Use this URL to cite or link to this record in EThOS:
Title: 17O solid state NMR study of ceria systems
Author: Vlachou, Maria C.
ISNI:       0000 0004 7425 621X
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2017
Availability of Full Text:
Access from EThOS:
Access from Institution:
Ceria is a highly commercial, valuable material. Its diverse set of real-world applications demonstrates its far-reaching influence on modern society. Indeed, one only has to consider its extensive employment as an essential component of automotive, three-way catalysis (TWC) for reducing pollutants in vehicular exhaust gases; a technology that is used on a daily basis by millions of people, to appreciate its importance. Its popularity is partially due to its extraordinary oxygen storage capacity, i.e. its ability to release and store oxygen through redox reactions mediated by the two oxidation states of cerium (Ce3+/Ce4+). This unique ability can be heavily influenced by ceria’s particle size and shape, dopant concentration and surface chemistry, and is still a very active area of research today. Whilst there have been over 26,000 scientific publications on ceria since the 1950s, and although the bulk-ceria oxygen chemical shift (877 ppm) was first observed with 17O solid-state NMR in 1989, it is only within the past decade that solid-state NMR has been employed as a probe for ceria’s structure-function relationships. This study presents an extensive 17O solid-state NMR investigation into various ceria systems, in conjunction with complementary Raman spectroscopy (for which the literature is abundant). An alternative spectral assignment for the 17O NMR spectrum of nanoceria based on experimental deductions and DFT quantum mechanical calculations is proposed. The current working assignment for nanoceria is based on the work of Wang et al., where DFT calculations of a core-shell model are used to deconvolute the NMR data. In contrast to this model, it is suggested that the most upfield peak at δCG = 822 ppm (that is actually part of a multicomponent region centred at ~830 ppm), corresponds to oxygen species displaced from their standard sublattice positions, to occupy a Frenkel type defect site. The resonance regions observed at ~830 and 920 ppm are proposed to be bulk oxygen environments feeling the effects of the Frenkel defect and concomitant oxygen vacancy. For reduced ceria systems, a broad component is detected that spans > 1000 ppm, and is assigned to oxygen directly bonded to Ce3+, in agreement with the current working model. Finally, it is observed that the most deshielded peak at ~1030 ppm is multi-component and (one of these components) possesses an extensive spinning sideband manifold in comparison to the other 17O resonances. Variable temperature investigations show a small inverse temperature dependence of the peak positions, suggesting weak pseudocontact paramagnetic shifts are influencing the spectrum. In light of this, the peak at ~1030 ppm is assigned to oxygen in closer proximity to (but not directly bonded) to Ce3+, as is reported by current 27Al solid-state NMR studies of Ce3+ doped systems and as is reflected by the extensive sideband manifold. The novel 17O preparation treatments implemented in this work were engineered to probe oxygen environments near defects. Ceria’s defects are manipulated by exposure to certain temperature/atmospheric conditions, and when these replicate those of possible catalyst operating temperatures with 17O enriched gas, 17O is able to probe the distribution of oxygen in distinct sites that are important to the OSC process. A prereduction of ceria was therefore implemented, following 17O2 reoxidation to target these sites. This process was also able to identify a surface reorganization mechanism in which a low reoxidation temperature/ pressure of 17O2 is insufficient to reverse the onset of bulk oxygen diffusion induced by the reduction, an effect which is seen to be enhanced with the loading of Pd. Furthermore, the storage of these treated systems dictates the evolution of the 17O species, with an almost closed-system (to air) detecting the pathway of reoxidised oxygen species to more stable sites over time. Ceria zirconia systems are also investigated in this work. The 17O solid-state NMR spectra show an even greater sensitivity to the 17O2 enrichment conditions. The pre-reduction of the systems induces a greater oxygen removal compared to pure ceria, and thus an increase in Ce3+ paramagnetic centres, i.e. the broad component (> 1000 ppm) characterising the oxygen-Ce3+ bond reveals a greater relative intensity. The complication of increasing Ce3+ paramagnetic centres near the 17O adsorption sites is evidenced by the significant loss in 17O spectral resolution. These effects are exacerbated when ceria zirconia is supported with Pd, known to (stably) reduce the state of the system even further. A straight exchange of the 17O isotope in ceria zirconia helps to inhibit these effects, allowing observation of (1) the chemical shift of the bulk-ceria oxygen move to a more shielded position compared to the pure ceria material at 877 ppm (caused by the inherent contraction of the ceria zirconia lattice), and (2) a broad resonance at ~730 ppm, attributed to oxygen species bridging cerium and zirconium.
Supervisor: Not available Sponsor: Johnson Matthey plc ; Integrated Magnetic Resonance Centre for Doctoral Training
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QC Physics