Design of Single-Atom Catalysts and Tracking Their Fate Using Operando and Advanced X-ray Spectroscopic Tools

The potential of operando X-ray techniques for following the structure, fate, and active site of single-atom catalysts (SACs) is highlighted with emphasis on a synergetic approach of both topics. X-ray absorption spectroscopy (XAS) and related X-ray techniques have become fascinating tools to characterize solids and they can be applied to almost all the transition metals deriving information about the symmetry, oxidation state, local coordination, and many more structural and electronic properties. SACs, a newly coined concept, recently gained much attention in the field of heterogeneous catalysis. In this way, one can achieve a minimum use of the metal, theoretically highest efficiency, and the design of only one active site-so-called single site catalysts. While single sites are not easy to characterize especially under operating conditions, XAS as local probe together with complementary methods (infrared spectroscopy, electron microscopy) is ideal in this research area to prove the structure of these sites and the dynamic changes during reaction. In this review, starting from their fundamentals, various techniques related to conventional XAS and X-ray photon in/out techniques applied to single sites are discussed with detailed mechanistic and in situ/operando studies. We systematically summarize the design strategies of SACs and outline their exploration with XAS supported by density functional theory (DFT) calculations and recent machine learning tools

Operando QEXAFS Study of Pt–Fe Ammonia Slip Catalysts During Realistic Driving Cycles

Bifunctional Fe–Pt ammonia slip catalysts were studied by operando quick-scanning extended X-ray absorption fine structure spectroscopy (QEXAFS) under conditions mimicking rapid temperature variations that occur in an automotive exhaust gas aftertreatment system during real driving. Two catalysts, Pt/Al2O3 and Fe-ZSM-5, were tested individually, as mixtures and in dual bed arrangements. Applying QEXAFS allowed to track changes of active metal state with high time resolution. It uncovered a strong dependence of the active metal state on reaction conditions and catalyst bed layout. For example, proximity to platinum stabilized iron species in their more active oxidized state and led to higher Fe-ZSM-5 activity. On the contrary, isolated iron species were more susceptible to overreduction by ammonia which led to deactivation and low selectivity. The use of transient conditions uncovered the influence of non-equilibrium phenomena on catalytic performance under industrially relevant conditions. Specifically, the effect of ammonia storage on the increase of activity was shown. This was also accompanied by elevated N2O production not observed during tests with gradual heating. Additionally, unusually high NOx selectivity was detected for Fe-ZSM-5 under these conditions. Lastly, tracking catalyst state under dynamic reaction conditions disclosed that Fe-ZSM-5 activity did not grow directly with temperature increase but rather depended on the oxidation state of Fe and surface concentration of ammonia

Palladium-Based Bimetallic Nanocrystal Catalysts for the Direct Synthesis of Hydrogen Peroxide

The direct synthesis of H$_{2}$O$_{2}$ from H$_{2}$ and O$_{2}$ is a strongly desired reaction for green processes and a promising alternative to the commercialized anthraquinone process. The design of efficient catalysts with high activity and H$_{2}$O$_{2}$ selectivity is highly desirable and yet challenging. Metal dopants enhance the performance of the active phase by increasing reaction rates, stability, and/or selectivity. The identification of efficient dopants relies mostly on catalysts prepared with a random and non‐uniform deposition of active and promoter phases. To study the promotional effects of metal doping on Pd catalysts, we employ colloidal, bimetallic nanocrystals (NCs) to produce catalysts in which the active and doping metals are colocalized to a fine extent. In the absence of any acid and halide promotors, PdSn and PdGa NCs supported on acid‐pretreated TiO$_{2}$ (PdSn/s‐TiO$_{2}$, PdGa/s‐TiO$_{2}$) were highly efficient and outperformed the monometallic Pd catalyst (Pd/s‐TiO$_{2}$), whereas in the presence of an acid promotor, the overall H$_{2}$O$_{2}$ productivity was also further enhanced for the Ni‐, Ga‐, In‐, and Sn‐doped catalysts with respect to Pd/s‐TiO$_{2}$