Different promoting roles of ruthenium for the oxidation of primary and secondary alcohols on PtRu electrocatalysts

This study shows remarkably different features between the oxidation of secondary and primary C3-C5 alcohols. The oxidation of primary alcohols is controlled by the oxidative removal of blocking adsorbates, such as CO, formed after the dissociative adsorption of alcohol molecules. Conversely, secondary alcohols do not undergo dissociative adsorption and therefore their oxidation is purely controlled by the energetics of the elementary reaction steps. In this respect, a different role of ruthenium is revealed for the electrooxidation of primary and secondary alcohols on bimetallic platinum-ruthenium catalysts. Ruthenium enhances the oxidation of primary alcohols via the established bifunctional mechanism, in which the adsorption of (hydr)oxide species that are necessary to remove the blocking adsorbates is favored. In contrast, the oxidation of secondary alcohols is enhanced by the Ru-assisted stabilization of an O-bound intermediate that is involved in the potential-limiting step. This alternative pathway enables the oxidation of secondary alcohols close to the equilibrium potential

Different promoting roles of ruthenium for the oxidation of primary and secondary alcohols on PtRu electrocatalysts

This study shows remarkably different features between the oxidation of secondary and primary C3-C5 alcohols. The oxidation of primary alcohols is controlled by the oxidative removal of blocking adsorbates, such as CO, formed after the dissociative adsorption of alcohol molecules. Conversely, secondary alcohols do not undergo dissociative adsorption and therefore their oxidation is purely controlled by the energetics of the elementary reaction steps. In this respect, a different role of ruthenium is revealed for the electrooxidation of primary and secondary alcohols on bimetallic platinum-ruthenium catalysts. Ruthenium enhances the oxidation of primary alcohols via the established bifunctional mechanism, in which the adsorption of (hydr)oxide species that are necessary to remove the blocking adsorbates is favored. In contrast, the oxidation of secondary alcohols is enhanced by the Ru-assisted stabilization of an O-bound intermediate that is involved in the potential-limiting step. This alternative pathway enables the oxidation of secondary alcohols close to the equilibrium potential.This work was funded by the Bavarian Ministry of Economic Affairs, Regional Development and Energy. F.C.-V. acknowledges funding from Spanish MICIUN RTI2018-095460-B-I00, Ramón y Cajal RyC-2015-18996 and María de Maeztu MDM-2017-0767 grants and partly by Generalitat de Catalunya 2017SGR13. O.P. thanks the Spanish MICIUN for a PhD grant (PRE2018-083811). We thank Red Española de Supercomputación (RES) for supercomputing time at SCAYLE (projects QS-2019-3-0018, QS-2019-2-0023, and QCM-2019-1-0034), MareNostrum (project QS-2020-1-0012), and CENITS (project QS-2020-2-0021). The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences, with financial support by NWO

Impact of catalyst loading, ionomer content, and carbon support on the performance of direct isopropanol fuel cells

Liquid Organic Hydrogen Carriers (LOHC) offer a promising solution for hydrogen storage in the existing infrastructure for conventional fuels. Within this framework, the isopropanol/acetone couple as a light-LOHC system is used to generate electricity in a direct isopropanol fuel cell (DIFC). This work focuses on the impact of catalyst loading, ionomer content and catalyst support on the performance of DIFCs. We achieve a performance rise from 95 mW cm-2 to 219 mW cm-2 under air operation by increasing the anode catalyst loading from 0.5 mg cm-2 to 4 mg cm-2, which can be attributed to the increased abundance of active catalyst sites with higher loadings. In contrast, we find that the cathode loading for the oxygen reduction reaction (ORR) plays a minor role in the performance of DIFCs. Therefore, the cathode loading can be minimized to decrease the total amount of platinum-group metals and, consequently, to save cost. It was also found that an ionomer content of 30% on the anode side is optimal. Additionally, different carbon supports were investigated, where advanced high surface area carbon support showed superior performance to Vulcan with an increase of 20% in power density, motivating the development of new carbon supports for DIFCs

Isopropanol electro-oxidation on Pt-Ru-Ir: A journey from model thin-film libraries towards real electrocatalysts

Liquid fuels are considered a promising alternative to hydrogen in proton exchange membrane fuel cells. In particular, isopropanol, which can be selectively oxidised to acetone and further hydrogenated back to isopropanol using electrochemical and heterogeneous catalysis routes, respectively, opens the possibility of zero-emission fuel cell operation without complex management of molecular H2. However, the maximum electric power of such fuel cells is still relatively low, which is attributed to the poisoning of state-of-the-art Pt-Ru electrocatalysts by adsorbed acetone and/or Ru oxide/hydroxide. Here, in order to mitigate Pt-Ru poisoning at higher anodic potentials during isopropanol oxidation in acidic media, the effect of the addition of Ir, a less oxophilic element than Ru, on the activity and stability during dynamic experiments of Pt-Ru is systematically investigated. To identify the most active compositions, Pt-Ru-Ir thin-film material libraries are prepared using magnetron co-sputtering. The electrocatalytic activity of the libraries is screened using a high-throughput scanning flow cell setup. Catalysts with the highest activity are further synthesised in the form of carbon-supported nanoparticles. Comparing the two systems, similar trends are observed, highlighting the model material libraries being an excellent starting point for novel catalyst development. Besides electrocatalytic activity, catalyst shelf-life and dissolution stability are studied. While significant ageing in the air is found, partial reactivation is possible using a reductive treatment. The dissolution of the most promising nanoparticulate electrocatalyst is evaluated using online inductively coupled plasma mass spectrometry to assess the effect of Ir addition on Pt and Ru stability. No significant stabilising role of Ir, however, is observed. Hence, further optimisation of Pt-Ru or Pt-Ru-Ir is still needed to improve isopropanol fuel cell performance