Olefins from Natural Gas by Oxychlorination

Ethylene and propylene are the key building blocks of the chemical industry, but current processes are unable to close the growing gap between demand and manufacture. Reported herein is an exceptional europium oxychloride (EuOCl) catalyst for the selective (≥95 %) production of light olefins from ethane and propane by oxychlorination chemistry, thus achieving yields of ethylene (90 %) and propylene (40 %) unparalleled by any existing olefin production technology. Moreover, EuOCl is able to process mixtures of methane, ethane, and propane to produce the olefins, thereby reducing separation costs of the alkanes in natural gas. Finally, the EuOCl catalyst was supported on suitable carriers and evaluated in extrudate form, and preserves performance for >150 h under realistic process conditions.     

Tuning the Structure of Platinum Particles on Ceria In Situ for Enhancing the Catalytic Performance of Exhaust Gas Catalysts

A dynamic structural behavior of Pt nanoparticles on the ceria surface under reducing/oxidizing conditions was found at moderate temperatures (<500 °C) and exploited to enhance the catalytic activity of Pt/CeO₂‐based exhaust gas catalysts. Redispersion of platinum in an oxidizing atmosphere already occurred at 400 °C. A protocol with reducing pulses at 250–400 °C was applied in a subsequent step for controlled Pt‐particle formation. Operando X‐ray absorption spectroscopy unraveled the different extent of reduction and sintering of Pt particles: The choice of the reductant allowed the tuning of the reduction degree/particle size and thus the catalytic activity (CO>H₂>C₃H₆). This dynamic nature of Pt on ceria at such low temperatures (250–500 °C) was additionally confirmed by in situ environmental transmission electron microscopy. A general concept is proposed to adjust the noble metal dispersion (size, structure), for example, during operation of an exhaust gas catalyst.     

NHC-Stabilized Iridium Nanoparticles as Catalysts in Hydrogen Isotope Exchange Reactions of Anilines

The preparation of N-heterocyclic carbene-stabilized iridium nanoparticles and their application in hydrogen isotope exchange reactions is reported. These air-stable and easy-to-handle iridium nanoparticles showed a unique catalytic activity, allowing selective and efficient hydrogen isotope incorporation on anilines using D₂ or T₂ as isotopic source. The usefulness of this transformation has been demonstrated by the deuterium and tritium labeling of diverse complex pharmaceuticals.     

Unraveling the Nature of Sites Active toward Hydrogen Peroxide Reduction in Fe‐N‐C Catalysts

Fe‐N‐C catalysts with high O₂ reduction performance are crucial for displacing Pt in low‐temperature fuel cells. However, insufficient understanding of which reaction steps are catalyzed by what sites limits their progress. The nature of sites were investigated that are active toward H₂O₂ reduction, a key intermediate during indirect O₂ reduction and a source of deactivation in fuel cells. Catalysts comprising different relative contents of FeN_x C_y moieties and Fe particles encapsulated in N‐doped carbon layers (0–100 %) show that both types of sites are active, although moderately, toward H₂O₂ reduction. In contrast, N‐doped carbons free of Fe and Fe particles exposed to the electrolyte are inactive. When catalyzing the ORR, FeN_x C_y moieties are more selective than Fe particles encapsulated in N‐doped carbon. These novel insights offer rational approaches for more selective and therefore more durable Fe‐N‐C catalysts.     

Pentacoordinated Al3+‐Stabilized Active Pd Structures on Al2O3‐Coated Palladium Catalysts for Methane Combustion

Supported Pd catalysts are active in catalyzing the highly exothermic methane combustion reaction but tend to be deactivated owing to local hyperthermal environments. Herein we report an effective approach to stabilize Pd/SiO₂ catalysts with porous Al₂O₃ overlayers coated by atomic layer deposition (ALD). ²⁷Al magic angle spinning NMR analysis showed that Al₂O₃ overlayers on Pd particles coated by the ALD method are rich in pentacoordinated Al³⁺ sites capable of strongly interacting with adjacent surface PdO_x phases on supported Pd particles. Consequently, Al₂O₃‐decorated Pd/SiO₂ catalysts exhibit active and stable PdO_x and Pd–PdO_x structures to efficiently catalyze methane combustion between 200 and 850 °C. These results reveal the unique structural characteristics of Al₂O₃ overlayers on metal surfaces coated by the ALD method and provide a practical strategy to explore stable and efficient supported Pd catalysts for methane combustion.