JULIO NANDENHA
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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 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 26619 Activation of methane on PdZn/C electrocatalysts in an acidic electrolyte at low temperatures2019 - NANDENHA, J.; NAGAHAMA, I.H.F.; YAMASHITA, J.Y.; FONTES, E.H.; AYOUB, J.M.S.; SOUZA, R.F.B. de; FONSECA, F.C.; NETO, A.O.PdZn/C electrocatalysts were prepared by sodium borohydride utilized as reducing agent for activation methane in an acidic medium at room temperature and in a proton exchange membrane fuel cell (PEMFC) at 80°C. The materials prepared were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The diffractograms of the PdZn/C electrocatalysts showed only peaks associated with Pd face-centered cubic (fcc) structure. Cyclic voltammograms (CV) of all electrocatalysts after adsorption of methane shown an increment in current during the anodic scan, this effect was more pronounced for Pd(70)Zn(30)/C. In situ ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared) experiments was not observed the formation of intermediates adsorbed for PdZn/C electrocatalysts, this behavior indicated that the methane oxidation occurs by parallel mechanisms. Polarization curves at 80°C in PEMFC show that Pd(90)Zn(10)/C has superior performance over the other electrocatalysts in methane oxidation.Artigo IPEN-doc 25826 Structural analysis of PdRh/C and PdSn/C and its use as electrocatalysts for ethanol oxidation in alkaline medium2019 - FONTES, ERIC H.; RAMOS, CARLOS E.D.; NANDENHA, JULIO; PIASENTIN, RICARDO M.; OLIVEIRA NETO, ALMIR; LANDERS, RICHARDThe 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 e 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.Artigo IPEN-doc 25731 Methanol oxidation in acidic and alkaline electrolytes using PtRuIn/C electrocatalysts prepared by borohydride reduction process2018 - SANTOS, M.C.L.; NANDENHA, J.; AYOUB, J.M.S.; ASSUMPÇAO, M.H.M.T.; NETO, A.O.PtRuIn/C electrocatalysts (20% metal loading by weight) were prepared by sodium borohydride reduction process using H2PtCl66H2O, RuCl3xH2O and InCl3xH2O as metal sources, borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction (XRD), energy dispersive analysis (EDX), transmission electron microscopy (TEM), cyclic voltammetry (CV), chronoamperommetry (CA) and polarization curves in alkaline and acidic electrolytes (single cell experiments). The XRD patterns show Pt peaks are attributed to the face-centered cubic (fcc) structure, and a shift of Pt (fcc) peaks indicates that Ru or In is incorporated into Pt lattice. TEM micrographs show metal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature, by CV and CA. PtRu/C (50:50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80°C show PtRuIn/C (50:25:25) with superior performance for methanol oxidation, when compared to Pt/C, PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C (50:25:25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Pt alloy.Artigo IPEN-doc 25213 Electrocatalytic performance of PtSn/C-In2O3 center dot SnO2 nanoparticles prepared by sodium borohydride reduction process for ethanol oxidation in acidic and alkaline electrolytes2018 - PEREIRA, C.V.; FONTES, E.H.; NANDENHA, J.; ASSUMPCAO, M.H.M.T.; NETO, A.O.PtSn/C-In2O3.SnO2 electrocatalysts were prepared by the borohydride reduction method in the single step using H2PtCl6.6H2O and SnCl2.2H2O as metal sources, sodium borohydride as reducing agent and a physical mixture of 85% Vulcan Carbon XC72 and 15% In2O3.SnO2 (indium tin oxide – ITO) as support. PtSn/C-In2O3.SnO2 electrocatalysts were characterized by X–ray diffraction (XRD), energy dispersive analysis (EDX), transmission electron microscopy (TEM), cyclic voltammetry (CV), chronoamperommetry (CA) and polarization curves in alkaline and acidic electrolytes (single cell experiments). The diffractograms of PtSn/C-In2O3.SnO2 electrocatalysts showed peaks associated to the face-centered cubic (fcc) structure of platinum, peaks which could be identified as a cassiterite SnO2 phase or with Indium-doped SnO2 (ITO) used as supports. TEM micrographs showed metal nanoparticles with average nanoparticle size between 2.4 and 2.7 nm. Ethanol oxidation in acidic and alkaline electrolytes was investigated at room temperature, by chronoamperommetry (CA), where PtSn/C-In2O3.SnO2 (70:30) showed the highest activity among all electrocatalysts in study considering ethanol oxidation for acid electrolyte, while for alkaline electrolyte the highest activity was observed for PtSn/C-In2O3.SnO2 (50:50). Polarization curves at 100oC showed PtSn/C-In2O3.SnO2 (70:30) with superior performance for ethanol oxidation for acidic electrolyte and PtSn/C (70:30) for alkaline electrolyte, when compared to Pt/C for both electrolytes. The best performance obtained by PtSn/C-In2O3.SnO2 (70:30) in real conditions could be associated with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of PtSn alloy or a synergetic effect between PtSn and In2O3.Artigo IPEN-doc 25122 Direct oxidation of methane at low temperature using Pt/C, Pd/C, Pt/C-ATO and Pd/C-ATO electrocatalysts prepared by sodium borohydride reduction process2018 - NANDENHA, J.; FONTES, E.H.; PIASENTIN, R.M.; FONSECA, F.C.; NETO, A.O.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.Artigo IPEN-doc 24800 PdxNby electrocatalysts for DEFC in alkaline medium2018 - SOUZA, F.M.; NANDENHA, J.; BATISTA, B.L.; OLIVEIRA, V.H.A.; PINHEIRO, V.S.; PARREIRA, L.S.; NETO, A.O.; SANTOS, M.C.PdxNby/C binary electrocatalysts supported on Vulcan carbon XC72 were prepared by the sol-gel method. The materials are characterized by transmission electron microscopy, X-ray diffraction analysis, inductively coupled plasma–mass spectrometry and contact angle measurements. The electrocatalytic activity for ethanol electrooxidation reaction was studied by cyclic voltammetry, chronoamperometry, Tafel slope and accelerated durability testing. The direct ethanol performance and the products after the experiments were studied by Fourier transform infrared spectroscopy. Pd1Nb1/C (50:50 wt%) shows superior activity for ethanol oxidation compared to the other electrocatalysts prepared in this work. All electrocatalysts containing Nb show the highest current exchange density. The Tafel slope results suggest that the Nb modified the Pd-electrocatalyst to obtain a reaction path with high selectivity with only a single determining step with low production of the intermediates for the ethanol oxidation reaction. The best performance is obtained using Pd1Nb1/C 18.11 mW cm−2. The Pd1Nb1/C electrocatalyst displays the highest production of CO2 and the lowest production of acetaldehyde. Pd1Nb1/C shows the highest peak current density during 1000 cycles of the experiment and the lowest mass loss of Pd after the cycling test. We find that the Nb modifies the Pd electrocatalysts from the bifunctional mechanism and reduces the loss of Pd during the accelerated durability test.