| Autor: |
Deschner BJ; Institute for Micro Process Engineering, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany., Doronkin DE; Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany., Sheppard TL; Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany., Rabsch G; Institute for Micro Process Engineering, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany., Grunwaldt JD; Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany., Dittmeyer R; Institute for Micro Process Engineering, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, Germany. |
| Abstrakt: |
A continuous-flow reactor and a continuous-flow setup compatible with operando x-ray absorption spectroscopy (XAS) were designed for safely studying liquid-phase reactions on solid high atomic number transition metal catalysts (e.g., Au, Pd, and Pt) under pressures up to 100 bars with temperatures up to 100 °C. The reactor has a stainless-steel body, 2 mm thick polyether ether ketone (PEEK) x-ray windows, and a low internal volume of 0.31 ml. The rectangular chamber (6 × 5 × 1 mm 3 ) between the PEEK x-ray windows allows us to perform XAS studies of packed beds or monoliths in the transmission mode at any position in the cell over a length of 60 mm. A 146° wide-angle beam access also allows recording complementary x-ray fluorescence or x-ray diffraction signals. The setup was engineered to continuously feed a single-phase liquid flow saturated with one or more gaseous reactants to the liquid-solid XAS reactor containing no free gas phase for enhanced process safety and sample homogeneity. The proof of concept for the continuous-flow XAS cell and high-pressure setup was provided by operando XAS measurements during the direct synthesis of hydrogen peroxide at room temperature and 40 bars using a 35 ± 5 mg catalyst (1 wt. % Pd/TiO 2 ) and inline near-infrared spectroscopy. The experiments prove that the system is well suited to follow the reaction in the liquid phase while recording high-quality XAS data, paving the way for detailed studies on the catalyst structure and structure-activity relationships. |
