We demonstrate that the reduction of p-nitrophenol to p-aminophenol by NaBH4 is catalyzed by both monometallic and bimetallic nanoparticles (NPs). We also demonstrate a straightforward and precise method for the synthesis of bimetallic nanoparticles using poly(amido)amine dendrimers. The resulting dendrimer encapsulated nanoparticles (DENs) are monodisperse, and the size distribution does not vary with different elemental combinations. Random alloys of Pt/Cu, Pd/Cu, Pd/Au, Pt/Au, and Au/Cu DENs were synthesized and evaluated as catalysts for p-nitrophenol reduction. These combinations are chosen in order to selectively tune the binding energy of the p-nitrophenol adsorbate to the nanoparticle surface. Following the Brønsted–Evans–Polanyi (BEP) relation, we show that the binding energy can reasonably predict the reaction rates of p-nitrophenol reduction. We demonstrate that the measured reaction rate constants of the bimetallic DENs is not always a simple average of the properties of the constituent metals. In particular, DENs containing metals with similar lattice constants produce a binding energy close to the average of the two constituents, whereas DENs containing metals with a lattice mismatch show a bimodal distribution of binding energies. Overall, in this work we present a uniform method for synthesizing pure and bimetallic DENs and demonstrate that their catalytic properties are dependent on the adsorbate’s binding energy.

The majority of nanocomposite olefin/paraffin separation membranes use silver nanoparticles or silver ions as the olefin binding agent. In this theoretical study, we characterize the olefin interaction with silver nanoparticles and show that silver is special in that it chemisorbs ethylene more weakly than other metals. Some variation with particle size is found; small 79 atom nanoparticles tend to bind ethylene more strongly than larger 140 atom particles, which in turn are well approximated by facets of bulk crystal surfaces. The effect of replacing cores of nanoparticles with different metals is demonstrated to selectively tune binding based on the relative d-band centers of the two metals. We identify silver-cored, gold-shelled nanoparticles as potentially more effective for olefin/paraffin separations. Random alloys of gold and silver were also considered. We find that 25%-75% Au-Ag random alloys are strong candidates for use in olefin/paraffin separation membranes due to the presence of reactive ( 111) faces without the cost of a strong increase in the binding energies on edges and corners. Nanocomposite membranes containing these nanoparticles hold promise for more efficiently separating olefins from paraffins.