Facile Synthesis of Surface-Clean Monodispersed CuOx Nanoparticles and Their Catalytic Properties for Oxidative Coupling of Alkynes

We show a facile method to prepare surface-clean monodispersed small and stable CuOx nanoparticles with controllable average sizes from below 1 nm up to ∼5 nm without using bulk capping agent. Structural and surface characterizations show that the chemical states of CuOx nanoparticles and their interactions with O2 are dependent on the particle size. To show their relevance to catalysis, the well-defined monodispersed CuOx nanoparticles have been used for oxidative coupling of alkynes. While the generally used CuCl catalysts presents a reaction induction period and agglomerate into CuOx nanoparticles during the reaction, the induction period disappears when monodispersed CuOx nanoparticles (∼2 nm) were used as catalyst. Supported CuOx nanoparticles on TiO2 behave in the same way as monodispersed CuOx nanoparticles. Kinetic, spectroscopic, and isotopic studies show that O2 activation is the rate-controlling step and that the nature of the oxygen species formed on supported CuOx nanoparticles is dependent on the size of CuOx and determine the catalytic properties for oxidative coupling of alkynes.