Nickel oxide electronic properties

Within the periodic Hartree-Fock approach it is possible to incorporate many of the variants that we have discussed, such as LFHF or RHF. Density functional theory can also be used. I his makes it possible to compare the results obtained from these variants. Whilst density functional theory is more widely used for solid-state applications, there are certain types of problem that are currently more amenable to the Hartree-Fock method. Of particular ii. Icvance here are systems containing unpaired electrons, two recent examples being the clci tronic and magnetic properties of nickel oxide and alkaline earth oxides doped with alkali metal ions (Li in CaO) [Dovesi et al. 2000]. 

The oxidation of carbon monoxide on nickel oxide has often been investigated (4, 6, 8, 9, II, 16, 17, 21, 22, 26, 27, 29, 32, 33, 36) with attempts to correlate the changes in the apparent activation energy with the modification of the electronic structure of the catalyst. Published results are not in agreement (6,11,21,22,26,27,32,33). Some discrepancies would be caused by the different temperature ranges used (27). However, the preparation and the pretreatments of nickel oxide were, in many cases, different, and consequently the surface structure of the catalysts—i.e., their composition and the nature and concentration of surface defects— were probably different. Therefore, an explanation of the disagreement may be that the surface structure of the semiconducting catalyst (and not only its surface or bulk electronic properties) influences its activity. 

Nature of Active Sites. There is no apparent correlation between the increase of catalytic activity and a modification of the electronic structure of nickel oxide, since the electrical properties of both catalysts are identical. It is probable that local modifications of the nickel oxide surface are responsible for the change of its activity and of the reaction mechanism. It should be possible to associate these structural modification with local modifications of the height of the Fermi level, but it would be difficult to explain the results by the electronic theory of catalysis which considers only collective electrons or holes. A discussion based only on the influence of surface defects seems, therefore, to be more straightforward. 

K. HAUFFE From our knowledge of the semiconducting properties of NiO, in particular the very low mobility of the holes, which is not understandable because of the unoccupied 3d level of the Ni ions, we believe that nickel oxide in contrast to other oxides has not a covalent but an overwhelmingly ionic structure. Nevertheless, under general conditions the charge carriers are the holes and not the nickel ions. Only under strong electric fields, at the very beginning of die oxide film formation at low temperatures, the electron transport via holes can become slower than the nickel ions. 

Figure 32 Schematic electron density-of-states diagrams for electrochromic, EC, multilayer design. The materials include ln203 Sn (ITO), nickel oxide (presiunably hydrous), tungsten oxide (also presumably hydrous) prepared so that the EC and chemically protective (PR) properties are emphasized, and an electrol)de. The Fermi energy is denoted Ep, with Epi and Ep2 pertaining to the case of an applied potential, Ucoi fiUed states are denoted by shadings. (Ref 235. Reproduced by permission of Springer Verlag)...

In order to confirm the nickel oxidation state in the active entity and to study the influence of the composition of its coordination sphere [coordination number, nature of the trialkylphosphine (TAP) ligands] on the catalytic performances, we have used a set of silica-supported unsaturated Ni complexes [58] with a given number of TAP ligands of different electronic and steric properties [59,60],... 

Certain reaction conditions and properties of the nickel complexes promote hydrocyanation. The oxidative addition of HCN requires an open coordination site. Catalysts containing P(0-o-Tol)3 as ligand are particularly reactive because the imsatu-rated L Ni complex is the most stable form of the Ni(0) complex, whereas the saturated 18-electron L Ni complex is the most stable form of the catalysts containing smaller phosphite ligands. The need to imderstand the steric and electronic properties of the ligand on the dissociation of phosphine led to the classic work of Tolman on cone angles and electronic parameters. ... 

Anodic Electrochromic Materials. The most commonly used anodic electrochromic materials are nickel oxide (Svensson and Granqvist [1986]) and iridium oxide (Gottesfeld et al. [1978]). They switch from a transparent state to a colored one upon extraction of protons. Charge-balancing electrons are simultaneously extracted from the valence band. The films are probably a mixture of oxide and hydroxide components in the bleached state, since there needs to exist a reservoir of protons in the films. Due to the high cost of iridium, the use of nickel oxide is favored for large scale appfications. Recently, a class of mixed nickel oxides with enhanced modulation between the transparent and the colored state have been discovered (Avendano et al. [2003]). Intercalation of Li into ifickel oxide films has been attempted, but the optical properties are not modulated very much (Decker et al. [1992]). The mechanism of optical absorption is not known in detail. However, in... 

---