Reduction phase

Boron exists naturally as 19.78% lOB isotope and 80.22% IIB isotope. High-purity crystalline boron may be prepared by the vapor phase reduction of boron trichloride or tribromide with hydrogen on electrically heated filaments. The impure or amorphous, boron, a brownish-black powder, can be obtained by heating the trioxide with magnesium powder. 

Manufacture. Tetrahydrofurfuryl alcohol is produced commercially by the vapor-phase catalytic hydrogenation of furfuryl alcohol. Liquid phase reduction is also possible. 

The vapor-phase reduction of acrolein with isopropyl alcohol in the presence of a mixed metal oxide catalyst yields aHyl alcohol in a one-pass yield of 90.4%, with a selectivity (60) to the alcohol of 96.4%. Acrolein may also be selectively reduced to yield propionaldehyde by treatment with a variety of reducing reagents. 

Fig. 3. Continuous fluidized-bed vapor phase reduction of nitrobenzene.

The use of tetraoctylammonium salt as phase transfer reagent has been introduced by Brust [199] for the preparation of gold colloids in the size domain of 1-3 nm. This one-step method consists of a two-phase reduction coupled with ion extraction and self-assembly using mono-layers of alkane thiols. The two-phase redox reaction controls the growth of the metallic nuclei via the simultaneous attachment of self-assembled thiol monolayers on the growing clusters. The overall reaction is summarized in Equation (5). 

Liquid-Phase Reductive Deposition of Metal Nanoclusters Selective onto Oxide Surfaces... 

Among various methods to synthesize nanometer-sized particles [1-3], the liquid-phase reduction method as the novel synthesis method of metallic nanoparticles is one of the easiest procedures, since nanoparticles can be directly obtained from various precursor compounds soluble in a solvent [4], It has been reported that the synthesis of Ni nanoparticles with a diameter from 5 to lOnm and an amorphous-like structure by using this method and the promotion effect of Zn addition to Ni nanoparticles on the catalytic activity for 1-octene hydrogenation [4]. However, unsupported particles were found rather unstable because of its high surface activity to cause tremendous aggregation [5]. In order to solve this problem, their selective deposition onto support particles, such as metal oxides, has been investigated, and also their catalytic activities have been studied. 

The liquid-phase reduction method was applied to the preparation of the supported catalyst [27]. Virtually, Muramatsu et al. reported the controlled formation of ultrafine Ni particles on hematite particles with different shapes. The Ni particles were selectively deposited on these hematite particles by the liquid-phase reduction with NaBFl4. For the concrete manner, see the following process. Nickel acetylacetonate (Ni(AA)2) and zinc acetylacetonate (Zn(AA)2) were codissolved in 40 ml of 2-propanol with a Zn/Ni ratio of 0-1.0, where the concentration of Ni was 5.0 X lO mol/dm. 0.125 g of Ti02... 

Current trends in GC relate to miniaturisation, fast-GC, improved selectivity (mainly for short columns), stability of column stationary phases (reduction of bleeding) and increasing use of MS detection [117]. Finally, GC can be readily hyphenated with spectroscopic techniques without using involved interfaces and thus can easily provide unambiguous solute identification. 

They have been prepared with several anions,332-335 the tetrafluoroborate salt exhibits SA and Sc phases332,333 but the triflate shows a nematic phase 334 One of the problems in studying these complexes was the very high temperatures at which the phases existed and the fact that decomposition was often observed in the upper reaches of the SA phases. Reduction of these temperatures was achieved by changing the small anions for dodecyl sulfate that also make that more materials exhibit nematic SA and Sc phases, and another more viscous phase appeared, named cubic phase So- With the anion octyl sulfate336 the crystal structure of one of the complex with 4-metoxystilbazole could be achieved (20), with this anion the cubic phase was not present. 

Considerable progress has been made on C02 fixation in photochemical reduction. The use of Re complexes as photosensitizers gave the best results the reduction product was CO or HCOOH. The catalysts developed in this field are applicable to both the electrochemical and photoelectrochemical reduction of C02. Basic concepts developed in the gas phase reduction of C02 with H2 can also be used. Furthermore, electrochemical carboxyla-tion of organic molecules such as olefins, aromatic hydrocarbons, and alkyl halides in the presence of C02 is also an attractive research subject. Photoinduced and thermal insertion of C02 using organometallic complexes has also been extensively examined in recent years. 

Oxide compounds are widely used as cathodic materials in the power sources and electrochemical generators. Some literature data indicates that cathodic materials based on nonstoichiometric oxide compounds make it possible to increase the solid-phase reduction process. The kinetics of electrochemical reactions and consequently the current density are the higher, the greater the degree of deviation from stoichiometry, and the lager the number of the defects in the compounds structure [1,2]. 

Romenets, V. A., Process of Liquid Phase Reduction of Iron Development and Implementation, Steel in the USSR, 20 366 (1990)... 

While the first electrochemical reduction potential provides an estimate for Ac (assuming it is a reversible process), the second and higher reduction potentials do not provide the spectrum of single electron affinity levels. Rather, they provide information about two-electron, three-electron, and higher electron reduction processes, and, therefore, depend on electron pairing energy. Thus, the utility of solution-phase reduction potentials for estimating solid-state affinity levels is... 

Other counterions besides chloride, such as trifluoroacetate and tosylate, are also appropriate for these solid-phase reductive aminations. 

Two phase reduction (Brust synthesis) This method is usually employed to make organic soluble quantum clusters [8]. This method consists of two steps. The first is the transfer of AuCLi from aqueous to the organic layer by a phase transfer reagent such as tetraoctyl ammonium bromide (TOABr). The next step is the subsequent reduction of AuCU in the presence of suitably selected ligands such as thiols, phosphines, etc. 

Single phase reduction Here, Au3+ ions are reduced to Au(I) by the addition of thiols followed by the complete reduction to Au(0) by adding reducing agents such as sodium borohydride (NaBH4) [2].The reaction can be represented as,... 

The two-phase reduction of cyclohexanones by sodium dithionite in the presence of a stoichiometric amount of Adogen gave higher yields of the cyclohexanols than those obtained by the standard procedure using sodium dithionite in a water dioxane system (Table 11.9). A marked improvement in yield was also observed with the reduction of sterically hindered 2,6-dimethylcyclohexanone and there was a greater degree of stereoselectivity, which was comparable to that noted for the corresponding reduction with the borohydride ion [4]. 

Liquid-phase chemical reduction is suitable for the formation of metal and metal oxide NPs on nanocarbons. Careful consideration is required in designing the nanocarbon-precursor interaction and choosing the reduction/oxidation method. The synthetic process is often quite time consuming and a number of filtering/washing steps are often required. As discussed, the concurrent liquid phase reduction of GO and precursor is a simple, efficient way to produce a hybrid but the lack of control of GO reduction may affect further applications. 

As noted before, many conventional methods rely on hydrolysis/precipi-tation chemistry to deposit Pt and other metals onto carbon, followed by chemical or gas-phase reduction. One common method is the use of metal sulfito chemistry. This method involves the preparation of metal sulfito complexes (e.g., Na3[Pt(S03)2(0H)2]) in water, the addition of carbon, and precipitation of metal by oxidation to deposit metal oxide particles. The route has advantages in that alkali metals and halides are excluded from the preparation. The method has been extended to bimetallics such as PtRu. 

Whole cells of bakers yeast [BMIM][PF6]/buffer (two-phase) Reduction of ketones 32... 

---