Particle Size Effects in the Selective Hydrogenation of Alkadienes over Supported Cu Nanoparticles

Copper is considered an excellent alternative to noble-metal selective hydrogenation catalysts. Herein, we systematically studied the effect of Cu nanoparticle size (2–10 nm) in the selective hydrogenation of 1,3-butadiene in excess of propene. The catalysts exhibited particle size-dependent activity, with particles above 4 nm being 3 to 4 times more active than the 2 nm ones, and at the same time more selective (up to 99 % at almost full butadiene conversion for 7–10 nm particles). The higher activity of larger particles was ascribed to a higher fraction of kinks and step sites, essential to activate hydrogen. The high selectivity of nanoparticulate Cu catalysts was explained by a very strong preferential adsorption of 1,3-butadiene compared to mono-olefin adsorption on the Cu surface (in particular on larger particles), as proven via adsorption measurements. These findings may guide both testing and catalyst design for reactions where hydrogen surface availability and selectivity play a key role.