In this study, we present an investigation aimed at characterizing and understanding the synergistic interactions in encapsulated catalytic structures between the metal core (i.e., Pd) and oxide shell (i.e., TiO2, ZrO2, and CeO2). Encapsulated catalysts were synthesized using a two-step procedure involving the initial colloidal synthesis of Pd nanoparticles (NPs) capped by various ligands and subsequent sol–gel encapsulation of the NPs with porous MO2 (M = Ti, Zr, Ce) shells. The encapsulated catalytic systems displayed higher activity than the Pd/MO2 supported structures due to unique physicochemical properties at the Pd–MO2 interface. Pd@ZrO2 exhibited the highest catalytic activity for CO oxidation. Results also suggested that the active sites in Pd encapsulated by an amorphous ZrO2 shell structure were significantly more active than the crystalline oxide encapsulated structures at low temperatures. Furthermore, CO DRIFTS studies showed that Pd redispersion occurred under CO oxidation reaction conditions and as a function of the oxide shell composition, being observed in Pd@TiO2 systems only, with potential formation of smaller NPs and oxide-supported Pd clusters after reaction. This investigation demonstrated that metal oxide composition and (in some cases) crystallinity play major roles in catalyst activity for encapsulated catalytic systems.
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Elucidation of Ce/Zr ratio effects on the physical properties and catalytic performance of CuOx/CeyZr1−yO2 catalysts
Although cerium oxide (CeO2) is widely used as a catalyst support, its limited defect sites and surface oxygen vacancy/mobility should be improved. The incorporation of zirconium (Zr) in the cerium (Ce) lattice is shown to increase the number of oxygen vacancies and improve catalytic activity. Using a fixed surface density (SD) of copper (∼2.3 Cu atoms per nm2) as a surface species, the role of the support (CeyZr1−yO2 (y = 1.0, 0.9, 0.6, 0.5, and 0.0)) and defect site effects in the CO oxidation reaction was investigated. Spectroscopic (e.g., Raman, XRD, XPS) and microscopic (e.g., SEM-EDX, HR-TEM) characterization techniques were applied to evaluate the defect sites, crystallite size, lattice parameters, chemical composition, oxidation states of elements and microstructure of the catalysts. The CO oxidation reaction with varied CO:O2 ratios (1 : 5, 1 : 1, and 1 :0.5 (stoichiometric)) was used as a model reaction to describe the relationship between the structure and the catalytic performance of each catalyst. Based on the characterization results of CeyZr1−yO2 materials, the addition of Zr causes physical and chemical changes to the overall material. The inclusion of Zr into the structure of CeO2 decreased the overall lattice parameter of the catalyst and increased the number of defect sites. The prepared catalysts were able to reach complete CO conversion (∼100%) at low temperature conditions (<200 °C), each showing varied reaction activity. The difference in CO oxidation activity was then analyzed and related to the structure, wherein Cu loading, surface oxygen vacancies, reduction–oxidation ability, CuOx–support interaction and oxygen mobility in the catalyst were the crucial descriptors.
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- Award ID(s):
- 2050824
- PAR ID:
- 10655967
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Catalysis Science & Technology
- Volume:
- 14
- Issue:
- 24
- ISSN:
- 2044-4753
- Page Range / eLocation ID:
- 7107-7123
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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