Towards a realistic prediction of catalyst durability from liquid half-cell tests.

Liquid half-cell measurements provide a convenient laboratory method for determining relevant parameters of electro-catalysts applied in e.g. polymer electrolyte membrane fuel cells. While these measurements may be effective in certain contexts, their applicability to real-world systems, such as single-cells in a membrane electrode assembly (MEA) configuration, is not always clear. This is particularly true when assessing the stability of these systems through accelerated stress tests (ASTs). Due to different electrode compositions and operating conditions, nanoscale degradation proceeds differently. Nevertheless, given the high demands of MEA measurements in terms of time, testing equipment complexity, and amount of catalyst material, application-relevant predictions of catalyst durability from liquid half-cell tests are highly desirable. This study combines electrochemical and nanoparticle analysis based on transmission electron microscopy to conduct a typical voltage cycling AST for rotating disc electrode (RDE) measurements, showing that the loss of the electrochemically active surface area (ECSA) of the used Pt/Vulcan catalyst is strongly enhanced at 80 °C compared to room temperature, which goes along with increased nanoparticle coarsening. Additionally, a high ionomer/carbon mass ratio (I/C = 0.7) accelerates the ECSA loss, and further investigations of its influence suggest a combination of several factors, including the high local proton concentration and the presence of adsorbing anions. At the same temperature (80 °C) and I/C ratio (0.7), the ECSA loss vs. AST cycle number of the Pt/Vulcan catalyst is essentially identical for a voltage cycling AST conducted in either an RDE half-cell or an MEA configuration, suggesting that liquid electrolyte half-cell based ASTs can provide application-relevant results. Thus, our study points out a way for predicting the stability of electro-catalysts in MEAs based on RDE experiments that require less specialized equipment and only µg-quantities of catalysts.

Engineering stable electrocatalysts by synergistic stabilization between carbide cores and Pt shells.

Core-shell particles with earth-abundant cores represent an effective design strategy for improving the performance of noble metal catalysts, while simultaneously reducing the content of expensive noble metals1-4. However, the structural and catalytic stabilities of these materials often suffer during the harsh conditions encountered in important reactions, such as the oxygen reduction reaction (ORR)3-5. Here, we demonstrate that atomically thin Pt shells stabilize titanium tungsten carbide cores, even at highly oxidizing potentials. In situ, time-resolved experiments showed how the Pt coating protects the normally labile core against oxidation and dissolution, and detailed microscopy studies revealed the dynamics of partially and fully coated core-shell nanoparticles during potential cycling. Particles with complete Pt coverage precisely maintained their core-shell structure and atomic composition during accelerated electrochemical ageing studies consisting of over 10,000 potential cycles. The exceptional durability of fully coated materials highlights the potential of core-shell architectures using earth-abundant transition metal carbide (TMC) and nitride (TMN) cores for future catalytic applications.

What is the trigger for the hydrogen evolution reaction? - towards electrocatalysis beyond the Sabatier principle.

The mechanism of the hydrogen evolution reaction, although intensively studied for more than a century, remains a fundamental scientific challenge. Many important questions are still open, making it elusive to establish rational principles for electrocatalyst design. In this work, a comprehensive investigation was conducted to identify which dynamic phenomena at the electrified interface are prerequisite for the formation of molecular hydrogen. In fact, what we observe as an onset of the macroscopic faradaic current originates from dynamic structural changes in the double layer, which are entropic in nature. Based on careful analysis of the activation process, an electrocatalytic descriptor is introduced, evaluated and experimentally confirmed. The catalytic activity descriptor is named as the potential of minimum entropy. The experimentally verified catalytic descriptor reveals significant potential to yield innovative insights for the design of catalytically active materials and interfaces.

Shape-Controlled Nanoparticles in Pore-Confined Space.

Increasing the catalyst's stability and activity are one of the main quests in catalysis. Tailoring crystal surfaces to a specific reaction has demonstrated to be a very effective way in increasing the catalyst's specific activity. Shape controlled nanoparticles with specific crystal facets are usually grown kinetically and are highly susceptible to morphological changes during the reaction due to agglomeration, metal dissolution, or Ostwald ripening. A strong interaction of the catalytic material to the support is thus crucial for successful stabilization. Taken both points into account, a general catalyst design is proposed, combining the enhanced activity of shape-controlled nanoparticles with a pore-confinement approach for high stability. Hollow graphitic spheres with narrow and uniform bimodal mesopores serve as model system and were used as support material. As catalyst, different kinds of particles, such as pure platinum (Pt), platinum/nickel (Pt3Ni) and Pt3Ni doped with molybdenum (Pt3Ni-Mo), have exemplarily been synthesized. The advantages, limits and challenges of the proposed concept are discussed and elaborated by means of time-resolved, in and ex situ measurements. It will be shown that during catalysis, the potential boundaries are crucial especially for the proposed catalyst design, resulting in either retention of the initial activity or drastic loss in shape, size and elemental composition. The synthesis and catalyst design can be adapted to a wide range of catalytic reactions where stabilization of shape-controlled particles is a focus.

Stability and Activity of Non-Noble-Metal-Based Catalysts Toward the Hydrogen Evolution Reaction.

A fundamental understanding of the behavior of non-noble based materials toward the hydrogen evolution reaction is crucial for the successful implementation into practical devices. Through the implementation of a highly sensitive inductively coupled plasma mass spectrometer coupled to a scanning flow cell, the activity and stability of non-noble electrocatalysts is presented. The studied catalysts comprise a range of compositions, including metal carbides (WC), sulfides (MoS2 ), phosphides (Ni5 P4 , Co2 P), and their base metals (W, Ni, Mo, Co); their activity, stability, and degradation behavior was elaborated and compared to the state-of-the-art catalyst platinum. The non-noble materials are stable at HER potentials but dissolve substantially when no current is flowing. Through pre- and post-characterization of the catalysts, explanations of their stability (thermodynamics and kinetics) are discussed, challenges for the application in real devices are analyzed, and strategies for circumventing dissolution are suggested. The precise correlation of metal dissolution with applied potential/current density allows for narrowing down suitable material choices as replacement for precious group metals as for example, platinum and opens up new ways in finding cost-efficient, active, and stable new-generation electrocatalysts.

The synthesis of nanostructured Ni5 P4 films and their use as a non-noble bifunctional electrocatalyst for full water splitting.

The investigation of nickel phosphide (Ni5 P4 ) as a catalyst for the hydrogen (HER) and oxygen evolution reaction (OER) in strong acidic and alkaline environment is described. The catalyst can be grown in a 3D hierarchical structure directly on a nickel substrate, thus making it an ideal candidate for practical water splitting devices. The activity of the catalyst towards the HER, together with its high stability especially in acidic solution, makes it one of the best non-noble materials described to date. Furthermore, Ni5 P4 was investigated in the OER and showed activity superior to pristine nickel or platinum. The practical relevance of Ni5 P4 as a bifunctional catalyst for the overall water splitting reaction was demonstrated, with 10 mA cm(-2) achieved below 1.7 V.

Catalyst durability in electrocatalytic H2O2 production: key factors and challenges.

On-demand electrocatalytic hydrogen peroxide (H2O2) production is a significant technological advancement that offers a promising alternative to the traditional anthraquinone process. This approach leverages electrocatalysts for the selective reduction of oxygen through a two-electron transfer mechanism (ORR-2e-), holding great promise for delivering a sustainable and economically efficient means of H2O2 production. However, the harsh operating conditions during the electrochemical H2O2 production lead to the degradation of both structural integrity and catalytic efficacy in these materials. Here, we systematically examine the design strategies and materials typically utilized in the electroproduction of H2O2 in acidic environments. We delve into the prevalent reactor conditions and scrutinize the factors contributing to catalyst deactivation. Additionally, we propose standardised benchmarking protocols aimed at evaluating catalyst stability under such rigorous conditions. To this end, we advocate for the adoption of three distinct accelerated stress tests to comprehensively assess catalyst performance and durability.

Engineering gold-platinum core-shell nanoparticles by self-limitation in solution.

Core-shell particles with thin noble metal shells represent an attractive material class with potential for various applications ranging from catalysis to biomedical and pharmaceutical applications to optical crystals. The synthesis of well-defined core-shell architectures remains, however, highly challenging. Here, we demonstrate that atomically-thin and homogeneous platinum shells can be grown via a colloidal synthesis method on a variety of gold nanostructures ranging from spherical nanoparticles to nanorods and nanocubes. The synthesis is based on the exchange of low binding citrate ligands on gold, the reduction of platinum and the subsequent kinetically hindered growth by carbon monoxide as strong binding ligand. The prerequisites for homogeneous growth are low core-binding ligands with moderate fast ligand exchange in solution, a mild reducing agent to mitigate homonucleation and a strong affinity of a second ligand system that can bind to the shell's surface. The simplicity of the described synthetic route can potentially be adapted to various other material libraries to obtain atomically smooth core-shell systems.

Correlation between the TiO2 encapsulation layer on Pt and its electrochemical behavior.

Supported metal catalysts with partial encapsulation resulting from strong metal-support interactions show distinctive structural features which strongly affect their functionalities. Yet, challenges in systematic synthesis and in-depth characterization for such systems limit the present understanding of structure-property relationships. Herein, the synthesis and characterization of two Pt/TiO2 models are conducted by a simple change of the synthesis order, while keeping all other parameters constant. They differ in containing either bare or encapsulated Pt nanoparticles. The presence of an extremely thin and inhomogeneous TiO2 layer is clearly demonstrated on 2-3 nm sized Pt nanoparticles by combination of imaging, energy dispersive X-ray spectroscopy and electron energy loss spectroscopy performed in a transmission electron microscope. The two Pt/TiO2 systems exhibit differences in morphology and local structure which can be correlated with their electrochemical activity and stability using cyclic voltammetry experiments. Beyond enhanced particle stability, we report an increase in H+ intercalation on titania and reduced Pt activity due to partial encapsulation by TiO2. Finally, the growth of an encapsulation layer as a result of cyclic voltammetry measurements is discussed. These results shed light on the in-depth structure-property relationship of catalysts with strong metal-support interactions which leads to enhanced functional materials for electrochromic devices and energy applications.

Carbon nanodots revised: the thermal citric acid/urea reaction.

Luminescent compounds obtained from the thermal reaction of citric acid and urea have been studied and utilized in different applications in the past few years. The identified reaction products range from carbon nitrides over graphitic carbon to distinct molecular fluorophores. On the other hand, the solid, non-fluorescent reaction product produced at higher temperatures has been found to be a valuable precursor for the CO2-laser-assisted carbonization reaction in carbon laser-patterning. This work addresses the question of structural identification of both, the fluorescent and non-fluorescent reaction products obtained in the thermal reaction of citric acid and urea. The reaction products produced during autoclave-microwave reactions in the melt were thoroughly investigated as a function of the reaction temperature and the reaction products were subsequently separated by a series of solvent extractions and column chromatography. The evolution of a green molecular fluorophore, namely HPPT, was confirmed and a full characterization study on its structure and photophysical properties was conducted. The additional blue fluorescence is attributed to oligomeric ureas, which was confirmed by complementary optical and structural characterization. These two components form strong hydrogen-bond networks which eventually react to form solid, semi-crystalline particles with a size of ∼7 nm and an elemental composition of 46% C, 22% N, and 29% O. The structural features and properties of all three main components were investigated in a comprehensive characterization study.

Self-Limiting Shell Formation in Cu@Ag Core-Shell Nanocrystals during Galvanic Replacement.

The understanding of synthetic pathways of bimetallic nanocrystals remains limited due to the complex energy landscapes and dynamics involved. In this work, we investigate the formation of self-limiting Cu@Ag core-shell nanoparticles starting from Cu nanocrystals followed by galvanic replacement with Ag ions. Bulk quantification with atomic emission spectroscopy and spatially resolved elemental mapping with electron microscopy reveal distinct nucleation regimes that produce nanoparticles with a tunable Ag shell thickness, but only up to a certain limiting thickness. We develop a quantitative transport model that explains this observed self-limiting structure as arising from the balance between entropy-driven interdiffusion and a positive mixing enthalpy. The proposed model depends only on the intrinsic physical properties of the system such as diffusivity and mixing energy and directly yields a high level of agreement with the elemental mapping profiles without requiring additional fit parameters.

Disclosing the High Activity of Ceramic Metallics in the Oxygen Evolution Reaction: Nickel Materials as a Case Study.

Here, we elucidate the activity origin of ceramic nickel electrocatalysts in the oxygen evolution reaction (OER), ranging from nitrides, sulfides, and phosphides, as a case study that may be projected on almost any ceramic metallic. Our results show that regardless of the starting material, the formation of an active (oxy)hydroxide layer, acting as the real electrocatalyst during the OER, is unavoidable. Nevertheless, the in situ transformation into highly active (oxy)hydroxides leads to the formation of active catalysts for various applications.