Theoretical study the catalytic performance and mechanism of novel designed single atom catalysts M1/2DMs for 1,3-butadiene hydrogenation

Selective hydrogenating 1,3-butadiene to butene is an important tool for the removal of 1,3-butadiene which is a by-product of olefin production. Traditional noble metal catalysts are expensive and relatively low selective for 1-butene. In order to decrease the catalyst cost and improve the 1-butene selective, single-atom catalysts were designed by doping non-noble metals single atom (Pd, Ru, Fe, Co, Ni) on two-dimensional material carriers, hexagonal BN and graphene. It is found that 1,3-butadiene tends to be dominated by mono-π-adsorption on single-atom catalysts, resulting in dissociated H atom preferentially attack the one end CC bond of 1,3-butadiene. Unlike the metallic nanomaterials, low energy barriers for the hydrogenation of 1,3-butadiene to 1-butene were obtained (Ru1/BN: 0.20 eV, Fe1/GR: 0.23 eV, Co1/BN: 0.36 eV, Ru1/GR: 0.44 eV, Co1/GR: 0.59 eV, Ni1/GR: 0.61 eV, Ni1/BN: 0.62 eV). The 1-butene desorption energies are smaller than the further hydrogenation energy barriers on the Pd1/GR, Ni1/GR, Pd1/BN Co1/BN and Ni1/BN surfaces, which indicated better selectivity on these catalysts’ surfaces. By contrast, Ni1/GR and Ni1/BN single-atom catalysts would be the best catalysts among all the studied catalyst in terms of adsorption energies of feed gas, dissociation ability of H2, hydrogenation energy barrier and 1-butene desorption energy.