Identification of Highly Active Co–O–Zn Sites in Silanol Nests for n -Butane Cascade Dehydrogenation to 1,3-Butadiene

n -Butane dehydrogenation (BDH) provides an on-purpose route to produce 1,3-BD. However, design of highly active and selective catalysts targeting BDH to 1,3-BD remains challenging because the activation barrier for the dehydrogenation of 1-butene (a primary product of BDH) is high and 1-butene readily isomerizes. Here, we report a bimetallic Co–O–Zn active site with the structure of ≡SiO–Co–O–Zn–OSi≡ prepared by reacting Co ions with ≡SiOZn–OH nests on dealuminated zeolite BEA (DeAlBEA), showing 3- and 34-fold activity advantages over monometallic Co and Zn counterparts, respectively. Co–O–Zn sites exhibit a high BDH rate of 354 mol·mol Co –1 ·h –1 and a 1,3-BD productivity of 110 mol·mol Co –1 ·h –1 (and selectivity to 1,3-BD of 31%) at 823 K. The forward rate coefficient for BDH is superior to state-of-the-art non-noble-metal catalysts and comparable to Pt-based catalysts. A kinetics investigation suggests that the Co–O–Zn interactions promote n -butane adsorption and activation of the C–H bond during both BDH and 1-butene dehydrogenation. Our work demonstrates a promising pathway for producing 1,3-BD via BDH using a catalyst that is free of expensive noble metals.