The dynamic interactions between noble metal particles and reducible metal-oxide supports can depend on redox reactions with ambient gases. Transmission electron microscopy revealed that the strong metal-support interaction (SMSI)–induced encapsulation of platinum particles on titania observed under reducing conditions is lost once the system is exposed to a redox-reactive environment containing oxygen and hydrogen at a total pressure of ~1 bar. Destabilization of the metal–oxide interface and redox-mediated reconstructions of titania lead to particle dynamics and directed particle migration that depend on nanoparticle orientation. A static encapsulated SMSI state was reestablished when switching back to purely oxidizing conditions. This work highlights the difference between reactive and nonreactive states and demonstrates that manifestations of the metal-support interaction strongly depend on the chemical environment.
The typical industrial catalyst used for methanol synthesis is a multi‐component catalyst based on Cu/ZnO/Al2O3. The synergies between various phases of this catalyst play a vital role in defining the overall catalytic function and performance. To gain insights into the role and interaction between the relevant components and phases, ex situ and in situ transmission electron microscopy (TEM) was deployed to investigate the structures and phases of an industrial Cu/ZnO/Al2O3 in its precursor, activated and reaction states. High structural inhomogeneity in this material is revealed, i. e. the presence of various phases with different morphologies and compositions. It is shown how structural and compositional changes occur during hydrogen treatment and how compositional inhomogeneity in the starting material translates into differences in the local composition of the activated and working catalyst. The formation of defective metallic copper particles (stacking faults and twins) that are in an intimate contact with zinc oxide (poorly crystalline, partially reduced ZnOx and crystalline ZnO), alumina, Zn−Al oxide and carbon‐zinc‐oxygen containing phases (such as zinc formate) is observed. It is also uncovered that alumina plays a potentially important role in stabilizing cationic zinc species. This work provides atomic‐level insight into the relevant state of an industrial methanol synthesis catalyst and the associated synergistic interplay between the involved phases in reactive atmosphere.
Dependent on the application or characterization method catalysts are exposed to different gas pressures, which results in different structures. The quantitative determination of the structure and composition of a catalyst as a function of its gas environment allows the establishment of structure−performance relationships. Herein, we determine the structure of a platinum− titania catalyst under hydrogen during temperature-programmed reduction over 3 orders of magnitude in pressure, from 1 to 950 mbar. The pressure significantly influences the hydrogen uptake kinetics and the consecutive structural transformations of the platinum−titania catalyst. The reduction of the platinum precursor becomes pressure-independent above 30 mbar. Yet, the related spillover and stability of adsorbed hydrogen on the titania are a function of pressure. Higher pressures promote higher hydrogen uptake and prevent desorption of hydrogen from the catalyst. The hydrogen uptake triggers a phase transformation of anatase to rutile which is, as a result, pressure dependent. The presented systematic approach establishes a pressure−structure relation which can be applied for the catalyst treatment and to frame existing results on the catalytic system. Treating the same material at two different pressures will lead to different structures.
Platinum nanoparticles (NPs) supported by titania exhibit a strong metal‐support interaction (SMSI)[1] that can induce overlayer formation and encapsulation of the NP's with a thin layer of support material. This encapsulation modifies the catalyst's properties, such as increasing its chemoselectivity[2] and stabilizing it against sintering.[3] Encapsulation is typically induced during high‐temperature reductive activation and can be reversed through oxidative treatments.[1] However, recent findings indicate that the overlayer can be stable in oxygen.[4, 5] Using in situ transmission electron microscopy, we investigated how the overlayer changes with varying conditions. We found that exposure to oxygen below 400 °C caused disorder and removal of the overlayer upon subsequent hydrogen treatment. In contrast, elevating the temperature to 900 °C while maintaining the oxygen atmosphere preserved the overlayer, preventing platinum evaporation when exposed to oxygen. Our findings demonstrate how different treatments can influence the stability of nanoparticles with or without titania overlayers. expanding the concept of SMSI and enabling noble metal catalysts to operate in harsh environments without evaporation associated losses during burn‐off cycling.
Platinum nanoparticles (NPs) supported by titania exhibit a strong metal‐support interaction (SMSI)[1] that can induce overlayer formation and encapsulation of the NP's with a thin layer of support material. This encapsulation modifies the catalyst's properties, such as increasing its chemoselectivity[2] and stabilizing it against sintering.[3] Encapsulation is typically induced during high‐temperature reductive activation and can be reversed through oxidative treatments.[1] However, recent findings indicate that the overlayer can be stable in oxygen.[4, 5] Using in situ transmission electron microscopy, we investigated how the overlayer changes with varying conditions. We found that exposure to oxygen below 400 °C caused disorder and removal of the overlayer upon subsequent hydrogen treatment. In contrast, elevating the temperature to 900 °C while maintaining the oxygen atmosphere preserved the overlayer, preventing platinum evaporation when exposed to oxygen. Our findings demonstrate how different treatments can influence the stability of nanoparticles with or without titania overlayers. expanding the concept of SMSI and enabling noble metal catalysts to operate in harsh environments without evaporation associated losses during burn‐off cycling.
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