A versatile multifunctional laboratory-based near ambient pressure x-ray photoelectron spectroscopy (XPS) instrument is presented. The entire device is highly customized regarding geometry, exchangeable manipulators and sample stages for liquid- and solid-state electrochemistry, cryochemistry, and heterogeneous catalysis. It therefore delivers novel and unique access to a variety of experimental approaches toward a broad choice of functional materials and their specific surface processes. The high-temperature (electro)catalysis manipulator is designed for probing solid state/gas phase interactions for heterogeneous catalysts including solid electrolyzer/fuel cell electrocatalysts at pressures up to 15 mbar and temperatures from room temperature to 1000 °C. The liquid electrochemistry manipulator is specifically designed for in situ spectroscopic investigations of polarized solid/liquid interfaces using aqueous electrolytes and the third one for experiments for ice and ice-like materials at cryogenic temperatures to approximately −190 °C. The flexible and modular combination of these setups provides the opportunity to address a broad spectrum of in situ and operando XPS experiments on a laboratory-based system, circumventing the limited accessibility of experiments at synchrotron facilities.

To identify the synergistic action of differently prepared Ni-ZrO₂ phase boundaries in methane dry reforming, we compared an “inverse” near-surface intermetallic NiZr catalyst precursor with the respective bulk-intermetallic Ni_xZr_y material and a supported Ni-ZrO₂ catalyst. In all three cases, stable and high methane dry reforming activity with enhanced anticoking properties can be assigned to the presence of extended Ni-ZrO₂ phase boundaries, which result from in situ activation of the intermetallic Ni-Zr model catalyst systems under DRM conditions. All three catalysts operate bifunctionally; methane is essentially decomposed to carbon at the metallic Ni⁰ surface sites, whereas CO₂ reacts to CO at reduced Zr centers induced by a spillover of carbon to the phase boundaries. On pure bulk Ni⁰, dissolved carbon accumulates in surface-near regions, leading to a sufficiently supersaturated state for completely surface-blocking graphitic carbon segregation. In strong contrast, surface-ZrO₂ modified bulk Ni⁰ exhibits virtually the best decoking and carbon conversion conditions due to the presence of highly dispersed ZrO₂ islands with a particularly large contribution of interfacial Ni⁰-ZrO₂ sites and short C-diffusion pathways to the latter.

Solid oxide cell technologies play a pivotal role in the realm of renewable energy storage, guiding us through the journey toward decarbonization. Understanding how electrocatalytic materials behave under high‐temperature conditions is an absolute necessity to push these technologies forward. Operando spectroscopic investigations, such as near‐ambient pressure X‐ray photoelectron spectroscopy (NAP–XPS), offer insights into the chemical nature of active working electrodes, including the dynamic response of redox states and adsorbate chemistry to changing electrochemical conditions. Mixed ceramic–metallic electrodes exhibit a limited region with electrochemically active triple‐phase‐boundary (TPB) sites, which are located close to the electrolyte/electrode interface. To monitor this specific region spectroscopically, metallic (Ni) and bimetallic (NiCu) network‐like structures are synthesized on a yttria‐stabilized zirconia electrolyte and the electrochemical state and performance are studied by using operando NAP–XPS. In the experiments, the surface oxidation states under different polarizations are revealed, the gas composition dependent Nernst shift is confirmed, electrocatalytic activities are unraveled, and hydrogen evolution is correlated with the applied potential. The findings demonstrate, the effectiveness of thin‐film model cells with spectroscopically accessible TPB regions for probing interfacial states and electrochemical processes. The obtained fundamental knowledge can provide valuable insights for the advancement of renewable energy storage technologies.

Solid oxide cell technologies play a crucial role in climate change mitigation by enabling the reversible storage of renewable energy. Understanding the electrochemical high-temperature reaction mechanisms and the catalytic role of the electrode and electrolyte materials is essential for advancing power-to-H₂ technologies. Despite its significance, limited in situ spectroscopic research focusing on nickel and yttria-stabilized zirconia (Ni/YSZ) is available. We employ near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) to investigate 2D porous Ni/YSZ model electrodes with variable YSZ domain sizes and triple phase boundary (TPB) lengths. Focusing on the hydrogen evolution reaction (HER), we provide a mechanistic explanation for why surface hydroxylation and electrochemical activity are correlated with the YSZ surface area and YSZ domain size and unravel the specific mechanistic role of the YSZ surface. A direct comparison of normalization of the measured total electrolysis current to the purely geometrical length of the TPB vs an electrified "catchment area" next to the TPB, exhibiting strong enough electric fields, is the key to a correct quantitative description of the individual elementary steps of water electrolysis on Ni/YSZ. By combining electrochemical impedance spectroscopy, NAP-XPS, and electric field modeling, the local water reduction process near the TPB can be described, indicating optimized structural parameters for improved HER performance.

For the direct reduction of CO₂ and H₂O in solid oxide electrolysis cells (SOECs) with cermet electrodes toward methane, a fundamental understanding of the role of elemental carbon as a key intermediate within the reaction pathway is of eminent interest. The present synchrotron-based in situ near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) study shows that alloying of Ni/yttria-stabilized-zirconia (YSZ) cermet electrodes with Cu can be used to control the electrochemical accumulation of interfacial carbon and to optimize its reactivity toward CO₂. In the presence of syngas, sufficiently high cathodic potentials induce excess methane on the studied Ni/yttria-stabilized-zirconia (YSZ)-, NiCu/YSZ- and Pt/gadolinium-doped-ceria (GDC) cermet systems. The hydrogenation of carbon, resulting from CO activation at the triple-phase boundary of Pt/GDC, is most efficient.

For the direct reduction of CO2 and H2O in solid oxide electrolysis cells (SOECs) with cermet electrodes toward methane, a fundamental understanding of the role of elemental carbon as a key intermediate within the reaction pathway is of eminent interest. The present synchrotron-based in situ near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) study shows that alloying of Ni/yttria-stabilized-zirconia (YSZ) cermet electrodes with Cu can be used to control the electrochemical accumulation of interfacial carbon, and to optimize its reactivity toward CO2. In the presence of syngas, sufficiently high cathodic potentials induce excess methane on the studied Ni/yttria stabilized zirconia (YSZ)-, NiCu/YSZ- and Pt/gadolinium doped ceria (GDC) cermet systems. The hydrogenation of carbon resulting from CO activation at the triple-phase boundary of Pt/GDC is most efficient.