Evolution of a GDE setup: Beyond ambient conditions

Gas diffusion electrode (GDE) setups recently and increasingly received attention as testing platforms for fuel cell catalysts. GDE setups provide realistic reaction conditions while remaining simple and efficient to use. Therefore, GDE setups bridge the gap between rotating disk electrode (RDE) measurements and membrane electrode assembly (MEA) testing. Here, we describe our initial GDE design development to its latest improvements that allow application of high temperatures. We point out experimental challenges we overcame, yet also discuss properly applying our new technique to avoid wrongful use. In particular, we advocate for implementing GDE setups in catalyst stability investigations where the technique so far has been used infrequently

On the electrooxidation of glucose on gold: Towards an electrochemical glucaric acid production as value-added chemical

The electrocatalytic oxidation of glucose to value-added chemicals, such as glucaric acid, has gathered increased interest in recent years. Glucose oxidation is a promising process which has the potential to contribute to establishing renewable resources as alternatives to fossil carbon sources. Herein, we present rotating disk electrode (RDE) studies on polycrystalline gold surfaces and subsequent Koutecký-Levich analysis as a benchmark to expand the understanding of reaction kinetics and competition between glucose, reaction intermediates and OH− at the catalyst surface. Based on the obtained results it follows that the glucose oxidation reaction (GOR) is predominately mass-transport controlled. Combining electrochemical studies and Raman spectroscopy, it is shown that increasing glucose concentrations lead to a delayed oxidation of the gold catalyst surface, presumably by increased consumption rates of Au-hydroxide species

On the electro-oxidation of small organic molecules: Towards a fuel cell catalyst testing platform based on gas diffusion electrode setups

The electrocatalytic oxidation of small organic compounds such as methanol or formic acid has been the subject of numerous investigations in the last decades. The motivation for these studies is often their use as fuel in so-called direct methanol or direct formic acid fuel cells, promising alternatives to hydrogen-fueled proton exchange membrane fuel cells. The fundamental research spans from screening studies to identify the best performing catalyst materials to detailed mechanistic investigations of the reaction pathway. These investigations are commonly performed at conditions quite different to fuel cell devices, where no liquid electrolyte will be present. We previously developed a gas diffusion electrode setup to mimic “real-life” reaction conditions and study electrocatalysts for oxygen gas reduction or water splitting. It is here demonstrated that the setup is also suitable to investigate the properties of catalysts for the electro-oxidation of small organic molecules simulating conditions of low temperature proton exchange membrane fuel cells

Oxygen Reduction Reaction on Polycrystalline Platinum: On the Activity Enhancing Effect of Polyvinylidene Difluoride

There have been several reports concerning the performance improving properties of additives, such as polyvinylidene difluoride (PVDF), to the membrane or electrocatalyst layer of proton exchange membrane fuel cells (PEMFC). However, it is not clear if the observed performance enhancement is due to kinetic, mass transport, or anion blocking effects of the PVDF. In a previous investigation using a thin-film rotating disk electrode (RDE) approach (of decreased complexity as compared to membrane electrode assembly (MEA) tests), a performance increase for the oxygen reduction reaction (ORR) could be confirmed. However, even in RDE measurements, reactant mass transport in the catalyst layer cannot be neglected. Therefore, in the present study, the influence of PVDF is re-examined by coating polycrystalline bulk Pt electrodes by PVDF and measuring ORR activity. The results on polycrystalline bulk Pt indicate that the effects of PVDF on the reaction kinetics and anion adsorption are limited, and that the observed performance increase on high surface area Pt/C most likely is due to an erroneous estimation of the electrochemical active surface area (ECSA) from CO stripping and Hupd

Following Paths of Maximum Catalytic Activity in the Composition Space of High‐Entropy Alloys

The search for better and cheaper electrocatalysts is vital in the global transition to renewable energy resources. High-entropy alloys (HEAs) provide a near-infinite number of different alloys with approximately continuous properties such as catalytic activity. In this work, the catalytic activity for the electrochemical oxygen reduction reaction as a function of molar composition of Ag-Ir-Pd-Pt-Ru HEA is treated as a landscape wherein it is shown that the maxima are connected through ridges. By following the ridges, it is possible to navigate between the maxima using a modified nudged elastic band (NEB) model integrated in a machine learning NEB algorithm. These results provide a new understanding of the composition space being similar to an evolutionary landscape. This provides a possible new search and design strategy for new catalysts in which the composition of known catalysts can be optimized by following ridges rather than exploring the whole alloy composition space

Investigating the Particle Growth in Bimodal Pt/C Catalysts by In-Situ Small-Angle X-ray Scattering: Challenges in the Evaluation of Stress Test Protocol-Dependent Degradation Mechanisms

The influence of different combinations of accelerated stress test (AST) protocols simulating load-cycle and start/stop conditions of a proton exchange membrane fuel cell (PEMFC) vehicle is investigated on a bimodal Pt/C catalyst. The bimodal Pt/C catalyst, prepared by mixing two commercial catalysts, serves as a model system and consists of two distinguishable size populations. The change in mean particle size was investigated by in situ small-angle X-ray scattering (SAXS). The comparison to the reference catalysts, i.e., the two single-size population catalysts, uncovers the presence of electrochemical Ostwald ripening as a degradation mechanism in the bimodal catalyst. Increasing the harshness of the applied AST protocol combinations by faster changing between load-cycle or start/stop conditions, the particle size of the larger population of the bimodal catalyst increases faster than expected. Surprisingly, the change in mean particle size of the smaller size population indicates a smaller increase for harsher AST protocols, which might be explained by a substantial electrochemical Ostwald ripening

Spatially Localized Synthesis and Structural Characterization of Platinum Nanocrystals Obtained Using UV Light

Platinum nanocrystals with a fine control of the crystal domain size in the range 1.0–2.2 nm are produced by tuning the NaOH concentration during the UV-induced reduction of H$_2$PtCl$_6$ in surfactant-free alkaline ethylene glycol. The colloidal solutions obtained are characterized by transmission electron microscopy and pair distribution function analysis, allowing analysis of both atomic and nanoscale structures. The obtained nanoparticles exhibit a face-centered cubic crystal structure even for the smallest nanoparticles, and the cubic unit cell parameter is significantly reduced with decreasing crystallite size. It is further demonstrated how the “UV-approach” can be used to achieve spatial control of the nucleation and growth of the platinum nanocrystals, which is not possible by thermal reduction

The gas diffusion electrode setup as a testing platform for evaluating fuel cell catalysts: A comparative RDE‐GDE study

Gas diffusion electrode (GDE) setups have been recently introduced as a new experimental approach to test the performance of fuel cell catalysts under high mass transport conditions, while maintaining the simplicity of rotating disk electrode (RDE) setups. In contrast to experimental RDE protocols, for investigations using GDE setups only few systematic studies have been performed. In literature, different GDE arrangements were demonstrated, for example, with and without an incorporated proton exchange membrane. Herein, we chose a membrane-GDE approach for a comparative RDE–GDE study, where we investigate several commercial standard Pt/C fuel cell catalysts with respect to the oxygen reduction reaction (ORR). Our results demonstrate both the challenges and the strengths of the new fuel cell catalyst testing platform. We highlight the analysis and the optimization of catalyst film parameters. That is, instead of focusing on the intrinsic catalyst ORR activities that are typically derived in RDE investigations, we focus on parameters, such as the catalyst ink recipe, which can be optimized for an individual catalyst in a much simpler manner as compared to the elaborative membrane electrode assembly (MEA) testing. In particular, it is demonstrated that ∼50% improvement in ORR performance can be reached for a particular Pt/C catalyst by changing the Nafion content in the catalyst layer. The study therefore stresses the feasibility of the GDE approach used as an intermediate “testing step” between RDE and MEA tests when developing new fuel cell catalysts

UV-induced syntheses of surfactant-free precious metal nanoparticles in alkaline methanol and ethanol

Surfactant-free UV-induced syntheses of Pt and Ir nanoparticles in alkaline methanol and ethanol are presented. Small size nanoparticles ca. 2 nm in diameter are obtained without surfactants in a wide range of base concentration