Navigating the Unkown With AI: Multiobjective Bayesian Optimization of Non-Noble Acidic OER Catalysts

Experimental catalyst optimization is plagued by slow and laborious efforts. Finding innovative materials is key to advancing research areas for sustainable energy conversion, such as electrocatalysis. Artificial intelligence (AI)-guided optimization bears great potential to autonomously learn from data and plan new experiments, identifying a global optimum significantly faster than traditional design of experiment approaches. Furthermore, it is vital to incorporate essential electrocatalyst features such as activity and stability into the optimization campaign to screen for a truly high-performing material. In this study, a multiobjective Bayesian optimization (MOBO) was used in conjunction with an experimental high-throughput (HT) pipeline to refine the composition of a non-noble Co-Mn-Sb-Sn-Ti oxide toward its activity and stability for the oxygen evolution reaction (OER) in acid. The viability of the MOBO algorithm was verified on a gathered data set, and an acceleration of 17x was achieved in subsequent experimental screening compared to a hypothetical grid search scenario. During the ML-driven assessment, Mn-rich compositions were critical to designing high-performing OER catalysts, while Ti incorporation into MnOx triggered an improved activity after short accelerated stress tests. To examine this finding further, an operando mass spectrometry technique was used to probe the evolution of activity, metal dissolution, and surface area over 3 h of operation. This work demonstrates the importance of respecting the multiobjective nature in electrocatalyst performance during HT campaigns. AI-based decision-making helps to bridge the gap between fast HT screening (limited property extraction) and slow fundamental research (rich property extraction) by avoiding less informative experiments

pH Dependence of Noble Metals Dissolution: Gold

The electrochemical applications of gold span the entire pH spectrum. Recently, gold dissolution in acidic and alkaline media has been studied, but less attention has been given to electrolytes at intermediate pH values. To address this gap, this work uses on‐line electrochemical dissolution inductively coupled plasma mass spectrometry (ICP‐MS) to examine gold dissolution across a pH range of 1 to 12.7 using phosphate buffer solutions. All experimental parameters, except pH, are kept constant, enabling a clear investigation of pH effects on anodic (gold oxidation) and cathodic (gold oxide reduction) dissolution processes. Results show that dissolution amounts are lowest at neutral pH values between 3 and 7, varying with the applied potential and exposure time. Anodic and cathodic dissolution dominate in acidic and alkaline electrolytes, respectively. Depending on the highest applied potentials and time exposure, the main dissolution mechanism shifts at pH=5, 7, and 9. The pH dependence of Au dissolution is proposed to be linked to the nature of gold oxides formed, the kinetics of oxide formation/reduction, gold ion redeposition, and the influence of the oxygen evolution reaction (OER) on dissolution. These results provide fundamental insights into gold dissolution under neutral pH conditions.Gold dissolution in a broad pH range is investigated by on‐line inductively coupled plasma mass spectrometry (ICP‐MS). Potential range with and without oxygen evolution reaction is chosen. In both cases, dissolution is highest at the edge pHs and decreases to neutral pHs. The results are of interest for gold applications in various electrolytes. imageERA-MIN2 project Reduction/Oxidation Recyclin

Phase- and Surface Composition-Dependent Electrochemical Stability of Ir-Ru Nanoparticles during Oxygen Evolution Reaction

The increasing scarcity of iridium (Ir) and its rutile-type oxide (IrO$_{2}$), the current state-of-the-art oxygen evolution reaction (OER) catalysts, is driving the transition toward the use of mixed Ir oxides with a highly active yet inexpensive metal (Ir$_{x}$M$_{1-x}$O$_{2}$). Ruthenium (Ru) has been commonly employed due to its high OER activity although its electrochemical stability in Ir-Ru mixed oxide nanoparticles (Ir$_{x}$Ru$_{1-x}$O$_{2}$ NPs), especially at high relative contents, is rarely evaluated for long-term application as water electrolyzers. In this work, we bridge the knowledge gap by performing a thorough study on the composition- and phase-dependent stability of well-defined Ir$_{x}$Ru$_{1-x}$O$_{2}$ NPs prepared by flame spray pyrolysis under dynamic operating conditions. As-prepared NPs (Ir$_{x}$Ru$_{1-x}$O$_{y}$) present an amorphous coral-like structure with a hydrous Ir-Ru oxide phase, which upon post-synthetic thermal treatment fully converts to a rutile-type structure followed by a selective Ir enrichment at the NP topmost surface. It was demonstrated that Ir incorporation into a RuO$_{2}$ matrix drastically reduced Ru dissolution by ca. 10-fold at the expense of worsening Ir inherent stability, regardless of the oxide phase present. Hydrous Ir$_{x}$Ru$_{1-x}$O$_{y}$ NPs, however, were shown to be 1000-fold less stable than rutile-type Ir$_{x}$Ru$_{1-x}$O$_{2}$, where the severe Ru leaching yielded a fast convergence toward the activity of monometallic hydrous IrO$_{y}$. For rutile-type Ir$_{x}$Ru$_{1-x}$O$_{2}$, the sequential start-up/shut-down OER protocol employed revealed a steady-state dissolution for both Ir and Ru, as well as the key role of surface Ru species in OER activity: minimal Ru surface losses (<1 at. %) yielded OER activities for tested Ir$_{0.2}$Ru$_{0.8}$O2 equivalent to those of untested Ir$_{0.8}$Ru$_{0.2}$O2. Ir enrichment at the NP topmost surface, which mitigates selective subsurface Ru dissolution, is identified as the origin of the NP stabilization. These results suggest Ru-rich Ir$_{x}$Ru$_{1-x}$O$_{2}$ NPs to be viable electrocatalysts for long-term water electrolysis, with significant repercussions in cost reduction

Microkinetic Analysis of the Oxygen Evolution Performance at Different Stages of Iridium Oxide Degradation

The microkinetics of the electrocatalytic oxygen evolution reaction substantially determines the performance in proton-exchange membrane water electrolysis. State-of-the-art nanoparticulated rutile IrO$_{2}$ electrocatalysts present an excellent trade-off between activity and stability due to the efficient formation of intermediate surface species. To reveal and analyze the interaction of individual surface processes, a detailed dynamic microkinetic model approach is established and validated using cyclic voltammetry. We show that the interaction of three different processes, which are the adsorption of water, one potential-driven deprotonation step, and the detachment of oxygen, limits the overall reaction turnover. During the reaction, the active IrO$_{2}$ surface is covered mainly by *O, *OOH, and *OO adsorbed species with a share dependent on the applied potential and of 44, 28, and 20% at an overpotential of 350 mV, respectively. In contrast to state-of-the-art calculations of ideal catalyst surfaces, this novel model-based methodology allows for experimental identification of the microkinetics as well as thermodynamic energy values of real pristine and degraded nanoparticles. We show that the loss in electrocatalytic activity during degradation is correlated to an increase in the activation energy of deprotonation processes, whereas reaction energies were marginally affected. As the effect of electrolyte-related parameters does not cause such a decrease, the model-based analysis demonstrates that material changes trigger the performance loss. These insights into the degradation of IrO$_{2}$ and its effect on the surface processes provide the basis for a deeper understanding of degrading active sites for the optimization of the oxygen evolution performance

Addressing stability challenges of using bimetallic electrocatalysts: the case of gold?palladium nanoalloys

Bimetallic catalysts are known to often provide enhanced activity compared to pure metals, due to their electronic, geometric and ensemble effects. However, applied catalytic reaction conditions may induce restructuring, metal diffusion and dealloying. This gives rise to a drastic change in surface composition, thus limiting the application of bimetallic catalysts in real systems. Here, we report a study on dealloying using an AuPd bimetallic nanocatalyst (1 : 1 molar ratio) as a model system. The changes in surface composition over time are monitored in situ by cyclic voltammetry, and dissolution is studied in parallel using online inductively coupled plasma mass spectrometry (ICP-MS). It is demonstrated how experimental conditions such as different acidic media (0.1 M HClO4 and H2SO4), different gases (Ar and O-2), upper potential limit and scan rate significantly affect the partial dissolution rates and consequently the surface composition. The understanding of these alterations is crucial for the determination of fundamental catalyst activity, and plays an essential role for real applications, where long-term stability is a key parameter. In particular, the findings can be utilized for the development of catalysts with enhanced activity and/or selectivity

Anodic and Cathodic Platinum Dissolution Processes Involve Different Oxide Species

The degradation of Pt-containing oxygen reduction catalysts for fuel cell applications is strongly linked to the electrochemical surface oxidation and reduction of Pt. Here, we study the surface restructuring and Pt dissolution mechanisms during oxidation/reduction for the case of Pt(100) in 0.1 M HClO4 by combining operando high-energy surface X-ray diffraction, online mass spectrometry, and density functional theory. Our atomic-scale structural studies reveal that anodic dissolution, detected during oxidation, and cathodic dissolution, observed during the subsequent reduction, are linked to two different oxide phases. Anodic dissolution occurs predominantly during nucleation and growth of the first, stripe-like oxide. Cathodic dissolution is linked to a second, amorphous Pt oxide phase that resembles bulk PtO2 and starts to grow when the coverage of the stripe-like oxide saturates. In addition, we find the amount of surface restructuring after an oxidation/reduction cycle to be potential-independent after the stripe-like oxide has reached its saturation coverage.Funding is acknowledged from Deutsche Forschungsgemeinschaft for OMM and SC (project number 418603497), for OMM by the German Federal Ministry of Education and Research (BMBF) via project 05K19FK3, and for DAH by the NSERC (grant RGPIN-2017-04045). FCV acknowledges that the grants PID2021-127957NB-I00 and TED2021-132550B-C21 were funded by MCIN/AEI/ 10.13039/501100011033 and by the European Union. The use of supercomputing facilities at SURFsara was sponsored by NWO Physical Sciences, with financial support by NWO. Open Access funding enabled and organized by Projekt DEAL

Heating up the OER: Investigation of IrO 2 OER Catalysts as Function of Potential and Temperature**

Abstract Despite intensive investigations for unravelling the water splitting reaction, the catalyst behavior during the oxygen evolution reaction (OER) is still not fully understood. This is especially true under more demanding conditions like high potentials and high temperatures. Rotating disk electrode measurements show a gradual increase of OER current when increasing the temperature up to 80 °C. However, strong bubble formation at elevated temperatures makes in‐situ characterization of the catalyst challenging. Here we utilize an in‐situ electrochemical and heated flow cell, which aims at an efficient removal of bubbles from the catalyst surface and enables structural studies by X‐ray absorption spectroscopy (XAS) at temperatures up to 80 °C. Changes in the Ir L3‐edge X‐ray absorption near edge spectra (XANES) were observed with respect to the white line position and principal components related to structural changes were extracted. At temperatures of 60 °C and above, the white line position of XANES spectra reaches a steady state, which is possibly caused by an equilibrium of different Ir oxidation states. These findings provide first spectroscopic insights in the behavior of OER catalysts at elevated temperatures which are typical for industrial applications and rarely addressed until now

Local Chemical Environment Governs Anode Processes in CO2 Electrolyzers

A major goal within the CO2 electrolysis community is to replace the generally used Ir anode catalyst with a more abundant material, which is stable and active for water oxidation under process conditions. Ni is widely applied in alkaline water electrolysis, and it has been considered as a potential anode catalyst in CO2 electrolysis. Here we compare the operation of electrolyzer cells with Ir and Ni anodes and demonstrate that, while Ir is stable under process conditions, the degradation of Ni leads to a rapid cell failure. This is caused by two parallel mechanisms: (i) a pH decrease of the anolyte to a near neutral value and (ii) the local chemical environment developing at the anode (i.e., high carbonate concentration). The latter is detrimental for zero-gap electrolyzer cells only, but the first mechanism is universal, occurring in any kind of CO2 electrolyzer after prolonged operation with recirculated anolyte