Rational Design of Pd-Based Alloys for 1,3-Butadiene Selective Hydrogenation via Equilibrium Models of Nanoparticles

The selective hydrogenation of conjugated dienes in monoolefine-rich steam is an important process to eliminate dienes from monoolefins in petroleum refining, where the discovery of a highly active, selective, and stable Pd-based alloy is beneficial to its large-scale application. Herein, we report an experimentally validated theoretical framework to discover promising Pd-based bimetal catalysts for 1,3-butadiene selective hydrogenation to butene, which combines density functional calculation, descriptor-based microkinetic modeling, and Wulff construction principle. Since the activity and selectivity of 1,3-butadiene hydrogenation on Pd-based bimetal surface could be expressed by H and CH₃ adsorption energy, our theoretical framework efficiently predicts the desorption rate of butene on equilibrium-state Pd-based bimetal nanoparticles. After high-throughput screening on the second component, the PdW nanoparticle, of which butene production is mainly contributed by PdW(100), is predicted to be promising and experimentally proven to outperform Pd in selective hydrogenation of the butene-rich C4 fraction, including butane yield and long-term stability. The work demonstrates the importance of comprehensively considering the contribution of diverse crystal surfaces to catalytic performance when high-throughput screening on an alloy component. The outlined approach is general and applicable to a range of different hydrogenation reactions over alloy catalysts.