Spectroscopic Studies of Nickel(II) and Nickel(III) Species Generated upon Thermal Treatments of Nickel/Ceria-Supported Materials

Abstract

On the basis of DRS, ESR, and XPS studies, the nature and the dispersion of nickel species deposited on ceria (by hydrolysis of an aqueous solution of nickel nitrate) have been investigated upon thermal activations in air. Before thermal activation, mainly octahedral Ni II species belonging to a Ni(OH) 2 deposit are observed by DRS (λ 1 ) 1230 nm). The concomitant presence of some Ni II ions grafted on ceria (via Ni II -O-Ce bridges) is suggested (i) in DRS, by a bathochromic shift leading to a λ 1 peak at 1400 nm, indicating the presence of some Ni II ions submitted to a weaker crystal field than in unsupported Ni(OH) 2 and (ii) in XPS, by a Ni II 2p 3/2 peak at 857.4 eV, 0.5 eV higher than the Ni II 2p 3/2 peak observed for unsupported Ni(OH) 2 according to a noticeable lowering of the Ni-O bond covalence. Some bulk NiO particles are also formed during the sample drying step as revealed by an XPS peak at 854 eV. These NiO particles are ESR silent at room temperature and at -196°C since NiO is an antiferromagnetic oxide with a Néel temperature of 250°C. In agreement with a previous EXAFS study dealing with the Ni/TiO 2 system, the calcination in air at 400°C mainly generates small NiO patches dispersed on ceria and giving a XPS Ni 2p 3/2 peak at 855.5 eV. This binding energy is notably greater than that observed with bulk NiO (854 eV), and this shift is due to either a size effect or an electronic interaction with ceria. The Ni II ions of these small patches are ESR silent, indicating that they are submitted to distorted crystal fields (S ) 0). In parallel, the formation of Ni III defects upon calcination at 400°C is indicated by a base-line drift of reflectance spectra and a XPS peak located at 857.5 eV. The coexistence of NiO particles and of Ni III -O x n-(x and n ) 1, 2) complexes grafted on the ceria surface is suggested. A thermal activation in air at 900°C induces the sintering of NiO particles as revealed by a decrease of the Ni 2p 3/2 binding energy (855 eV) and of the normalized surface area ratio of the Ni 2p 3/2 and Ce 3d XPS contributions, which indicates that 60% of the nickel ions are no longer detected on the ceria surface after calcination at 900°C. The agglomeration of adjacent small NiO domains giving a "mosaic-like" NiO material, characterized by an isotropic ESR signal whose position (signal A:g within the range 2.47-2.2) and line width (∆H pp ) 1200-1750 G) vary as a function of measurement temperature (from room temperature to -196°C) is proposed. In parallel, a well-resolved ESR signal (signal B:g ⊥ ) 2.358 ( 0.002; g | ) 2.018 ( 0.002; ∆H pp ) 10-15 G) indicates the presence of bulk Ni III ions, magnetically diluted inside ceria. These bulk Ni III ions could be generated either during the sintering of adjacent ceria particles or via bulk diffusion mechanisms.

Surface properties of LiCoO2, LiNiO2 and LiNi1−xCoxO2

“…For these materials, the O 1s is comparable with that of NiO [62] and [63]. Ni 3+ has been reported as a "defect structure" in NiO and oxidized nickel metal substrates [64], [65], [66], [67] and [68]; however the O 1s binding energy associated with this species is generally reported at values well in excess of 530 eV. Indeed, there are very few transition metal oxides that have reported lattice oxygen O 1s binding energies at such low binding energy values [52] and the lattice oxygen in the lithium metal oxides is a very electron-rich species.…”

Deposition and characterization of NiOx coatings by magnetron sputtering for application in dye-sensitized solar cells

“…5b indicates two peaks at 529.4 eV and 531.4 eV, these are assigned to the oxides of NiO and Ni 2 O 3 respectively [34,35]. The similarities between the XPS spectra confirm that the increase in the deposition pressure does not affect the chemical composition of the NiO x coatings.…”

“…5a. They are composed of two peaks at 853.9 eV and 855.5 eV which have been assigned to Ni +2 (NiO) and Ni +3 (Ni 2 O 3 ) respectively [34,35]. This is in addition to the very broad peak at ~861 eV, which is the shake up satellite peak of Ni +2 and Ni +3 .…”

Influence of Growth Temperature on the Properties of DC Reactive Magnetron Sputtered NiO Thin Films

“…Fig. 3 (b) and (c) shows the narrow scan XPS spectra of core-level binding energy of O 1s and C 1s in the binding energies at 530.4 and 284.5 eV respectively (Davidson, et al, 1996), (Hager, et al, 2009) (Fig. 4).…”