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Pt/C, PtBi(95:5)/C, Pd/C, and PdBi(95:5)/C were synthesized by the sodium borohydride reducing method to produce metal nanoparticles with advanced electronic properties to enhance the ethanol oxidation reaction (EOR) mechanism. The Transmission Electron Microscopy (TEM) images and X-ray photoelectron spectroscopy (XPS) showed that a small Bi content does not affect the nanoparticle size PdBi/C; in contrast, it does affect the PtBi ones. The X-ray diffraction analysis revealed a lattice parameter modification by Bi dope in Pt crystalline structure. Furthermore, the ATR-FTIR results indicated the suppression of carbonate formation and increment in acetate production. The results of polarization and power density curves on DEFC, the material PtBi/C presented the more high power density, almost six times bigger than Pt/C. PtBi/C also has the highest current density (44 mW/cm2) and the lowest onset potential (−0.6 V) in linear sweep voltammetry experiments. It also has the highest final current density in current-time experiments. Hence, PtBi/C is a very promising electrocatalyst for DEFC.

The CO poisoning effect was overcome using a novel synthesis method. This method consists of using sodium borohydride reducing agent assisted by magnetic field and radiofrequency pulses in the time-domain NMR spectrometer. This synthesis was useful to disperse the Pt nanoparticles over the carbon support and to compress the lattice strain of the Pt crystalline structure. Besides that, Pt/C MFP90° showed a multi-CO oxidation component in cyclic voltammetry, and this can avoid the poisoning effect by creating a large availability of CO species to be adsorbed, desorbed, and re-adsorbed. Pt/C MFP90° has also shown the best performance in the PEMFC regarding H2 and CO + H2 experiments.

PtRh/C–ITO electrocatalysts were prepared in a single-step method using H2PtCl6·6H2O and RhCl3·xH2O as metal sources, sodium borohydride as the reducing agent and a physical mixture of 85% Vulcan Carbon XC72 and 15% In2O3·SnO2 (indium tin oxide—ITO) as support. PtRh/C–ITO were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry, chronoamperommetry, attenuated total reflectance, Fourier transform infrared spectroscopy and performance test on direct alkaline ethanol fuel cell. X-ray diffraction patterns for all PtRh/C–ITO indicated a shift in Pt (fcc) peaks, showing that Rh was incorporated into Pt lattice. Transmission electron microscopy for PtRh/C–ITO showed nanoparticles homogeneously distributed over the support with particles size between 3.0 and 4.0 nm. The XPS results for Pt70Rh30/C–ITO showed the presence of mixed oxidation states of Sn0 and SnO2 that could favor the oxidation of adsorbed intermediates by bifunctional mechanism. Pt90Rh10/C–ITO was more active in electrochemical studies, which could be associated with the C–C bond break. Experiments in direct alkaline ethanol fuel cells showed that the power density values obtained for Pt70Rh30/C–ITO and Pt90Rh10/C–ITO were higher than Pt/C, indicating the beneficial effect of Rh addition to Pt and the use of C–ITO support.

The aim of this work was to produce methanol through partial oxidation of methane. The gas fed in a solid membrane reactor-PEM fuel cell type (H2/H2O2 + CH4) has been used for electrosynthesis of methanol at room temperature, with electricity cogeneration as a benefit. It was observed that the current density measured when injected CH4 in the cathode decreased about 45%. This occurs due to the conversion of methane in methanol in some ranges of potentials. In the other hand, in lower ranges of cell potential, formaldehyde was found. In this work, methane was injected on the cathode together with H2O2 solution, where it was observed that the catalytic layer adsorbed CH4 and H2O2 in active sites, which produced OH− radicals that reacted with the hydrocarbon.

Made available in DSpace on 2021-06-25T10:17:59Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-04-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) The glycerol oxidation reaction (GLYOR) was evaluated using an Au/C electrocatalyst under alkaline conditions and varying glycerol (GLY) concentration. This electrocatalyst was synthesized by the borohydride reduction method. Au/C was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and electrochemical techniques associated with in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR). XRD diffractograms showed the presence of Au (fcc). Cyclic voltammetry assisted by ATR-FTIR in situ measurements revealed that GLY oxidation on gold leads to the formation of a high amount of glyceraldehyde (GLYAD) for low GLY concentrations, while a lower amount of GLYAD was observed and the formation of dihydroxyacetone (DHA) was prevalent for high GLY concentrations. For high GLY concentrations DHA is almost stable, whereas for low GLY concentration DHA is fast oxidized to hydroxypyruvate. The excellent GLYOR activity of the Au/C catalyst in low GLY concentrations leads to the formation of deeper oxidized C1 species. Instituto de Pesquisas Energéticas e Nucleares IPEN/CNEN-SP, Av. Prof. Lineu Prestes, 2242 Cidade Universitária Biosciences Institute São Paulo State University - UNESP Coastal Campus Scuola di Scienza dei Materiali, Via 25 aprile 22, Cogoleto Biosciences Institute São Paulo State University - UNESP Coastal Campus FAPESP: 2014/09087-4 FAPESP: 2014/50279-4 FAPESP: 2017/11937-4 CNPq: 300816/2016-2 CAPES: 88882.315566/2019

Made available in DSpace on 2021-06-25T10:20:00Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-04-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Pd−In/C electrocatalysts were synthesized by the adapted borohydride reduction method in different atomic ratios. Electrocatalysts were evaluated by conventional electrochemical techniques and direct glycerol fuel cells. X-ray diffraction profiles indicated the structure of Pd and In (fcc) phases, as well as the presence of In higher oxidation states. Regarding Transmission electron microscopy, it showed the particle‘s average diameters between 6.1–12.7 nm. All PdIn/C electrocatalysts showed high current values for −0.30 V vs. Ag/AgCl, which the best one was PdIn/C 90 : 10. Higher performance for glycerol oxidation was observed in polarization curves at 90 °C for PdIn/C (30 : 70) composition. Instituto de Pesquisas Energéticas e Nucleares IPEN/CNEN-SP, Av. Prof. Lineu Prestes, 2242 Cidade Universitária, CEP São Paulo State University (UNESP) Instituto de Estudos Avançados do Mar (IEAMar) São Paulo State University São Paulo State University (UNESP) Instituto de Estudos Avançados do Mar (IEAMar) São Paulo State University CNPq: 300816/2016-2 CNPq: 429727/2018-6

Au core and Pd shell supported on carbon structure Au@Pd/C can cleave the C–C bond of ethanol molecules leading to the production of a relatively high amount of CO2 when compared with Pd/C electrocatalyst as the attenuated total reflectance - Fourier transform infrared (ATR-FTIR) experiment shows. Density functional theory (DFT) calculations showed that this could be explained by the oxidation of CO species adsorbed into Pd sites that has a modified electronic structure compared with Pd/C. In terms of DFT analysis, the highest thermodynamical stability of CO in Pd shell with Au core atoms, when compared with Pd/C is because of the increase of virtual orbital states near Fermi level that can be occupied by valence electrons of CO molecule. The d-band center shift is experimentally verified using the valence band X-ray photoelectron spectroscopy and theoretically predicted by the Generalized Koopmans’ Theorem. Besides that, Au@Pd/C electrocatalyst has a better electrochemical activity when compared with Pd/C.

The Pd/C, PdRh(50:50)/C and PdSn(50:50)/C nanomaterials were used as electrocatalysts for ethanol (EtOH) oxidation in Direct Ethanol Fuel Cell (DEFC) in an alkaline medium. This work aims to provide a complete physical characterization of the nanomaterials, elucidate the bifunctional mechanism concerning ethanol oxidation reaction and understand the influence of carbon – metal bonding in the electrochemical activity. These nanomaterials were investigated by X-ray photoelectron spectroscopy (XPS) and revealed that the atomic percentage of the surface is different of those obtained by Energy Dispersive X-ray spectroscopy (EDS). Raman spectroscopy showed a bonding between palladium and carbon atoms which can play a decisive role in the performance of the materials. Attenuated Total Reflectance technique coupled to the Fourier Transform Infrared spectroscopy (ATR-FTIR) made possible to investigate the oxidation products originated by the ethanol oxidation, and all the electrocatalysts showed the presence of acetaldehyde, carbonate ions, acetate and carbon dioxide, suggesting that the mechanism of oxidation is incomplete. Among all the nanomaterials studied, PdSn(50:50)/C showed the best electrochemical and Fuel Cell's results. It is about 33% better than Pd/C. The micrographs obtained by Transmission Electron Microscopy (TEM) revealed some agglomerate regions, but they are consistent with the literature data.

Ethanol electro-oxidation reaction was investigated considering conventional electrochemical experiments in alkaline media, direct ethanol fuel cell (DEFC), and in situ ATR-FTIR. The working electrode/anodes were composed of monometallic Pt/C, Au/C, Ir/C, and trimetallic PtAuIr/C nanoparticles with atomic Pt/Au/Ir ratios of 40:50:10, 50:40:10, 60:30:10, 70:20:10, and 80:10:10. X-ray diffraction (XRD) suggests PtAuIr/C alloy formation, and according to transmission electron micrographs, the mean particle sizes are from 4 to 6 nm for all catalyst compositions. PtAuIr/C 40:50:10 showed the highest catalytic activity for ethanol electro-oxidation in the electrochemical experiments; using this material, the peak current density from ethanol electro-oxidation on cyclic voltammetry experiment was 50 mA per g of Pt, 3.5 times higher than that observed with Pt/C. The fuel cell performance was superior using all PtAuIr/C compositions than using Pt/C. Au/C and Ir/C presented very poor catalytic activity toward ethanol electro-oxidation. The improved results obtained using PtAuIr/C might be related to the OHads species formed at low overpotential on Ir and to the decrease on adsorption energy of poisoning intermediates on Pt sites, promoted by Au.

Pt/C, Rh/C and PtRh/C electrocatalysts with different Pt:Rh atomic ratios supported on Vulcan XC 72 carbon were prepared using borohydride as reducing agent and tested for ethanol electro-oxidation in alkaline medium. X-ray diffraction patterns showed the formation of PtRh alloy. Transmission electron micrographs showed the nanoparticles with particle sizes between 3 and 6 nm for all materials. Electrochemical experiments showed PtRh/C (50:50) the most promising material for ethanol electro-oxidation; however, in situ ATR-FTIR experiments was observed that the ethanol oxidation is incomplete due to the formation of acetate and carbonate.

The main objective of this paper was to characterize the voltammetric profiles of the Pt/C, Pt/C-ATO, Pd/C and Pd/C-ATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte at 25°C and in a direct methane proton exchange membrane fuel cell at 80°C. The electrocatalysts prepared also were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The diffractograms of the Pt/C and Pt/C-ATO electrocatalysts show four peaks associated with Pt face-centered cubic (fcc) structure, and the diffractograms of Pd/C and Pd/C-ATO show four peaks associated with Pd face-centered cubic (fcc) structure. For Pt/C-ATO and Pd/C-ATO, characteristic peaks of cassiterite (SnO2) phase are observed, which are associated with Sb-doped SnO2 (ATO) used as supports for electrocatalysts. Cyclic voltammograms (CV) of all electrocatalysts after adsorption of methane show that there is a current increase during the anodic scan. However, this effect is more pronounced for Pt/C-ATO and Pd/C-ATO. This process is related to the oxidation of the adsorbed species through the bifunctional mechanism, where ATO provides oxygenated species for the oxidation of CO or HCO intermediates adsorbed in Pt or Pd sites. From in situ ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared) experiments for all electrocatalysts prepared the formation of HCO or CO intermediates are observed, which indicates the production of carbon dioxide. Polarization curves at 80°C in a direct methane fuel cell (DMEFC) show that Pd/C and Pt/C electroacatalysts have superior performance to Pd/C-ATO and Pt/C-ATO in methane oxidation.