Microporous transition metal oxide materials

There are two examples of transition metal oxides forming ordered microporous materials (1) manganese oxide and (2) molybdenum vanadium mixed oxide, both of which contain MOg octahedra as the basic structural units to form one-dimensional channel pores. 

The first ordered microporous transition metal oxides were microporous manganese oxides, known as octahedral molecular sieves (OMS). The manganese oxide OMS are classified into three families the pyrolusite-ramsdellite family with a (1 x n) channel structure the hollandite-romanechite family with a (2 x n) channel structure  

Pore sizes estimated by the nitrogen and argon adsorption techniques were reasonable, because the size corresponds to the short width of the pore and the longest diagonal length of the pores. Furthermore, the molecular sieve property of todorokite, which adsorbed cyclohexane but not 1,3,5-triisopropylbenzene, has been reported.  

Because of the mixed-valent manganese framework, valences of manganese are (-1-2, - -3, and - -4) or (-1-3 and 3-4), a small number of guest cations usually being required for charge balance in the channel of the manganese oxide. These cations do not completely block the pores. 

Name Formula Channel structure Calc, pore Obs. pore sizes (nm) size (nm) Ref. 

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Both microporous manganese oxides " and the Mo-V were prepared by heating aqueous solutions of the metal precursors. In order to produce pure samples, conditions (pH, temperature, reaction time, and concentration of metal precursor) must be carefully controlled. Further investigation is needed to demonstrate the importance of these bifunctional (redox and microporosity) materials for understanding the formation mechanism of these microporous materials and for the development of a new strategy to form other microporous transition metal oxides. 

Both aluminum oxide and zirconium oxide are catalytically interesting materials. Pure zirconium oxide is a weak acid catalyst and to increase its acid strength and thermal stability it is usually modified with anions such as phosphates. In the context of mesoporous zirconia prepared from zirconium sulfate using the S+X I+ synthesis route it was found that by ion exchanging sulfate counter-anions in the product with phosphates, thermally stable microporous zirconium oxo-phosphates could be obtained [30-32]. Thermally stable mesoporous zirconium phosphate, zirconium oxo-phosphate and sulfate were synthesized in a similar way [33, 34], The often-encountered thermal instability of transition metal oxide mesoporous materials was circumvented in these studies by delayed crystallization caused by the presence of phosphate or sulfate anions. 

The history of mesoporous material synthesis is unintentionally or intentionally duplicating the development of zeolites and microporous molecular sieve. It starts from silicate and aluminosilicate, through heteroatom substitution, to other oxide compounds and sulfides. It is worth mentioning that many unavailable compositions for zeolite (e.g., certain transition metal oxides, even pure metals and carbon) can be made in mesoporous material form. 

Zeolite catalysts incorporated or encapsulated with transition metal cations such as Mo, or Ti into the frameworks or cavities of various microporous and mesoporous molecular sieves were synthesized by a hydrothermal synthesis method. A combination of various spectroscopic techniques and analyses of the photocatalytic reaction products has revealed that these transition metal cations constitute highly dispersed tetrahedrally coordinated oxide species which enable the zeolite catalysts to act as efficient and effective photocatalysts for the various reactions such as the decomposition of NO into N2 and O2 and the reduction of CO2 with H2O into CH3OH and CH4. Investigations on the photochemical reactivities of these oxide species with reactant molecules such as NOx, hydrocarbonds, CO2 and H2O showed that the charge transfer excited triplet state of the oxides, i.e., (Mo - O ), - O ), and (Ti - O ), plays a significant role in the photocatalytic reactions. Thus, the present results have clearly demonstrated the unique and high photocatalytic reactivities of various microporous and mesoporous zeolitic materials incorporated with Mo, V, or Ti oxide species as well as the close relationship between the local structures of these transition metal oxide species and their photocatalytic reactivities. 

Lithium batteries using solid cathodes typically use a thin lithium-metal foil or disk as the anode a transition metal oxide, metal sulfide, or a fluoride as the cathode and an organic electrolyte. The cathode material is either coated onto a foil substrate (often aluminum) or embedded into an expanded metal or perforated metal substrate. The anode and cathode are separated by a microporous plastic membrane separator, usually polyethylene and/or polypropylene. 

The oxide catalysts are microporous or mesoporous materials or materials containing both types of pores. In the latter case, the applicability is larger in terms of the molecular size of the reactants. Acid-base properties of these materials depend on the covalent/ionic character of the metal-oxygen bonds. These sites are involved in several steps of the catalytic oxidation reactions. The acid sites participate with the cation redox properties in determining the selective/unselective catalyst behavior [30,31]. Thus, many studies agree that partial oxidation of organic compounds almost exclusively involves redox cycles and acid-base properties of transition metal oxides and some authors have attempted to relate these properties with activity or selectivity in oxidation reactions [31,42]. The presence of both Bronsted and Lewis acid sites was evidenced, for example, in the case of the metal-modified mesoporous sihcas [30,39,43]. For the bimetallic (V-Ti, Nb-Ti) ions-modified MCM-41 mesoporous silica, the incorporation of the second metal led to the increase of the Lewis sites population [44]. This increased concentration of the acid sites was well correlated with the increased conversion in oxidation of unsaturated molecules such as cyclohexene or styrene [26,44] and functionalized compounds such as alcohols [31,42] or phenols [45]. 

We may thus conclude after this short overview on DeNO technologies that NH3-SCR using catalysts based on V-W-oxides supported on titania is a well-established technique for stationary sources of power plants and incinerators, while for other relevant sources of NO, such as nitric acid tail gases, where emissions are characterized from a lower temperature and the presence of large amounts of NOz, alternative catalysts based on transition metal containing microporous materials are possible. Also, for the combined DeNO -deSO, alternative catalysts would be necessary, because they should operate in the presence of large amounts of SO,.. Similarly, there is a need to develop new/improved catalysts for the elimination of NO in FCC emissions, again due to the different characteristics of the feed with respect to emissions from power plants. 

The second example demonstrated immobilization via ship in a bottle , ionic, metal center, and covalent bonding approaches of the metal-salen complexes. Zeolites X and Y were highly dealuminated by a succession of different dealumi-nation methods, generating mesopores completely surrounded by micropores. This method made it possible to form cavities suitable to accommodate bulky metal complexes. The catalytic activity of transition metal complexes entrapped in these new materials (e.g, Mn-S, V-S, Co-S, Co-Sl) was investigated in stereoselective epoxidation of (-)-a-pinene using 02/pivalic aldehyde as the oxidant. The results obtained with the entrapped organometallic complex were comparable with those of the homogeneous complex. 

From the examples above, it is clear that oxidation reactions using redox-active molecular sieves is an active area of research for the synthesis of fine chemicals and intermediates. The novel chemistry is possible because of the location of the transition metal ions at specific crystallographic sites in the framework and also the pore structure of microporous materials. 

There are now four major classes of materials in which organic components exert a significant structural role in controlling the inorganic oxide microstructure zeolites, mesoporous oxides of the MCM-41 class, biomineralized materials, and microporous octahedral-tetrahedral or square pyramidal-tetrahedral transition metal phosphate frameworks (TMPO) with entrained organic cations. ... 

The higher the active surface area of the catalyst, the greater the number of product molecules produced per unit time. Therefore, much of the art and science of catalyst preparation deals with high-surface-area materials. Usually materials with 100- to 400-m /g surface area are prepared from alumina, silica, or carbon and more recently other oxides (Mg, Zr, Ti, V oxides), phosphates, sulfides, or carbonates have been used. These are prepared in such a way that they are often crystalline with well-defined microstructures and behave as active components of the catalyst system in spite of their accepted name supports. Transition-metal ions or atoms are then deposited in the micropores, which are then heated and reduced to produce small metal particles 10-10" A in size with virtually all the atoms located on the surface... 

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