Mechanism driven design of trimer Ni1Sb2 site delivering superior hydrogenation selectivity to ethylene

Mechanism driven catalyst design with atomically uniform ensemble sites is an important yet challenging issue in heterogeneous catalysis associated with breaking the activity-selectivity trade-off. Herein, a trimer Ni1Sb2 site in NiSb intermetallic featuring superior selectivity is elaborated for acetylene semi-hydrogenation via a theoretical guidance with a precise synthesis strategy. The trimer Ni1Sb2 site in NiSb intermetallic is predicted to endow acetylene reactant with an adequately but not excessively strong σ-adsorption mode while ethylene product with a weak π-adsorption one, where such compromise delivers higher ethylene formation rate. An in-situ trapping of molten Sb by Ni strategy is developed to realize the construction of Ni1Sb2 site in the intermetallic P63/mmc NiSb catalysts. Such catalyst exhibits ethylene selectivity up to 93.2% at 100% of acetylene conversion, significantly prevailing over the referred Ni catalyst. These insights shed new lights on rational catalyst design by taming active sites to energetically match targeted reaction pathway. Designing atomically uniform ensemble sites for matching targeted reaction pathway is important yet challenging in heterogeneous catalysis. Here, the authors fabricate a trimer Ni1Sb2 site featuring superior selectivity for acetylene semi-hydrogenation via a mechanism-driven design strategy.