Interlayers reduction

A candidate interlayer consisting of dual coatings of Cu and Nb has been identified successfully for the SiC-Ti3Al-I-Nb composite system. The predicted residual thermal stresses resulting from a stress free temperature to room temperature (with AT = —774°C) for the composites with and without the interlayers are illustrated in Fig. 7.23. The thermo-mechanical properties of the composite constituents used for the calculation are given in Table 7.5. A number of observations can be made about the benefits gained due to the presence of the interlayer. Reductions in both the radial, and circumferential, o-p, stress components within the fiber and matrix are significant, whereas a moderate increase in the axial stress component, chemical compatibility of Cu with the fiber and matrix materials has been closely examined by Misra (1991). 

In the pyroaurite structure the brucite layers are cationic. However, on oxidation the resultant brucite layers in y - NiOOH are anionic. To preserve electroneutrality, cations and anions are exchanged in the intercalated layer during the oxidation-reduction process. This is illustrated in Fig. 4. In the case of Mn-substituted materials, some Mn can be reduced to Mn(II). This neutralizes the charge in the brucite layer this part of the structure reverts to the P - Ni(OH)2 structure and the intercalated water and anions are expelled from the lattice. With this there is a concomitant irreversible contraction of the interlayer spacing from 7.80 to 4.65A [72]. 

The intercalated catalysts can often be regarded as biomimetic oxidation catalysts. The intercalation of cationic metal complexes in the interlamellar space of clays often leads to increased catalytic activity and selectivity, due to the limited orientations by which the molecules are forced to accommodate themselves between sheets. The clays have electrostatic fields in their interlayer therefore, the intercalated metal complexes are more positively charged. Such complexes may show different behavior. For example, cationic Rh complexes catalyze the regioselective hydrogenation of carbonyl groups, whereas neutral complexes are not active.149 Cis-Alkenes are hydrogenated preferentially on bipyridyl-Pd(II) acetate intercalated in montmorillonite.150 The same catalyst was also used for the reduction of nitrobenzene.151... 

Figure 7. Schematic model based on the TEM image analysis and on in situ 7Li-NMR during galvanostatic reduction/oxidation of the carbon composite. During insertion, ionic lithium penetrates at first in the smallest interlayer spacings, then it diffuses in the slit-shaped pores where quasi-metallic clusters are formed.

The practical applications of NaBH4 reductions on mineral surfaces for in situ generated SchifFs bases have been successfully demonstrated. The solid-state reductive amination of carbonyl compounds on various inorganic solid supports such as alumina, clay, silica etc. and especially on K 10 clay surface rapidly afford secondary and tertiary amines [126]. Clay behaves as a Lewis acid and also provides water from its interlayers thus enhancing the reducing ability of NaBH4 [22],... 

Research on cathode materials focuses on reduction of the high chemical activity of the lower WF metals (e.g., Ca/Al), the increase of the chemical stability, and improvement of the sticking coefficient of the interlayer materials (e.g., LiF/Al). 

The enhancement in luminous efficiency achieved by inserting an ultrathin interlayer between the ITO and NPB is mainly due to the reduction of hole injection from ITO to NPB in OLEDs. For a simple approximation, luminous efficiency (rj) can be related directly to a ratio of the recombination current (/r) to the total current density of OLEDs (/tot). If one denotes the current contributions from holes and electrons in OLEDs as. /h and /e, respectively, then the sum of hole and electron currents, /tot. /h + /e, and tj can be expressed as... 

The reaction of benzene with Cu(II) and Fe(III)-exchanged hectorites at elevated temperatures produced a variety of organic radical products, depending on the concentration of water in the reaction medium and the reaction time (90). The formation of free radicals was accompanied by a reduction in oxidation state of the metals, a process that had a zero-order dependence on the metal ion concentration. Under anhydrous conditions the free radicals appeared to populate sites in the interlayer region, the activation energies under these conditions being lower than in the hydrated samples. 

Yang HB, Guo CX, Guai GH, Song QL, Jiang SP, Li CM. Reduction of charge recombination by an amorphous titanium oxide interlayer in layered graphene/quantum dots photochemical cells, ACSAppl. Mater. Interfaces 2011, 3,1940-1945. 

Only one naturally relevant abiotic Se(VI) reduction process has been documented to date. Se(Vl) can be reduced to Se(TV) and ultimately to Se(0) by green rust , an Fe(II)- and Fe(lll)-bearing phase with sulfate occupying interlayer spaces (Myneni et al. 1997). Johnson and Bullen (2003) obtained an ese(vi)-se(iv) value of 7.4%o ( 0.2) for the Se(VI) reduction reaction. The result was not sensitive to changes in pH or solution composition within the ranges over which green rust is stable. 

Because this reaction must involve two steps, diffusion of selenate into the interlayer spaces of the green rust followed by electron transfer from Fe(ll) green rust, Johnson and Bullen (2003) interpreted this result using a two-step model similar to that discussed above. The diffusion step presumably has very little isotopic fractionation associated with it. Step 2 might be expected to involve a kinetic isotope effect similar to that observed in the HCl reduction experiments. As is discussed above, if the diffusion step is partially rate-limiting, the isotopic fractionation for the overall process should be less than the kinetic isotope effect occurring at the reduction step. This appears to be the case, as the ese(vi)-se(iv) value of 7.4%o is somewhat smaller than that observed for reduction by strong HCl (12%o). 

Initially, the starting material, which exhibits a strong Bragg reflection at 8.7 A, is observed. As addition of the guest solution continues, a peak at 14.8 A evolves. This is the first stage intercalate of 1,2-BDA, with all interlayer spaces occupied by the dicarboxylate. No second stage intermediates are observed. Continued addition of 1,2-BDA causes a reduction in the intensity of the 14.8 A reflection, and a reflection with a d-spacing of at 11.2 A to evolve. 

Eor the purpose of modeling, consider a planar SOEC divided into anode gas channel, anode gas diffusion electrode, anode interlayer (active electrode), electrolyte, cathode interlayer (active electrode), cathode gas diffusion electrode, and cathode gas channel. The electrochemical reactions occur in the active regions of the porous electrodes (i.e., interlayers). In an SOFC, oxidant reduction occurs in the active cathode. The oxygen ions are then transported through the electrolyte, after which oxidation of the fuel occurs in the active anode by the following reactions. 

Based on these characterizations, a model structure of 0.1 wt% Ni-loaded K4Nb60i7 was proposed as shown in Fig. 16.5. During the loading of the catalyst with nickel, most of the nickel enters the interlayer region I as Ni2+ by replacing K+ ions, leaving a very small fraction on the external surface. During reduction at 700°C, the Ni2+ cations are reduced to metallic nickel in the form of ultrafine particles of about 0.5 nm size. 

---