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CO2 is one of the leading greenhouse gases, so studies that turn this gas into higher value-added products, that function as simpler and cheaper hydrogen stores, as an alcohols, are extremely important. In this work we using a polymeric Electrolyte Reactor– fuel cell type supplied with H2 on platinum anode and dry CO2 in the cathode with a copper-carbon electrocatalyst. Copper nanoparticles supported on carbon Vulcan XC72 were produced by the sodium borohydride reduction method. The XRD revealed the presence of two different phases, CuO and Cu2O. In addition, the TEM images revealed agglomerates presence. The water, formaldehyde, methanol, methane, formic acid, dimethyl ether, oxalic acid, dimethyl carbonate, and ethylene-glycol were observed by differential mass spectroscopy on line with the reaction and the onset potential for each product and these results were confirmed by infrared spectroscopy – ATR-FTIR setup. This work showed the mapping CO2 reduced compounds for onset potential proposing some contributions to the literature.

PdxCuy/C catalysts combinations were employed to CH4 partial oxidation in mild condition using a solid electrolyte reactor—alkaline fuel cell type. The differential mass spectroscopy on line method was used to monitor the oxidation products obtained as methanol, dimethyl ether, methyl formate and potassium formate. It was observed that as the electrical potential of the reactor increases, the generation of products decreases. The best results for conversion of methane into methanol and energy co-generation was obtained from Pd90Cu10/C and Pd50Cu50/C due to better H2O activation effects and adsorption site for CH4 oxidation.

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.

PdNi electrocatalysts supported on carbon were used as anode materials for methane oxidation in alkaline direct methane fuel cells (ADMEFCs). The electrocatalysts were successfully synthesized by the NaBH4 reduction method. X-ray diffraction measurements showed the formation of non-alloyed Pd in the face- centered cubic (FCC) structure for all materials and formation of NiO and Ni(OH)2 species. TEM images showed that the metal particles are well dispersed on the support with small agglomeration regions. Information about the surface structure of the catalyst were obtained by Raman spectra, mainly confirming the presence of Ni(OH)2. The species observed by DEMS, that is, methanol (m/z = 32), CO2 (m/z = 44) and potassium formate (m/z = 84) were confirmed by FTIR, which also showed the presence of a high amount of carbonate in the methane oxidation products of the ADMEFC with Pd50Ni50/C as the anode catalyst. Tests in ADMEFCs showed that the dependence of the maximum power density on nickel content in the catalysts goes through a maximum value of 13.5 μW cm−2 at 50 at% Ni. Moreover, the amount of produced methanol decreases with increasing Ni content in the PdNi/C catalysts. Both these results can be explained by the enhanced methanol oxidation in the presence of nickel.

PtRuIn/C electrocatalysts (20% metal loading by weight) were prepared by sodium borohydride reduction process using H2PtCl6(6H2O, RuCl3(xH2O and InCl3(xH2O 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.