Roland Hauert

Passive films on the superaustenitic stainless steel 1.4652 were studied using angular resolved hard X‐ray photo‐electron spectroscopy (HAXPES), which provides an increased information depth compared to conventional X‐ray photo‐electron spectroscopy (XPS). Elemental depth profiles in the oxide as well as gradients in the underlying metal were established using a dedicated algorithm. The utility was exemplified for three different conditions of film formation: (i) as polished and as polarized to the high passive end in (ii) 1 M H ₂ SO ₄ and (iii) 1 M NaOH. The use of a superaustenitic material ascertained that metal signals from the main contributors to film formation: Fe, Cr, Ni, and Mo remained above the detection limit throughout the data set. With the dual‐source technique (XPS, HAXPES), it was possible to investigate metal gradients underneath the passive film. For polarizations in an acidic environment, a metallic nickel enrichment of the order of 5 Å was found. For a corresponding polarization in an alkaline environment, the metal region closest to the oxide/metal interface was enriched in iron, followed by concentration gradients down to about 50 Å into the metal.

Chemical modifiers enhance the efficiency of metal catalysts in numerous applications, but their introduction often involves toxic or expensive precursors and complicates the synthesis. Here, we show that a porous boron nitride carrier can directly modify supported palladium nanoparticles, originating unparalleled performance in the continuous semi‐hydrogenation of alkynes. Analysis of the impact of various structural parameters reveals that using a defective high surface area boron nitride and ensuring a palladium particle size of 4–5 nm is critical for maximizing the specific rate. The combined experimental and theoretical analyses point towards boron incorporation from defects in the support to the palladium subsurface, creating the desired isolated ensembles determining the selectivity. This practical approach highlights the unexplored potential of using tailored carriers for catalyst design.

Chemical modifiers enhance the efficiency of metal catalysts in numerous applications, but their introduction often involves toxic or expensive precursors and complicates the synthesis. Here, we show that a porous boron nitride carrier can directly modify supported palladium nanoparticles, originating unparalleled performance in the continuous semi‐hydrogenation of alkynes. Analysis of the impact of various structural parameters reveals that using a defective high surface area boron nitride and ensuring a palladium particle size of 4–5 nm is critical for maximizing the specific rate. The combined experimental and theoretical analyses point towards boron incorporation from defects in the support to the palladium subsurface, creating the desired isolated ensembles determining the selectivity. This practical approach highlights the unexplored potential of using tailored carriers for catalyst design.

Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom‐efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non‐scalable regime in which each atom counts. Almost all trends in this ultra‐small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence application‐dependent requirements of the active ensemble. In the semi‐hydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well‐defined numbers of atoms.

Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom‐efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non‐scalable regime in which each atom counts. Almost all trends in this ultra‐small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence application‐dependent requirements of the active ensemble. In the semi‐hydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well‐defined numbers of atoms.

Ensemble control has been intensively pursued for decades to identify sustainable alternatives to the Lindlar catalyst (PdPb/CaCO₃) applied for the partial hydrogenation of alkynes in industrial organic synthesis. Although the geometric and electronic requirements are known, a literature survey illustrates the difficulty of transferring this knowledge into an efficient and robust catalyst. Here, we report a simple treatment of palladium nanoparticles supported on graphitic carbon nitride with aqueous sodium sulfide, which directs the formation of a nanostructured Pd₃S phase with controlled crystallographic orientation, exhibiting unparalleled performance in the semi-hydrogenation of alkynes in the liquid phase. The exceptional behavior is linked to the multifunctional role of sulfur. Apart from defining a structure integrating spatially-isolated palladium trimers, the active ensembles, the modifier imparts a bifunctional mechanism and weak binding of the organic intermediates. Similar metal trimers are also identified in Pd₄S, evidencing the pervasiveness of these selective ensembles in supported palladium sulfides.

The electroreduction of CO₂ to fuels and chemicals is an attractive strategy for the valorization of CO₂ emissions. In this study, a Cu₂O electrocatalyst prepared by a simple and potentially scalable solvothermal route effectively targeted CO evolution at low‐to‐moderate overpotentials [with a current efficiency for CO (CE_CO) of ca. 60 % after 12 h at −0.6 V vs. reversible hydrogen electrode, RHE], and its selectivity was tuned by the introduction of p‐block elements (In, Sn, Ga, Al) into the catalyst. SEM, HRTEM, and voltammetric analyses revealed that the Cu₂O catalyst undergoes extensive surface restructuring (favorable for CO evolution) under the reaction conditions. The modification of Cu₂O with Sn and In further enhanced the current efficiency (CE) for CO (ca. 75 % after 12 h at −0.6 V). In contrast, the introduction of Al altered the selectivity profile of the catalyst significantly, decreasing the selectivity toward CO but promoting the reduction of CO₂ to ethylene (CE≈7 %), n‐propanol, and ethanol (CE≈2 % each) at −0.8 V vs. RHE. This result is related to a decreased reducibility of Al‐doped Cu₂O that might preserve Cu⁺ species (favorable for C₂H₄ production) under the reaction conditions, which is supported by XRD, X‐ray photoelectron spectroscopy, and H₂ temperature‐programmed reduction observations.