Ethanol electrooxidation on Pt-Sn and Pt-Sn-W bulk alloys

Ethanol oxidation has been studied on Pt-Sn and Pt-Sn-W electrodes prepared in an arc-melting furnace. Different electrochemical techniques like cyclic voltammetry and chronoamperometry were used to evaluate the catalytic activity of these materials. The electro-oxidation process was also investigated by in situ infrared reflectance spectroscopy in order to determine adsorbed intermediates and reaction products. Experimental results indicated that Pt-Sn and Pt-Sn-W alloys are able to oxidize ethanol mainly to acetaldehyde and acetic acid. Adsorbed CO was also detected, demonstrating the viability of splitting the C-C bond in the ethanol molecule during the oxidation process. The adsorbed CO was further oxidized to CO2.This reaction product was clearly detected by SNIFTIRS. Pt-Sn-W catalyst showed a better electrochemical performance than Pt-Sn that, in it turn, is better than Pt-alone.A oxidação de etanol foi estudada sobre eletrodos Pt-Sn e Pt-Sn-W preparados em forno a arco elétrico. Diferentes técnicas eletroquímicas, tais como voltametria cíclica e cronoamperometria foram utilizadas para avaliar a atividade catalítica desses materiais. O processo de eletro-oxidação também foi investigado in situ por espectroscopia de reflectância na região do infravermelho para determinar intermediários adsorvidos e produtos da reação. Os resultados experimentais indicaram que as ligas Pt-Sn e Pt-Sn-W são capaz de oxidar etanol principalmente para acetaldeído e ácido acético. CO adsorvido também foi detectado, demonstrando a viabilidade do rompimento da ligação C-C na molécula de etanol durante o processo de oxidação. Adicionalmente, o CO adsorvido foi oxidado a CO2. Esse produto de reação foi claramente detectado por SNIFTIRS. O catalisador Pt-Sn-W mostrou um melhor desempenho eletroquímico em relação ao Pt-Sn e este, por sua vez, é melhor do que Pt pura.CAPES - COFECUBCNP

Effect of palladium on gold in core-shell catalyst for electrooxidation of ethanol in alkaline medium

In this paper the effect of small amounts of palladium deposited on gold nanoparticles supported on Vulcan XC-72 carbon (core-shell structure denoted Au@Pd/C) is studied. Different nominal atomic compositional ratios of Au@Pdx maintaining fixed gold nuclei and varying the amount of palladium (x = 0.10; 0.80 and 1.60) were synthesized via seed growth method for the ethanol oxidation reaction in alkaline medium. UV–Vis spectrometric, X-ray powder diffraction, X-ray energy dispersive spectroscopy, transmission electron microscopy and electrochemical measurements were performed for the characterization of these catalysts. Electrocatalytic activity toward ethanol oxidation on Au@Pd/C catalysts were investigated by cyclic voltammetry and chronoamperometry showed that [email protected]/C electrocatalyst has the highest current density and low onset potential for ethanol oxidation reaction in alkaline medium. In-situ Fourier transform infrared spectroscopy measurements demonstrated that acetate is the main product of ethanol oxidation and CO2 can be slightest observed, the latter could be visualized in greater quantity on catalyst [email protected]/C catalyst

Glycerol electro-oxidation on bismuth-modified platinum single crystals

Catalysis and Surface Chemistr

Synthesis of Fe/Ti oxides from a single source alkoxide precursor under inert atmosphere

The heterometal alkoxide [FeCl{Ti2(OPr i)9}] (1) was employed as a single source precursor for the preparation of Fe/Ti oxides under inert atmosphere. Three different synthetic procedures were adopted in the processing of 1, either employing aqueous HNO3 or HCl solutions, or in the absence of mineral acids. Products were characterised by powder X-ray diffractometry, scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM/EDS) and Raman, electron paramagnetic resonance (EPR) and Mössbauer spectroscopies. Oxide products contained titanium(IV) and either iron(III) or iron(II), depending on reaction conditions and thermal treatment temperatures. An interesting iron(III)→iron(II) reduction was observed at 1000 ºC in the HNO3-containing system, leading to the detection of ilmenite (FeTiO3). SEM/EDS studies revealed a highly heterogeneous metal distribution in all products, possibly related to the presence of a significant content of carbon and of structural defects (oxygen vacancies) in the solids.O alcóxido heterometálico [FeCl{Ti2(OPr i)9}] (1) foi utilizado como um precursor de fonte única para a preparação de óxidos de Fe/Ti sob atmosfera inerte. Três procedimentos sintéticos distintos foram adotados no processamento de 1, com o emprego de soluções aquosas ácidas (HNO3 ou HCl), ou na ausência de ácido mineral. Os produtos foram caracterizados por difratometria de raios X (pó), microscopia eletrônica de varredura combinada com espectroscopia de dispersão de raios X (MEV/EDS) e espectroscopias Raman, de ressonância paramagnética eletrônica (RPE) e Mössbauer. Os óxidos produzidos contêm titânio(IV) e ferro(III) (ou ferro(II)), dependendo das condições de reação e das temperaturas de tratamento térmico. Uma interessante redução de ferro(III) a ferro(II), que levou à obtenção de ilmenita (FeTiO3), foi observada a 1000 ºC no sistema contendo HNO3. Estudos por MEV/EDS revelaram uma distribuição altamente heterogênea dos metais em todos os produtos, possivelmente relacionada com a presença de um conteúdo significativo de carbono e de defeitos estruturais (vacâncias de oxigênio) nos sólidos.Biotechnology and Biological Sciences Research Council (BBSRC) U

Poly(dimethylsiloxane) as a pre-coating in layer-by-layer films containing phosphotungstate nanoclusters electrochemically sensitive toward s-triazines

One of the major advantages of the Layer-by-Layer (LbL) deposition technique is the possible control of molecular architecture, not only to achieve optimized properties but also to seek synergy among different materials. In this study, LbL films containing nanoclusters of a Keggin type polyoxometalate, phosphotungstic acid (HPW), alternated with the polycation poly(allylamine hydrochloride) (PAH) were deposited on indium-tin oxide (ITO) substrates. The electrochemical properties of the hybrid LbL film investigated in acidic conditions indicated no significant desorption of HPW, when a layer of poly(dimethylsiloxane) terminated with 3-aminopropyl groups (PDMS) was previously deposited on the ITO substrate. Such effect occurred because PDMS prevents desorption of HPW from the hybrid film, as shown by X-ray Photoelectron Spectroscopy (XPS) analyses. The porous structures of the films were revealed by Fourier transform infrared reflection absorption spectroscopy, scanning electron microscopy and XPS. PDMS/PAH as a pre-coating allowed the HPW/PAH films to be sensitive to the electrochemical detection of the triazines atrazine and melamine. In conclusion, the precise control of the LbL films architecture is important to develop opportunities for new applications. © 2014 The Royal Society of Chemistry.One of the major advantages of the Layer-by-Layer (LbL) deposition technique is the possible control of molecular architecture, not only to achieve optimized properties but also to seek synergy among different materials. 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Engineering polycotton fiber surfaces, with an timicrobial activity against S. aureus, E. Coli, C. albicans and SARS-CoV-2

Pathogenic microorganisms are becoming a potential threat to the health of human beings and the environment worldwide. In this present study, we have developed a polycotton fiber, in which by incorporation and functionalization of aggregated Ag NPs are achieved by using the pad-dry-cure meth- od. Upon contact, this coating shows antimicrobial activity against S. aureus, E. Coli, C. albicans and SARS-CoV-2. The polycotton AgNP, inhibiting nearly of the virus was able to prevent cross-infections, and does not causes allergies or photoirritation, proving the safety of its use. To the best of our knowledge, this is the first report of an antimicrobial coating that could rapidly reduce the infective load of bacteria, fungi, and inhibit SARS--CoV-2. Taken together, the antimicrobial coating reported herein holds great promise to be developed for further application in healthcare settings

Surface restructuring of Pt films on Au stepped surfaces: effects on catalytic behaviour

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)In this paper, the reconstruction of Pt films deposited on stepped Au(hkl) surfaces belonging to the [n(111) x (110)] family of planes has been studied. Pt films were deposited using the galvanic displacement procedure of a pre-deposited Cu monolayer. We experimentally found that the Pt film deposition onto Au(hkl) surfaces is not fully epitaxial suggesting an atomic arrangement different from the underlying substrate. Additionally, we found that even though voltammetric profiles are not much different from those reported in the literature for Pt single crystals having the same crystallographic orientation, there is a reconstruction of the Pt layers on all Pt/Au(hkl) surfaces upon CO adsorption/oxidation as indicated by comparing the active areas of the Pt films before and after stripping. Additional FTIR in situ experiments on ethanol oxidation confirm that film reconstruction affects the reaction by product yield modification.o TEXTO COMPLETO DESTE ARTIGO, ESTARÁ DISPONÍVEL À PARTIR DE AGOSTO DE 2015.15311318413189Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)CNPq [Proc. 142507/2007-5]FAPESP [Proc. 2011/12566-3

Influence of substrate steps on the catalytic properties of Pt layers: the ethanol electrooxidation reaction

CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPThe ethanol oxidation reaction (EOR) is investigated on Pt/ Au(hkl) electrodes. The Au(hkl) single crystals used belong to the [n(111)x(110)] family of planes. Pt is deposited following the galvanic exchange of a previously deposited Cu monolayer using a Pt2+ solution. Deposition is not epitaxial and the defects on the underlying Au(hkl) substrates are partially transferred to the Pt films. Moreover, an additional (100)-step-like defect is formed, probably as a result of the strain resulting from the Pt and Au lattice mismatch. Regarding the EOR, both vicinal Pt/Au(hkl) surfaces exhibit a behavior that differs from that expected for stepped Pt; for instance, the smaller the step density on the underlying Au substrate, the greater the ability to break the C-C bond in the ethanol molecule, as determined by in situ Fourier transform infrared spectroscopy measurements. Also, we found that the acetic acid production is favored as the terrace width decreases, thus reflecting the inefficiency of the surface array to cleave the ethanol molecule.The ethanol oxidation reaction (EOR) is investigated on Pt/Au(hkl) electrodes. The Au(hkl) single crystals used belong to the [n(111)x(110)] family of planes. Pt is deposited following the galvanic exchange of a previously deposited Cu monolayer using a Pt2+ solution. Deposition is not epitaxial and the defects on the underlying Au(hkl) substrates are partially transferred to the Pt films. Moreover, an additional (100)-step-like defect is formed, probably as a result of the strain resulting from the Pt and Au lattice mismatch. Regarding the EOR, both vicinal Pt/Au(hkl) surfaces exhibit a behavior that differs from that expected for stepped Pt; for instance, the smaller the step density on the underlying Au substrate, the greater the ability to break the CC bond in the ethanol molecule, as determined by in situ Fourier transform infrared spectroscopy measurements. Also, we found that the acetic acid production is favored as the terrace width decreases, thus reflecting the inefficiency of the surface array to cleave the ethanol molecule.151738643870CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPCONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESP142507/2007-52011/12566-3Tremiliosi-Filho, G., Gonzalez, E.R., Motheo, A.J., Belgsir, E.M., Leger, J.M., Lamy, C., (1998) J. Electroanal. Chem., 444, pp. 31-39Tereshchuk, P., Da Silva, J.L.F., (2012) J. Phys. Chem. C, 116, pp. 24695-24705Iwasita, T., Rasch, B., Cattaneo, E., Vielstich, W., (1989) Electrochim. Acta, 34, pp. 1073-1079Ren, H., Humbert, M.P., Menning, C.A., Chen, J.G., Shu, Y., Singh, U.G., Cheng, W.-C., (2010) Appl. Catal. A, 375, pp. 303-309Antolini, E., (2007) J. 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