l~lb~ el bu~rgrmic Chemi,~lr~' aml Catra!vsix, EindhoPen tJni,~6(1~) MB Eimlhocen. Netherlands Received 16 December 1Ot)0; revised 31 January 1997 AhsiraelThe: c~,clroca|alyliqr |vdBcIion of uilrale has been investigated on Pt, Pd and Pl k Pd elecu~od¢,~ covered wi|h a ,~ubmonolayeJ of gern~aniunk PI + Pd eleo,~des were prepared by electrol¢~s deposition of stubmnnolayer~ of Pd on Pl by exchange of PdCI~ for preadsod~ed eopl~,r, Underpote~ ~i,dly deposited germanium enhances the reduction rale of nitrate strongly. The reduction of nitrite i~ euhanced to a lesser extent, whezeas germanium is inactive for NO and hydroxylamine reduction. Furlher. cyclic voltammetry shows that the well known inhibition of the nitrate reduction at low potentials is absent fi~r germaniumomodified electrodes. Amperometry shows lhat the cun~nt densities for nitrate reduction at 0.1 V depend strongly on the composition of the electrode surface. The activities increase in the order Pd, PI and Pt + Pd and all electrodes display a plopurtional relation between the activity and the germanium coverage. This shows that gemmnium is involved in the rate determining step, which is the reduction of nitrate to nitrite and its role is to bind the oxygen atom of nitrate, The higher activities for Pt + Pd electrodes can be understood in terms of changes in the electronic structure of the metals as a result of alloying. Selectivity measurements with a rotating ring-disk electrode have shown for all electrodes that the hydroxylamine selectivity increases for increasing germanium coverage. Pd displays higher hydroxylamine ,;electivides than Pt and Pt + Pd electrode~. No gaseous products were observed for Pi. whereas for Pt + Pd and Pd N~O selectivitie~ up to 8% were found. © 1997 Elsevier Science S.A.

Surface segregation processes in Pd−Pt alloys and bimetallic Pd−Pt nanoclusters on alumina and carbon supports (technical catalysts) have been investigated by determining the metal surface composition of these systems by low-energy ion scattering (LEIS). Both Pd-rich (Pd80Pt20) and Pt-rich (Pd20Pt80) systems have been studied. The surface of the Pd−Pt alloys is enriched in Pd after heating in ultrahigh vacuum and thermodynamic equilibrium is reached at about 700 °C. Pd surface segregation is enhanced by heating the alloys in hydrogen or oxygen, and thermodynamic equilibrium is reached already at about 400−500 °C. For Pd−Pt catalysts with low metal dispersions of about 0.3 and 0.8, Pd surface segregation does take place during heating in hydrogen to approximately the same extent as in the Pd−Pt bulk alloys. For Pd−Pt catalysts with a high metal dispersion close to 1, however, surface segregation is completely suppressed during heating in hydrogen and oxygen. We attribute this to the limited supply of Pd atoms from the bulk to the surface of the nanoclusters.

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The effect of polydispersity and inhomogeneity of supported bimetallic catalysts on the EXAFS analysis is investigated with some simple model calculations. These show that EXAFS is very insensitive to polydispersity. Polydispersity and inhomogeneous distribution of the metals over the particles however have only limited influence on the ability to distinguish between core-shell particles and particles with random distribution of both metals.

The desorption of products from a series of alkaline-earth exchanged Y zeolites after room-temperature propane selective oxidation was investigated by in situ infrared and mass spectroscopy. The intermediate product, isopropylhydroperoxide (IHP), did not desorb during temperature-programmed-desorption experiments but converted into acetone and water. Decomposition rate of IHP, produced from propane and oxygen at room temperature, into acetone increased in the order BaY < SrY < CaY (250 °C) under dry conditions. Addition of water, however, results in gas phase acetone already at room temperature. From the results it can be concluded that water clearly facilitates acetone desorption, most likely via shielding of the electrostatic field and creation of additional sites.