Catalysis by Chemical Society (Great Britain)
By Chemical Society (Great Britain)
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Extra resources for Catalysis
The authors point out that their arguments are not conclusive. This paper has a very thoughtful discussion which looks at the wider issues of bonding of acetylene to transition metals. The authors examine trends in organometallic and surface bonding. First they note that the interaction of acetylene (and benzene) is stronger with Pt than with Fe, Ni, and Cu. In the case of acetylene there is an increased splitting of the u orbitals, interpreted as a rehybridization. This situation also exists for (100) Ir and W.
The behaviour of ethylene depends upon the geometry of the substrate. On Ir(100)-(5 x 1) at room temperature C-C scission occurs, whereas on Ir(100)(1 x 1) dehydrogenation occurs giving a stretched and bent acetylene molecule. Benzene behaves differently from both acetylene and ethylene. It neither fragments nor distorts on Ir(100)-(5 x 1) or (1 x 1) surfaces. Having examined interactions on Ir we now turn to adsorptions on Pt. Catalyst chemists must wonder what AES, UPS, LEED, and flash desorption have revealed about acetylene and benzene adsorption on Pt(100).
High-resolution electron energy loss spectroscopy with LEED for benzene on Ni( 100) and (1 11) confirms flat bonding of benzene. g. cumene over Cu. Allara and Robertss6 used XPS in their study to examine catalysts for the presence of Cu+, Cu2+,0 2 -and , OH-. t-Butyl hydroperoxide was used as an initiator for their catalytic runs on oxidation of hexadecane. It appears that rin the presence of C u 2 + 0 2 - , t-Bu02H produces free radical products which bring about catalysis. In contrast over Cu(OH), non-free-radical species are produced with inhibition of reaction.