Influence of Pt/Ru anodic ratio on the valorization of ethanol by PEM electrocatalytic reforming towards value-added products

The ethanol electro-reforming process was studied over PtRu/C catalysts synthesized by the modified polyol method with different compositions.In particular,this work reports the influence of anodic Pt:Ru ratio(5:1,2:1 and 1:2)on the organic product distribution(acetaldehyde,acetic acid and ethyl acetate)and pure hydrogen generation at different current densities operation levels.Physicochemical characterization of the catalysts was made by X-ray diffraction(XRD),temperature-programmed reduction(TPR)and N_(2) adsorption-desorption measurements.XRD patterns showed that Ru is introduced into the Pt structure,forming an alloy between both metals.Also,the degree of alloy was higher by increasing the Ru amounts.From TPR profiles Pt was found to be properly reduced while Ru was both in metallic state and forming RuO2.The electrochemical behaviour of each catalyst towards ethanol electroreforming process was investigated through electrochemical techniques in a half cell and a single proton exchange membrane(PEM)cell systems.An intermediate Pt:Ru ratio was found to result in high current density and electrochemical surface area(ECSA)values along with lower amounts of adsorbed species.Also,Ru addition seems to diminish the degree of degradation of the catalyst.Based on characterization and in agreement with essays carried out in a PEM cell at mild conditions(80℃ and 1 atm),PtRu/C 2:1 anode provided the best electrocatalytic results in terms of current density(740 mA cm^(-2)),hydrogen production and selectivity toward acetic acid(up to 15%apart from acetaldehyde and ethyl acetate)while requiring the lowest energy consumption.

Boosting hydrogen and chemicals production through ethanol electro-reforming on Pt-transition metal anodes

The aim of this work is to boost the combined hydrogen and added-values compounds generation(acetaldehyde, acetic acid and ethyl acetate) through ethanol electrochemical reforming using bimetallic anodes. In particular, the influence of the secondary metal on the electrochemical performance as well as on the product distribution was studied. For that purpose, Pt X/C electrocatalysts(where X corresponds to Cu, Co, Ni and Ru) were synthesized by the modified polyol method and tested in both half-cell and proton exchange membrane(PEM) cell configurations. Characterization results showed that incorporation of Ni and Co into the Pt matrix enhances the morphological properties of the material, providing smaller crystallite sizes, higher active surface areas and hence, better dispersion when comparing to Ru and Cu-based electrocatalysts. Ethanol oxidation reaction(EOR) was evaluated by cyclic, linear voltammetry and chronopotentiometry assays. Pt Co/C and Pt Ni/C exhibited the highest electrocatalytic activity at high polarization levels, which translate into an improvement of more than 30%(up to 1050 m A cm^(-2)) in the hydrogen production and chemical yields. On the other hand, Pt Ru/C results more advantageous for a lower potential interval(<0.85 V) promoting the acetic acid production despite sacrificing ethanol conversion. Pt Cu/C presented the lowest results in both electrochemical performance and product distribution. Such differences in the electrochemical performance can be rationalized in terms of the synergistic effect between both metals(particle size distribution, grade of dispersion and hydrophilic behavior), which demonstrate that the incorporation of a different secondary metal plays an essential role in the EOR development.

PtRu nanoparticles supported on noble carbons for ethanol electrooxidation

In this work,three cytosine derived nitrogen doped carbonaceous materials(noble carbons,NCs)with different atomic C/N ratios and porous networks have been synthesized and used as supports for Pt Ru electrocatalysts in the ethanol oxidation reaction(EOR)for clean hydrogen production.Both,the metal phase and the carbon support play critical roles in the electrocatalysts final performance.Lower NPs size distribution was obtained over supports with low atomic C/N ratios(i.e.,4 and 6)and defined porosity(i.e.,1701 m^(2)g^(-1)for Pt Ru/CNZ and 1834 m^(2)g^(-1)for Pt Ru/CLZ,respectively).In contrast,a lower C/N ratio and poor porous network(i.e.,65 m^(2)g^(-1),Pt Ru/CLK)led to the largest particle size and fostered an increase of the alloying degree between Pt and Ru NPs(i.e.,3%for C/N~6 and 28%for C/N~3).Electrochemical active surface area was found to increase with decreasing NPs size and the alloy extent,due to a higher availability of Pt active sites.Accelerated degradation tests showed that Pt Ru/NCs outperform similar to Pt Ru NPs on commercial carbon pointing at the stabilizing effect of NCs.Pt Ru/CNZ exhibited the best electrochemical performance(i.e.,69.1 m A mgPt-1),outperforming Pt Ru/CLZ and Pt Ru/CLK by3-and 9-fold,respectively,due to a suitable compromise between particle sizes,degree of alloy,textural properties and elemental composition.Best anodes were scaled-up to a proton exchange membrane cell and Pt Ru/CNZ was proved to provide the best electrocatalytic activity(262 m A cm^(-2)and low energy requirements),matching the values obtained by the state of the art of EOR electrocatalysts.