Facet-Dependent Catalytic Activity of Gold Nanocubes, Octahedra, and Rhombic Dodecahedra toward 4-Nitroaniline Reduction

Abstract

In this study, cubic, octahedral, and rhombic dodecahedral gold nanocrystals synthesized by a seed-mediated growth method were employed as catalysts for the examination of facet-dependent catalytic activity toward NaBH4 reduction of p-nitroaniline to p-phenylenediamine at different temperatures. Different amounts of the nanocrystal solutions were used so that all samples contain particles with the same total surface area. UV–vis absorption spectra monitored the reaction progress. Rhombic dodecahedra showed the best catalytic efficiency at all the temperatures examined. Nanocubes have higher reaction rates than those of octahedra from 25 to 36 °C, so the catalytic activity for the reduction reaction follows the order of {110} > {100} > {111}. However, the reaction rates for octahedra increase rapidly with rising temperature; their reaction rate surpasses that for the nanocubes at 40 °C. Rate constants and activation energies were determined, again showing that the activation energy is lowest for rhombic dodecahedra. Density functional theory (DFT) calculations indicate highest binding energy between p-nitroaniline and the Au(110) plane. The results reveal rhombic dodecahedral gold nanocrystals as highly efficient catalysts.