Electrochemistry for biofuels waste valorization: vinasse as a reducing agent for Pt/C and its application to the electrolysis of glycerin and vinasse

Waste vinasse has been used, for the first time, as a reducing agent to prepare a 20 wt% Pt/C electrocatalyst. After alkalization and subsequent filtration, abundant cations such as Ca, Mg and Fe were effectively removed, precipitating as hydroxides and insoluble phosphates. Pt chemical reduction was carried out under reflux in the presence of Vulcan XC-72R carbon by the action of reductive species such as sugars and phenols present. Reduction was confirmed by thermal analysis and X-ray diffractograms displaying the typical Pt fcc structure formed by nanocrystals. In the transmission images, an irregular dispersion of the Pt nanoparticles was observed on the carbon support, with the presence of large agglomerations with a cotton-like structure. This structure was found to be very active for glycerol electrolysis in an alkaline membrane electrolysis cell, comparable to commercial materials. Finally, results for electrolysis of the vinasse were also presented, demonstrating the possibility of valorizing this residue by the production of hydrogen

Preparation of PtSnCu/C and PtSn/C electrocatalysts and activation by dealloying processes for ethanol electro-oxidation

Foram preparados eletrocatalisadores PtSnCu/C (com diferentes razões atômicas Pt:Sn:Cu) e PtSn/C (50:50) com 20 % em massa de metais pelos métodos da redução por borohidreto (IRB) e redução por álcool (RA). Utilizou-se H2PtCl6.6H2O, SnCl2.2H2O e CuCl2.2H2O como fonte de metais, NaBH4 e etilenoglicol como agentes redutores, 2-propanol e etilenoglicol/água como solventes e carbono como suporte. Numa segunda etapa, estes eletrocatalisadores foram ativados pelos processos de dealloying químico (DQ), por tratamento com HNO3 e dealloying eletroquímico (DE), utilizando a técnica de eletrodo de camada fina porosa. Os materiais obtidos foram caracterizados por energia dispersiva de raios-X (EDX), difração de raios-X (DRX), microscopia eletrônica de transmissão (MET), energia dispersiva de raios-X de varredura linear (EDX-VL) e voltametria cíclica (VC). Estudos eletroquímicos para a oxidação eletroquímica do etanol foram realizados por voltametria cíclica, cronoamperometria e células unitárias (conjunto eletrodos/membrana). Os efluentes anódicos provenientes dos testes em células unitárias foram analisados por cromatografia a gás de alta eficiência (CG). Os difratogramas de raios-X dos eletrocatalisadores sintetizados mostraram a típica estrutura cúbica de face centrada (CFC) de liga de platina e após tratamento por dealloying, observou-se que a estrutura (CFC) foi preservada. O tamanho de cristalito dos eletrocatalisadores como preparados variou na ordem de 2 nm a 3 nm e, após processos de dealloying, não foram observadas variações de tamanho significativas. Análises por EDX dos eletrocatalisadores como preparados mostraram similaridade entra a razão atômica Pt:Sn e Pt:Sn:Cu obtida e a nominal. Após dealloying químico e eletroquímico, observou-se variação nas razões atômicas Pt:Sn e Pt:Sn:Cu, indicando a remoção parcial de Cu e Sn. Contudo, o processo de dealloying químico mostrou-se mais eficiente para a remoção de Cu e o dealloying eletroquímico para a remoção de Sn. As análises por EDX-VL mostraram que os processos de dealloying foram efetivos na remoção dos átomos mais superficiais de Cu e/ou Sn da estrutura CFC da Pt. Os resultados obtidos por cronoamperometria e voltametria cíclica mostraram que os eletrocatalisadores com teores de Pt maiores ou iguais a 30 %, após dealloying químico e eletroquímico apresentaram melhora significativa na atividade eletrocatalítica para a oxidação eletroquímica do etanol no potencial de interesse (0,5 V). Os eletrocatalisadores que apresentaram maior eficiência para oxidação eletroquímica do etanol foram PtSn/C (50:50) IRB/DE > PtSnCu/C (50:40:10) RA/DE > PtSnCu/C (50:10:40) IRB/DQ. Foram testados em células unitárias alimentadas diretamente com etanol os eletrocatalisadores PtSn/C (50:50) IRB/DQ, PtSnCu/C (50:10:40) IRB/DQ, PtSnCu/C (50:40:10) RA/DQ e os eletrocatalisadores comerciais Pt/C BASF e PtSn/C (75:25) BASF. Os eletrocatalisadores apresentaram a seguinte ordem de desempenho: PtSn/C (50:50) IRB/DQ > PtSnCu/C (50:40:10) RA/DQ > PtSn/C (75:25) BASF > PtSnCu/C (50:10:40) IRB/DQ > Pt/C BASF. Análises por cromatografia gasosa dos efluentes anódicos desses eletrocatalisadores mostraram formação de ácido acético e acetaldeído como produtos principais.PtSnCu/C (with different Pt:Sn:Cu atomic ratios) and PtSn/C (50:50) electrocatalysts were prepared by borohydride (BR) and alcohol-reduction (AR) processes using H2PtCl6.6H2O, SnCl2.2H2O and CuCl2.2H2O as metal sources, NaBH4 and ethylene glycol as reducing agents, 2-propanol and ethylene glycol/water as solvents and carbon black as support. In a further step, these electrocatalysts were activated by chemical (CD) and electrochemical (ED) dealloying processes through acid treatment and thin porous coating technique, respectively. These materials were characterized by energy dispersive X-ray, X-ray diffraction, transmission electron microscopy, line scan energy dispersive X-ray and cyclic voltammetry. Electrochemical studies for ethanol electro-oxidation were performed by cyclic voltammetry, chronoamperometry and in single Direct Ethanol Fuel Cell using Membrane Electrode Assembly (MEA). The anodic efluents were analised by gas chromatrography. The X-ray diffractograms of the as-synthesized electrocatalysts showed the typical face-centered cubic structure (FCC) of platinum and its alloys. After dealloying, the X-ray diffractograms showed that the Pt FCC structure was preserved. The crystallite sizes of the as-synthesized electrocatalysts were in the range of 2 nm to 3 nm and after dealloying there were no significant variations in sizes. The energy dispersive X-ray analysis of the as-synthesized electrocatalysts showed a Pt:Sn and Pt:Sn:Cu atomic ratios similar to the nominal values. After chemical and electrochemical dealloying of the electrocatalysts the ranged Pt:Sn and Pt:Sn:Cu atomic ratios showed that Cu and Sn atoms were removed. However, chemical dealloying process proved to be more efficient for removing Cu and electrochemical dealloying for removing Sn. The line scan energy dispersive X-ray analysis showed that acid and electrochemichel treatments were efficient to dealloying Cu and/or Sn superficial atoms of the FCC structure of Pt. The results obtained by cyclic voltammetry and chronoamperometry showed that electrocatalysts containing 30 at % or more of platinum, after chemical and electrochemical dealloying had significant improvement in electrocatalytic activity for ethanol electro-oxidation in the potential of interest. The electrocatalysts with higher efficiency for electrochemical oxidation of ethanol were PtSn/C (50:50) BR/ED > PtSnCu/C (50:40:10) AR/ED > PtSnCu/C (50:10:40) BR/CD. PtSn/C (50:50) BR/CD, PtSnCu/C (50:10:40) BR/CD, PtSnCu/C (50:40:10) AR/CD electrocatalysts and Pt/C BASF, PtSn/C (75:25) BASF commercial electrocatalysts were tested in single Direct Ethanol Fuel Cell. The results showed the following peformance for ethanol electro-oxidation: PtSn/C (50:50) BR/CD > PtSnCu/C (50:40:10) AR/CD > PtSnCu/C > PtSn/C (75:25) BASF > PtSnCu/C (50:10:40) BR/CD > Pt/C BASF

Preparação de Eletrocatalisadores PtSnCu/C e PtSn/C e Ativação por Processos de Dealloying para Aplicação na Oxidação Eletroquímica do Etanol

Documentos apresentados no âmbito do reconhecimento de graus e diplomas estrangeirosForam preparados eletrocatalisadores PtSnCu/C (com diferentes razões atômicas Pt:Sn:Cu) e PtSn/C (50:50) com 20 % em massa de metais pelos métodos da redução por borohidreto (IRB) e redução por álcool (RA). Utilizou-se H2PtCl6.6H2O, SnCl2.2H2O e CuCl2.2H2O como fonte de metais, NaBH4 e etilenoglicol como agentes redutores, 2-propanol e etilenoglicol/água como solventes e carbono como suporte. Numa segunda etapa, estes eletrocatalisadores foram ativados pelos processos de dealloying químico (DQ), por tratamento com HNO3 e dealloying eletroquímico (DE), utilizando a técnica de eletrodo de camada fina porosa. Os materiais obtidos foram caracterizados por energia dispersiva de raios-X (EDX), difração de raios-X (DRX), microscopia eletrônica de transmissão (MET), energia dispersiva de raios-X de varredura linear (EDX-VL) e voltametria cíclica (VC). Estudos eletroquímicos para a oxidação eletroquímica do etanol foram realizados por voltametria cíclica, cronoamperometria e células unitárias (conjunto eletrodos/membrana). Os efluentes anódicos provenientes dos testes em células unitárias foram analisados por cromatografia a gás de alta eficiência (CG). Os difratogramas de raios-X dos eletrocatalisadores sintetizados mostraram a típica estrutura cúbica de face centrada (CFC) de liga de platina e após tratamento por dealloying, observou-se que a estrutura (CFC) foi preservada. O tamanho de cristalito dos eletrocatalisadores como preparados variou na ordem de ≤ 2 nm a 3 nm e, após processos de dealloying, não foram observadas variações de tamanho significativas. Análises por EDX dos eletrocatalisadores como preparados mostraram similaridade entra a razão atômica Pt:Sn e Pt:Sn:Cu obtida e a nominal. Após dealloying químico e eletroquímico, observou-se variação nas razões atômicas Pt:Sn e Pt:Sn:Cu, indicando a remoção parcial de Cu e Sn. Contudo, o processo de dealloying químico mostrou-se mais eficiente para a remoção de Cu e o dealloying eletroquímico para a remoção de Sn. As análises por EDX-VL mostraram que os processos de dealloying foram efetivos na remoção dos átomos mais superficiais de Cu e/ou Sn da estrutura CFC da Pt. Os resultados obtidos por cronoamperometria e voltametria cíclica mostraram que os eletrocatalisadores com teores de Pt maiores ou iguais a 30 %, após dealloying químico e eletroquímico apresentaram melhora significativa na atividade eletrocatalítica para a oxidação eletroquímica do etanol no potencial de interesse (0,5 V). Os eletrocatalisadores que apresentaram maior eficiência para oxidação eletroquímica do etanol foram PtSn/C (50:50) – IRB/DE > PtSnCu/C (50:40:10) – RA/DE > PtSnCu/C (50:10:40) – IRB/DQ. Foram testados em células unitárias alimentadas diretamente com etanol os eletrocatalisadores PtSn/C (50:50) – IRB/DQ, PtSnCu/C (50:10:40) – IRB/DQ, PtSnCu/C (50:40:10) – RA/DQ e os eletrocatalisadores comerciais Pt/C – BASF e PtSn/C (75:25) – BASF. Os eletrocatalisadores apresentaram a seguinte ordem de desempenho: PtSn/C (50:50) – IRB/DQ > PtSnCu/C (50:40:10) – RA/DQ > PtSn/C (75:25) – BASF > PtSnCu/C (50:10:40) – IRB/DQ > Pt/C – BASF. Análises por cromatografia gasosa dos efluentes anódicos desses eletrocatalisadores mostraram formação de ácido acético e acetaldeído como produtos principais

An alkaline-acid glycerol electrochemical reformer for simultaneous production of hydrogen and electricity

This study shows the results, for the first time, of an glycerol alkaline-acid electrolyzer. Such a configuration allows spontaneous operation, producing energy and hydrogen simultaneously as a result of the utilization of the neutralization and fuel chemical energy. The electroreformer—built with a 20 wt% Pd/C anode and cathode, and a Na+-pretreated Nafion® 117—can simultaneously produce hydrogen and electricity in the low current density region, whereas it operates in electrolysis mode at high current densities. In the spontaneous region, the maximum power densities range from 1.23 mW cm−2 at 30 °C to 11.9 mW cm−2 at 90 °C, with a concomitant H2 flux ranging from 0.0545 STP m−3 m−2 h−1 at 30 °C to 0.201 STP m−3 m−2 h−1 at 90 °C, due to the beneficial effect of the temperature on the performance. Furthermore, over a chronoamperometric test, the electroreformer shows a stable performance over 12 h. As a challenge, proton crossover from the cathode to the anode through the cation exchange Nafion® partially reduces the pH gradient, responsible for the extra electromotive force, thus requiring a less permeable membrane.Instituto de Química (IQ

The Promotional Effect of Rare Earth on Pt for Ethanol Electro-Oxidation and Its Application on DEFC

Bimetallic Pt3Eu/C, Pt3La/C, and Pt3Ce/C electrocatalysts have been prepared, characterized, and tested for ethanol electro-oxidation (EEO). The materials were synthesized by chemical reduction with NaBH4, rendering nanosized particles with actual compositions close to the nominals and no alloy formation. X-ray photoelectron spectroscopy (XPS) confirmed that the auxiliary rare-earth metals were present on the surface in oxide form. The electrochemical analyses in acid and alkaline EEO evidenced that, compared to Pt/C, the addition of rare earth metals in the form of oxides reduced the onset potential, increased the current density, and enhanced the stability. The results were fully confirmed in the DEFC single-cell measurements. Finally, the presence of rare earth metals in the oxidized form increased the percentage of acetic acid as the final product, making the electrocatalysts more selective and efficient than Pt/C, where acetaldehyde was the main product

Promoting Effect of Cu on Pd Applied to the Hydrazine Electro-Oxidation and Direct Hydrazine Fuel Cells

Use of liquid fuels in fuel cells is advantageous due to the easier and safer handling, transportation, and storage. Among the different options, hydrazine is of interest since the formation of highly poisoning carbonaceous species is avoided, in addition to its high energy density. In the search for more active direct hydrazine fuel cells (DHFC), this study analyzes the influence of Cu as an auxiliary metal on Pd. Three different PdxCu/C (x = 3, 1, and 0.33) catalysts were prepared by chemical reduction with NaBH4. The materials were physiochemically characterized by X-ray diffraction, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Electrochemical analysis in a three-electrode glass cell and a single-cell DHFC was also carried out to study the impact on the electroactivity. Cu exerts a beneficial effect by reducing the adsorption energies of the adsorbed species and donating oxidized species for the completion of the hydrazine electro-oxidation, optimally balanced in the Pd1Cu/C (maximum power density of 180 mW cm−2). As a counterpoint, Cu slightly promotes the non-faradaic decomposition of hydrazine, seen by a larger H2 signal in mass spectroscopy in the anode exhaust at high current densities, which results in a slight loss in faradaic efficiency

Promoting Effect of Cu on Pd Applied to the Hydrazine Electro-Oxidation and Direct Hydrazine Fuel Cells

Use of liquid fuels in fuel cells is advantageous due to the easier and safer handling, transportation, and storage. Among the different options, hydrazine is of interest since the formation of highly poisoning carbonaceous species is avoided, in addition to its high energy density. In the search for more active direct hydrazine fuel cells (DHFC), this study analyzes the influence of Cu as an auxiliary metal on Pd. Three different PdxCu/C (x = 3, 1, and 0.33) catalysts were prepared by chemical reduction with NaBH4. The materials were physiochemically characterized by X-ray diffraction, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Electrochemical analysis in a three-electrode glass cell and a single-cell DHFC was also carried out to study the impact on the electroactivity. Cu exerts a beneficial effect by reducing the adsorption energies of the adsorbed species and donating oxidized species for the completion of the hydrazine electro-oxidation, optimally balanced in the Pd1Cu/C (maximum power density of 180 mW cm−2). As a counterpoint, Cu slightly promotes the non-faradaic decomposition of hydrazine, seen by a larger H2 signal in mass spectroscopy in the anode exhaust at high current densities, which results in a slight loss in faradaic efficiency