JULIO NANDENHA
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Artigo IPEN-doc 29680 Conversão de metano em metanol com co-geração de energia elétrica a partir de catalisadores de paládio suportados em carbono2023 - SILVA, ARACELI J.; ZAMBIAZI, PRISCILLA J.; GOMES, PAULO V.R.; NANDENHA, JULIO; GODOI, CAMILA M.; SOUZA, RODRIGO F.B. de; NETO, ALMIR O.; AZEREDO, NATHALIA F.B.The application of solid electrolyte reactors for methane oxidation and energy co-generation is attractive, especially with the use of catalysts synthesized from noble metals such as palladium. In this work, we prepared three different compositions of palladium on carbon support to evaluate the composition that had the greatest potential for energy generation. Catalysts in the proportions of 5, 10 and 20% of Pd/C were tested for the conversion of greenhouse gases into organic molecules of higher added value using electrochemical fuel cell solid electrolyte reactors. The focus of this work was the conversion of methane into methanol, using the fuel cell as a reactor and the commercial Pd/C as electrocatalyst. The electrocatalysts were tested at the anode, analyzed by infrared (IR) spectroscopy and their activities verified by experiments with rotating ring disk electrode (RRDE). Higher levels of palladium (Pd/C 20%) favored obtaining electrical power, and the intermediate composition (Pd/C 10%) showed a greater production of less oxidized compounds, such as methanol, in addition to generating electricity.Artigo IPEN-doc 29604 Effect of TiO2 and synthesis strategies on formate oxidation2023 - GUIMARAES, VITORIA P.; NANDENHA, JULIO; ORZARI, LUIZ O.; FATIBELLO-FILHO, ORLANDO; OLIVEIRA NETO, ALMIR; JANEGITZ, BRUNO C.; VICENTINI, FERNANDO C.; ASSUMPCAO, MONICA H.M.T.Direct formate fuel cells have gained increasing attention since formate can be obtained by CO2 reduction, being shown as a renewable power source. This paper reports the use of Pd nanoparticles supported on physical mixtures of Vulcan carbon and TiO2 in different ratios and different Pd reduction methodologies. The materials were prepared using sodium borohydride as a reducing agent and analyzed toward formate oxidation in alkaline media. The prepared electrocatalysts showed peaks of Pd face-centered cubic and TiO2 anatase and rutile phases and an average particle size between 3.7 and 7.9 nm. Experiments considering formate electro-oxidation (voltammetry and chronoamperometry) showed that the presence of TiO2 is favorably using both synthesis methodologies while single cells revealed Pd nanoparticles supported on physical mixtures of carbon and TiO2, in the proportion of 75:25 as the most efficient, which was explained by the carbon high electrical conductivity and small quantities of TiO2 working as co-catalyst.Artigo IPEN-doc 29047 Pd, Ag and Bi carbon-supported electrocatalysts as electrochemical multifunctional materials for ethanol oxidation and dopamine determination2022 - ORZARI, LUIZ O.; ASSUMPCAO, MONICA H.M.T.; NANDENHA, JULIO; OLIVEIRA NETO, ALMIR; MARCOLINO JUNIOR, LUIZ H.; BERGAMINI, MARCIO; JANEGITZ, BRUNO C.This manuscript describes the investigation towards the multifunctional synthesis, characterization, and application of different Pd, Ag and Bi-carbon black supported electrocatalysts in two different fields in electrochemistry: fuel cells and electrochemical sensors. Throughout morphological and electrochemical characterizations, comprising scanning and transmission electron microscopies, X-ray powder diffraction, electrochemical impedance spectroscopy, and cyclic voltammetry techniques, the materials were characterized to better understand their properties towards proposed applications. Afterward, the materials were employed for ethanol oxidation in alkaline media, with investigations by chronoamperometry, cyclic voltammetry, and by closing a direct alkaline fuel cell, which the Pd50Ag45Bi05/C composite presented attractive ethanol catalysis behavior, with a maximum power density of 19.70 mW cm−2, at 30.59 mA cm−2. Also, the proposed device was applied for dopamine determination by square wave voltammetry. In this sense, two linear behaviors, respectively ranging from 0.2 to 1.0 and 4.0 to 40 μmol L−1 were obtained, due to two distinctive mechanisms. This higher activity has been attributed to the synergism among the used metals and proportions contributing to the bifunctional and electronic effects. As synthetic samples investigations were accomplished, data reinforces the proposed material as a possible interfacing composite in electrochemistry.Artigo IPEN-doc 28995 cis-[6-(pyridin-2-yl)-1,3,5-triazine-2,4-diamine](dichloride) palladium(II)-based electrolyte membrane reactors for partial oxidation methane to methanol2022 - GARCIA, LUIS M.S.; ZAMBIAZI, PRISCILLA J.; CHAIR, KHAOULA; DOAN, TUAN D.; RAMOS, ANDREZZA S.; NANDENHA, JULIO; SOUZA, RODRIGO F.B. de; OTUBO, LARISSA; DUONG, ADAM; NETO, ALMIR O.Methane is an abundant resource and the main constituent of natural gas. It can be converted into higher value-added products and as a subproduct of electricity co-generation. The application of polymer electrolyte reactors for the partial oxidation of methane to methanol to co-generate power and chemical products is a topic of great interest for gas and petroleum industries, especially with the use of materials with a lower amount of metals, such as palladium complex. In this study, we investigate the ideal relationship between cis-[6-(pyridin-2-yl)-1,3,5-triazine-2,4-diamine(dichloride)palladium(II)] (Pd-complex) nanostructure and carbon to obtain a stable, conductive, and functional reagent diffusion electrode. The physical and structural properties of the material were analyzed by Fourier transform infrared (FT-IR) and Raman spectroscopies, transmission electron microscopy (TEM), and X-ray powder diffraction (XRD) techniques. The electrocatalytic activity studies revealed that the most active proportion was 20% of Pd-complex supported on carbon (m/m), which was measured with lower values of open-circuit and power density but with higher efficiency in methanol production with reaction rates of r = 4.2 mol L–1·h–1 at 0.05 V.Artigo IPEN-doc 28154 Addition of bismuth to Pt and Pd for electric power generation with selective cogeneration of acetate from ethanol in a fuel cell type reactor2021 - LIMA, F.S.; FONTES, E.H.; NANDENHA, J.; SOUZA, R.F.B. de; NETO, A.O.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.Artigo IPEN-doc 27782 Borohydride reduction method for PdIn/C electrocatalysts synthesis towards glycerol electrooxidation under alkaline condition2021 - NANDENHA, JULIO; RAMOS, CARLOS E.D.; SILVA, SIRLANE G. da; SOUZA, RODRIGO F.B. de; FONTES, ERIC H.; OTTONI, CRISTIANE A.; OLIVEIRA NETO, ALMIRPd−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.Artigo IPEN-doc 27425 Methane activation on PdMn/C‑ITO electrocatalysts using a reactor‑type PEMFC2020 - NANDENHA, J.; YAMASHITA, J.Y.; SOUZA, F.M.; FONTES, E.H.; BATISTA, B.L.; SANTOS, M.C.; LINARDI, M.; NETO, A.O.Various palladium and manganese supported in a mix of carbon and indium thin oxide (PdMn/C-ITO) compositions were synthesized by a sodium borohydride reduction process for methane activation at low temperatures in a proton exchange membrane fuel cell (PEMFC) reactor. These electrocatalysts were characterized by X-ray diffraction, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy XPS, inductively coupled plasma mass spectrometry ICP-MS, attenuated total reflection-Fourier transform infrared spectroscopy, cyclic voltammetry and a PEMFC reactor. The diffractograms of PdMn/C-ITO electrocatalysts revealed the face-centered cubic structure of palladium and the bixbyite cubic structure of In2O3. TEM experiments showed mean nanoparticle sizes between 4.7 and 5.2 nm for all electrocatalysts. XPS results showed the presence of palladium and manganese oxides, as well as Pd0 species. Cyclic voltammograms of PdMn/C-ITO electrocatalysts showed an increase in current density values after the methane adsorption, this result is related to formation of methanol or formic acidic. Polarization curves at 80 °C acquired in a PEMFC reactor showed that PdMn(70:30)/C-ITO and PdMn(50:50)/C-ITO have superior performance when compared to Pd/C-ITO indicating the beneficial effect of adding Mn, this behavior can be attributed to the bifunctional mechanism or to the electronic effect of support.Artigo IPEN-doc 27219 The effect of support on Pd1Nb1 electrocatalysts for ethanol fuel cells2020 - SOUZA, FELIPE M.; NANDENHA, JULIO; OLIVEIRA, VITOR H.A.; PAZ, EDSON C.; PINHEIRO, VICTOR S.; AVEIRO, LUCI R.; PARREIRA, LUANNA S.; SILVA, JULIO C.M.; BATISTA, BRUNO L.; NETO, ALMIR O.; SANTOS, MAURO C.Pd1Nb1/C on different kinds of carbon black were prepared by a modified sol-gel method. The alkaline direct ethanol fuel cell (ADEFC) performance was performed first with the Pd1Nb1 electrocatalysts and then by varying the fuel concentration. In CV, Pd1Nb1/Printex 6L (50:50 wt%) exhibited 2.2 times higher mass activity than that of the Pd/C (Alfa Aesar); their mass activities were 1300 and 590 mA mg 1 Pd , respectively. The best performance for the ADEFC was obtained using Pd1Nb1/Printex 6L, which yielded a maximum power density and cell voltage of 28 mW cm 2 and 1.17 V, respectively. The Pd1Nb1/Printex 6L electrocatalyst exhibited a more negative onset potential for the CO stripping reaction. We suggest that the higher hydrophilicity (contact angle) and higher degree of disorder of Printex 6L (Raman) corroborates these results. In addition, both bifunctional and electronic effects operated on the electrocatalyst due to the presence of metal oxides and alloys of PdNb (XRD), respectively, in the synthesized electrocatalysts. Therefore, it was notable that the support has an essential roledas important as the cocatalystdin the electrocatalytic performance.Artigo IPEN-doc 27171 Au core stabilizes CO adsorption onto Pd leading to CO2 production2020 - FONTES, E.H.; NANDENHA, J.; SOUZA, R.F.B. de; ANTONIO, F.C.T.; HOMEM-DE-MELLO, P.; NETO, A.O.Au core and Pd shell supported on carbon structure Au@Pd/C can cleave the CeC 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.Artigo IPEN-doc 26874 High activity of Pt–Rh supported on C–ITO for ethanol oxidation in alkaline medium2020 - CAMARGO, V.F. de; FONTES, E.H.; NANDENHA, J.; SOUZA, R.F.B. de; NETO, A.O.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.