Doping reducible metal oxides

Catalysts considered in the present discussion cover a wide spectrum of solids reducible multivalent metal oxides as well as non reducible basic compounds Reducible metal oxides possess some inherent problems whereas these problems are less for the alkali ions promoted alkaline earth oxides. Alkaline earth oxides seem to be more suitable for working at low partial pressure of oxygen. By doping alkaline earth oxides with alkali metal compounds it is conceivable that O species can be stabilized for dissociative absorption of methane. Reducible metal oxides will tend to transform into lower valent oxides or even upto metallic state partly under applied reaction conditions specially at low partial pressure of O2. Both activity and selectivity will be deteriorated. But for the non reducible basic oxides structural changes will be quite different. They will tend to reach an equilibrium state in the surface level amongst the oxide, hydroxide and carbonate phases on reacting with evolved H2O and CO. Both the lattice distortion and the formation of O species can occur in the alkali earth oxides in doping with alkali ions as they can not build a mixed oxide lattice. 

Reducible metal oxides, which are able to provide their lattice oxygen for methane activation, are potential catalytic materials for alternating feeding of CH4 and O2. Mn- and Co-based perovskites were identified as effective catalysts for such OCM operation [24]. At best, the yield of C2 hydrocarbons of 20% with the corresponding selectivity of 73% was obtained at 1073 K over S1C0O3 doped with the oxides or hydroxides of K and Na applying a 1.5-min cycle of methane. However, the catalyst productivity remained still low. 

Some insulating oxides become semiconducting by doping. This can be achieved either by inserting certain heteroatoms into the crystal lattice of the oxide, or more simply by its partial sub-stoichiometric reduction or oxidation, accompanied with a corresponding removal or addition of some oxygen anions from/into the crystal lattice. (Many metal oxides are, naturally, produced in these mixed-valence forms by common preparative techniques.) For instance, an oxide with partly reduced metal cations behaves as a n-doped semiconductor a typical example is Ti02. 

Semiconductor electrodes seem to be attractive and promising materials for carbon dioxide reduction to highly reduced products such as methanol and methane, in contrast to many metal electrodes at which formic acid or CO is the major reduction product. This potential utility of semiconductor materials is due to their band structure (especially the conduction band level, where multielectron transfer may be achieved)76 and chemical properties (e.g., C02 is well known to adsorb onto metal oxides and/ or noble metal-doped metal oxides to become more active states77-81). Recently, several reports dealing with C02 reduction at n-type semiconductors in the dark have appeared, as described below. 

The analysis of tetramethylammonium hydroxide (TMAH) solutions manufactured by SACHEM Inc. of Cleburne, Texas, includes the determination of trace elements. These elements cause less-than-optimum performance of integrated circuit boards manufactured by SACHEM s customers that use these solutions in their processes. Alkali and alkaline earth metals (e.g., Li, Na, K, Mg, Ca, and Ba) can reduce the oxide breakdown voltage of the devices. In addition, transition and heavy metal elements (e.g., Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Au, and Pb) can produce higher dark current. Doping elements (e.g., B, Al, Si, P, As, and Sn) can alter the operating characteristics of the devices. In SACHEM s quality control laboratory, ICP coupled to mass spectrometry is used to simultaneously analyze multiple trace elements in one sample in just 1 to 4 min. This ICP-MS instrument is a state-of-the-art instrument that can provide high throughput and low detection Emits at the parts per thousand level. Trace elemental determination at the parts per thousand level must be performed in a clean room so that trace elemental contamination from airborne particles can be minimized. 

Chemoselective reduction of conjugated enones to allylic alcohols via hydrogen transfer from propan-2-ol over metal oxides is investigated in vapour phase conditions. The unique ability of Mgo to reduce exclusively carbonyl group is observed. However, because of the high basicity of MgO side reactions are present. It is shown that by doping the Mgo catalyst with HC1 a significant decrease of its basicity occurs and consequently side reactions are minimized. 

Fullerenes show quite different electronic properties to other carbon al-lotropes. The carbon in diamond has a nonconductive sp hybrid orbital, while that in graphite is conductive since it has an sp hybrid orbital. Fullerene carbons have orbitals that are intermediate between sp and sp, and so the fullerenes behave hke semiconductors. Graphite can be oxidized and reduced. In contrast, fullerenes are easily reduced but difficult to oxidize. Fullerenes can also be doped with metal ions (Fig. 3.2). In doped fullerenes, the metal ion is... 

Unlike polyacetylene, polydiacetylenes cannot be doped , i.e. oxidized or reduced to give a polymeric salt of metal-like conductivity. Nevertheless, polydiacetylenes are interesting materials for possible applications in electronic devices. 

In heterogeneously catalyzed gas-phase reactions, one of the problems encountered in the first publication was the fact that only relatively large thermal signals could be detected. This problem was solved by the work of Holzwarth et al. [18], who used a background subtraction technique to reduce the detection limit to differences of about 0.1 K. With this set-up it was possible to analyze the activity of several metal-doped, amorphous, mixed metal oxides in total oxidation reactions of hydrocarbons. 

A somewhat similar theory10 postulates the formation of colloidal lead by the decomposition of lead tetraethyl, which deposits on sharp points, edges, and projections in the cylinder which would otherwise aid reaction to an extent that a detonation wave would result. The theory fails to explain the action of organic amines, of di- and tetravalent. selenium, of the colloidal metal sols, and fails to account for the immediate recurrence of knocking when the antiknock dope is discontinued in the gasoline feed. However, tubes coated with lead oxide have been found to reduce the oxidation of hexane more than lead tetraethyl vapors.1158 On the basis of this finding the hypothesis was advanced that oxidation occurs to some extent prior to compression and at the first contact of the gaseous mixture with the hot walls, aud that in the presence of the lead... 

---