Catalyst synergism

Hemnann, W. A. Kohlpaintner, C. W. Water-Soluble Ligands, Metal Complexes, and Catalysts Synergism of Homogeneous and Heterogoieous Catalysis. Amew. Chem. M. Ed. Enel. 1993. 32, 1524-1544. 

Herrmaim, W.A. and Kohlpaintner, C.W., Water-soluble hgands. Metal complexes, and catalysts synergism of homogeneous and heterogeneous catalysts, Angew. Chetrt, Int Ed. Engl, 1993,32, 1524. 

Direct conversion of methane to ethane and ethylene (C2 hydrocarbons) has a large implication towards the utilization of natural gas in the gas-based petrochemical and liquid fuels industries [ 1 ]. CO2 OCM process provides an alternative route to produce useful chemicals and materials where the process utilizes CO2 as the feedstock in an environmentally-benefiting chemical process. Carbon dioxide rather than oxygen seems to be an alternative oxidant as methyl radicals are induced in the presence of oxygen. Basicity, reducibility, and ability of catalyst to form oxygen vacancies are some of the physico-chemical criteria that are essential in designing a suitable catalyst for the CO2 OCM process [2]. The synergism between catalyst reducibility and basicity was reported to play an important role in the activation of the carbon dioxide and methane reaction [2]. 

Promotional effects of sulfide can evidently be explained, because exposure of reduced metals Is Increased on reduced sulfided catalysts. The role of cobalt Is less clear. It Is normally not fully reduced. It apparently does not promote greater exposure of Mo In any form detected, either In the presence or absence of sulfide. On the contrary. It evidently only decreases the concentration of exposed Mo atoms, although, at concentrations typically used, most. Mo atoms are unaffected by Co. Either some property of Co alone or some local cooperative effect of adjacent Co and Mo must explain promotion. Simple mechanical mixtures will not give the synergism observed, however (1-4). 

The same group, in a previous work, reported on the realization of a hybrid anode electrode [197]. An appreciable improvement in methanol oxidation activity was observed at the anode in direct methanol fuel cells containing Pt-Ru and Ti02 particles. Such an improvement was ascribed to a synergic effect of the two components (photocatalyst and metal catalyst). A similar behavior was also reported for a Pt-Ti02-based electrode [198]. Another recent study involved the electrolysis of aqueous solutions of alcohols performed on a Ti02 nanotube-based anode under solar irradiation [199]. 

In the NO-SCR by NH3, we note the highest reduction activity and selectivity on catalyst containing both vanadium and molybdenum than catalysts issued containing Mo or V, only. Furthermore, it should be underlined that a higher efficiency is obtained with ZSM-5 as host structure than samples issued from USY and MOR. Where a higher loss of porous volume were observed. On the basis of characterization data it has been suggested that the observed synergism in the SCR reaction is related to the existence of electronic interaction between the V and Mo species. In particular, it has been proposed that the presence of such electronic interactions modifies the catalysts redox properties, which have been claimed an essential property in the NO-SCR by NH3 reaction. 

The effectiveness of zeolites in catalysis and separation can often be improved by the textural and chemical properties of the matrices in which they are imbedded. Chitosan gels issued from renewable resources are already used as supports for the preparation of heterogeneous catalysts in the form of colloids, flakes or gel beads [1, 2], In this study we present several methods for the incorporation of zeolites in chitosan matrices and characterize the synergic effect of the components on the properties of the composite. 

The synergism of a dual-catalyst system comprising of Pt/ZSM-12 and H-Beta aiming to improve the benzene product purity during transalkylation of aromatics has been studied. Catalyst compositions of the dual-catalyst system were optimized at various reaction temperatures in terms of benzene product purity and premium product yields. Accordingly, a notable improvement in benzene purity at 683 K that meets the industrial specification was achieved using the cascade dual-bed catalyst. 

Previously, we have developed several techniques for platinum supported zeolite catalysts to improve the benzene product purity, including on-line sulfiding [3], precoking [6], and dual-bed catalyst system [7]. We report herein an in-depth investigation on the synergism of proton zeolite and platinum supported ZSM-12 catalyst (Pt/Z12) in a cascade dual-catalyst system. 

Catalyst solutions of Fe and Ru or Fe/Ru mixed metal carbonyls were found to exhibit two orders of magnitude higher activity than either the Ru or Fe carbonyl catalysts alone. A weaker synergistic behavior was observed for Fe/Ir mixed metal carbonyls, which were 50% more active. Rh carbonyl catalysts were the most active ( 590 mol H2/mol catalyst per day), but did not display a synergism in combination with other metal carbonyls. 

Using the dendrimer route, it is possible to prepare supported catalysts not available via traditional routes. Dendrimer derived Pt-Au catalysts having compositions within the bulk miscibility gap can be prepared on several oxide supports. For all the supports studied, the bimetallic catalysts exhibited synergism with respect to mono- and cometallic catalysts for the CO oxidation and hydrocarbon NOx SCR reactions. The bimetallic Pt-Au catalysts also showed evidence of exchanging surface and subsurface atoms in response to strongly binding ligands such as CO. 

Rh, are the base of active catalysts for CO hydrogenation and the hydroformylation of olefins. The presence of several promoters modifies their catalytic behavior and synergic effects on the base-metal have been observed Table 8.5 illustrates several examples in which homonuclear or heteronuclear carbonyl compounds have been used in the preparation of Co- or Co-Rh-based catalysts for the CO hydrogenation and/or hydroformylation reactions. 

A highly interesting class of catalysts is represented by bimetallic systems, which in many important catalytic processes show improved activity or selectivity compared with catalysts involving only one metal. Understanding their better performance is still a challenge. One metal can tune and/or modify the catalytic properties of the other metal as the result of both electronic or/and structural effects. Several mechanisms for synergism can be proposed, but it is difficult to assess their relative importance. It is clear that each metal can play a very important role in proper circumstances [41]. 

An alluring field of research is the mechanism of action of oxidation inhibitors. This research will undoubtedly yield in the near future a theory for inhibition of undesirable oxidation processes. The relatively stable free radicals observed on such inhibition display extremely interesting properties. Of great interest are the effects of synergism, of inhibitor mixtures, and of mixtures of inhibitors with catalysts. A strictly quantitative and elegant description of all these phenomena may be made within the scope of the chain theory for slow oxidation. 

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