria Rosaria Tinè,
Barbara Valtancoli,
Marcella Venturini
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ABSTRACT: The synthesis of the Fe(III), Co(II), Mn(II), and Ru(III) complexes with two polyamine-polycarboxylate ligands, N-(2-hydroxyethyl)ethylenediamine-N, N', N'-triacetic acid (H3L1) and ethylene bisglycol tetraacetic acid (H4L2) is reported. Potentiometric studies showed that these ligands form stable complexes in aqueous solution and no metal release occurs, thus accounting for their low toxicity in cultured RAW 264.7 macrophages. X-ray characterization of the [Co(L1)](-) complex showed that binding sites are available at the metal for NO binding. Efficiency of these compounds to bind NO was studied by UV-vis spectrophotometry. Then their NO-scavenging properties were assayed in a cell-free system under physiological conditions, using S-nitroso-N-acetyl-D,L-penicillamine (SNAP) as NO source. The L1 complexes caused the most effective reduction of free NO, [Mn(L1)](-) being the most efficient. Conversely, in NOS II induced RAW 264.7 macrophages, the Ru(III) and Co(II) complexes with L2 were the most effective compounds. [Ru(L2)](-) also afforded significant protection against lipopolysaccharide-induced endotoxic shock in the mouse in vivo.
Journal of Medicinal Chemistry 07/2008; 51(11):3250-60. · 5.25 Impact Factor
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ABSTRACT: Palladium and platinum–ruthenium nanoparticles supported on multi-walled carbon nanotubes (MWCNT) are prepared by the impregnation-reduction procedure. The materials obtained, Pd/MWCNT and Pt–Ru/MWCNT, are characterized by TEM, ICP-AES and XRPD. Electrodes coated with Pd/MWCNT are scrutinized for the oxidation of methanol, ethanol or glycerol in 2 M KOH solution in half cells. The catalyst is very active for the oxidation of all alcohols, with glycerol providing the best performance in terms of specific current density and ethanol showing the lowest onset potential. Membrane-electrode assemblies have been fabricated using Pd/MWCNT anodes, commercial cathodes and anion-exchange membrane and evaluated in both single passive and active direct alcohol fuel cells fed with aqueous solutions of 10 wt.% methanol, 10 wt.% ethanol or 5 wt.% glycerol. Pd/MWCNT exhibits unrivalled activity as anode electrocatalyst for alcohol oxidation. The analysis of the anode exhausts shows that ethanol is selectively oxidized to acetic acid, detected as acetate ion in the alkaline media of the reaction, while methanol yields carbonate and formate. A much wider product distribution, including glycolate, glycerate, tartronate, oxalate, formate and carbonate, is obtained from the oxidation of glycerol. The results obtained with Pt–Ru/MWCNT anodes in acid media are largely inferior to those provided by Pd/MWCNT electrodes in alkaline media.
Journal of Power Sources.
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ABSTRACT: The selective conversion of ethanol into potassium acetate with concomitant production of electrical energy has been achieved in both passive and active direct fuel cells containing platinum-free electrodes and an anion-exchange polymer membrane. The power densities supplied by the passive systems at r.t. can be as high as 55 mW cm−2, while the active systems can deliver up to 170 mW cm−2 at 80 °C. Such high values have never been reported for direct ethanol fuel cells with whatsoever electrocatalyst in either alkaline or acidic media.
Electrochemistry Communications.
