The "volcano"-relationship for the electrocatalytic hydrogen evolution reaction seems to be a generally accepted phenomenology in electrochemistry. Based on the Sabatier principle, which suggests a not too strong, nor too weak binding of reaction intermediates as prerequisite for high reaction rates, it provides a straightforward and intuitive explanation for a plethora of experimental results. However, while the Sabatier principle as a main paradigm of heterogeneous catalysis was never really disputed in the case of gas-phase reactions, it remains questionable if it can be the main driving principle that governs activity trends of electrocatalytic reactions. This work provides an overview on this topic for the model hydrogen evolution reaction (HER), pointing out certain inconsistencies and contradictions found in literature. The critical assessment provides a viewpoint which could have important practical consequences and could provide different perspective on future catalyst design

For a successful replacement of Pt, tremendous efforts have hitherto been made to develop high-performing Fe-N-C catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs). In comparison to the remarkable progress in activity, the stability of Fe-N-C catalysts still remains critical, however. Fe demetallation in acidic medium is hypothesized to be one critical factor for the overall lifetime. In contrast to the general belief, we herein demonstrate using an operando spectroscopic analysis that catalytically inactive Fe particles exposed to acid electrolytes cannot be fully removed by acid washing due to a relatively high open circuit potential (ca. 0.9 VRHE) leading to the formation of insoluble ferric species, whereas these particles dissolve under PEMFC operating conditions (E cathode < 0.7 VRHE) due to operando reduction to soluble ferrous cations. To overcome this issue, we demonstrate two approaches: (i) synthesis of Fe-N-C catalysts free of Fe particles and (ii) postsynthesis removal of exposed Fe particles through the control of potential using an external potentiostat or an internal reducing agent (i.e., SnCl2). Operando spectroscopic analyses verified that Fe demetallation during a given voltammetric protocol was dramatically decreased for both synthetically and postsynthetically modified Fe-N-C catalysts, while the initial ORR activity did not significantly change. However, all of these catalysts showed similar performance decay over short-term PEMFC durability tests, demonstrating the lack of a role played by ferrous cations leached from inactive Fe particles on catalyst deactivation. This supports the view that the activity is mainly imparted by FeN x C y moieties. Nevertheless, the presented guidelines are generally applicable to the whole class of Fe-N-C catalysts in order to minimize Fe demetallation in PEMFCs, which provides important advances for the future design of stable electrocatalytic systems for long-term operation.

Corrosion resistance of a transition-metal-rich PtCu3/C oxygen reduction reaction (ORR) catalyst as a representative of Pt alloy-based materials has been significantly improved by doping with small amounts of gold (<1 at. %). Transmission electron microscopy imaging shows near-surface segregation of both platinum and gold with the underlying core consisting predominantly of intermetallic PtCu3. The resulting PtAu skin catalyst shows improved resistance against Cu dissolution, as well as against carbon corrosion if compared to its PtCu3 precursor. Also, it exhibits a much higher Pt and carbon stability than a widely used Pt/C standard. Most importantly, the Au doped sample shows a substantial improvement in stability at the elevated temperature (60 degrees C) degradation test (10 000 cycles; 0.4-1.2 Vim) simulating a real PEM fuel cell environment

High oxygen evolution reaction activity of ruthenium and long term stability of iridium in acidic electrolytes make their mixed oxides attractive candidates for utilization as anodes in water electrolyzers. Indeed, such materials were addressed in numerous previous studies. The application of a scanning flow cell connected to an inductively coupled plasma mass spectrometer allowed us now to examine the stability and activity toward oxygen evolution reaction of such mixed oxides in parallel. The whole composition range of Ir-Ru mixtures has been covered in a thin film material library. In the whole composition range the rate of Ru dissolution is observed to be much higher than that of Ir. Eventually, due to the loss of Ru, the activity of the mixed oxides approaches the value corresponding to pure IrO 2 . Interestingly, the loss of only a few percent of a monolayer in Ru surface concentration results in a significant drop in activity. Several explanations of this phenomenon are discussed. It is concluded that the herein observed stability of mixed Ir-Ru oxide systems is most likely a result of high corrosion resistance of the iridium component, but not due to an alteration of the material's electronic structure. Renewable primary energies such as solar energy, wind energy and ocean energy receive more and more attention and are increasingly installed around the world.1-3 It is anticipated that renewables will eventually replace traditional fossil fuel-burning and nuclear power plants. However, intermittent power supply of renewables means that energy needs to be buffered. Thereby, hydrogen produced by water electrolysis is considered as an ideal energy carrier to adjust the balance between the generation of power by renewable primary energy and energy demand for end-use.3-5 Currently, acidic proton exchange membrane water electrolysis (PEMWE) is considered as a promising technology for this purpose. However, the widespread use of PEMWE is hindered by high capital costs, low efficiency, and shortages related to performance deterioration with time. 6 In this connection the nature of electrocatalysts and the procedure of their production and application conditions play a critical role. Materials used as electrocatalysts must be as active as possible to improve efficiency, while at the same time they need to be stable to maintain this efficiency throughout the lifetime of the electrolyzer. This is especially critical for materials catalyzing the anodic oxygen evolution reaction (OER), because of the detrimental positive potential and highly corrosive acidic environment. Only a few catalysts are able to withstand these harsh conditions, while providing sufficient activity, conductivity and mechanical stability. In fact, only iridium oxide anodes are proven to provide the required longevity of operation. On the other hand, ruthenium shows the highest electrocatalytic activity toward this reaction. 7,8 During the last decades, the electrochemical and surface properties of anodes based on these metals and their oxides we...

A major step in the development of (electro)catalysis would be the possibility to estimate accurately the energetics of adsorption processes related to reaction intermediates. Computational chemistry (e.g. using DFT) developed significantly in that direction and allowed the fast prediction of (electro)catalytic activity trends and improved the general understanding of adsorption at electrochemical interfaces. However, building a reliable and comprehensive picture of electrocatalytic reactions undoubtedly requires experimental assessment of adsorption energies. In this way, the results obtained by computational chemistry can be complemented or challenged, which often is a necessary pathway to further advance the understanding of electrochemical interfaces. In this work an interfacial descriptor of the electrocatalytic activity for hydrogen evolution reaction, analogue to the adsorption energy of the H intermediate, is identified experimentally using in situ probing of the surface potentials of the metals, under conditions of continuous control of the humidity and the gas exposure. The derived activity trends give clear indication that the electrocatalytic activity for hydrogen evolution reaction is a consequence of an interplay between metal-hydrogen and metal-water interactions. In other words it is shown that the M-H bond formation strongly depends on the nature of the metal-water interaction. In fact, it seems that water dipoles at the metal/electrolyte interface play a critical role for electron and proton transfer in the double layer.

This study focuses on the synthesis and electrochemical performance (i.e, activity and stability) of advanced electrocatalysts for the oxygen reduction reaction (ORR), made of Pt–Ni nanoparticles embedded in hollow graphitic spheres (HGS). The mechanism of the confined space alloying, that is, the controlled alloying of bimetallic precursors with different compositions (i.e., Pt3Ni, PtNi, and PtNi3) within the HGS mesoporous shell, was examined in detail. It was found that the presence of platinum during the reduction step, as well as the application of high annealing temperatures (at least 850 °C for 3.5h in Ar), are necessary conditions to achieve the complete encapsulation and the full stability of the catalysts. The evolution of the activity, the electrochemical surface area, and the residual alloy composition of the Pt–Ni@HGS catalysts was thoroughly monitored (at the macro- and nanoscale level) under different degradation conditions. After the initial activation, the embedded Pt–Ni nanoparticles (3–4 nm in size) yield mass activities that are 2- to 3.5-fold higher than that of pure Pt@HGS (depending on the alloy composition). Most importantly, it is demonstrated that under the normal operation range of an ORR catalyst in PEM-FCs (potential excursions between 0.4 and 1.0 VRHE) both the nanoparticle-related degradation pathways (particle agglomeration) and dealloying phenomena are effectively suppressed, irrespectively of the alloy composition. Thus, the initial enhanced activity is completely maintained over an extended degradation protocol. In addition, owing to the peculiar configuration of the catalysts consisting of space-confined nanoparticles, it was possible to elucidate the impact of the dealloying process (as a function of alloy composition and severity of the degradation protocols) separately from other parallel phenomena, providing valuable insight into this elusive degradation mechanism.

The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling aqua regia; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an ‘electrode-less' process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable.

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