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Polyoxometalate-Based Metal-Organic Framework as Molecular Sieve for Highly Selective Semi-Hydrogenation of Acetylene
Yiwei Liu1,2, Bingxue Wang3, Qiang Fu3,4
1Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Abstract:
Achieving highly selective acetylene semi-hydrogenation in an ethylene-rich gas stream is of great industrial importance. Herein, we construct isolated single Pd atom in a polyoxometalate-based metal-organic framework (POMOF). The unique internal environment allows this POMOF to separate acetylene from acetylene/ethylene gas mixtures and confine it close to the single Pd atom. After semi-hydrogenation, the resulting ethylene is preferentially discharged from the pores, achieving a selectivity of 92.6 %. First-principles simulations reveal that the adsorbed acetylene/ethylene molecules form hydrogen bond networks with oxygen atoms of SiW12 O40 4- and create dynamic confinement regions, which preferentially release the produced ethylene. Besides, at the Pd site, the over-hydrogenation of ethylene exhibits a higher reaction energy barrier than the semi-hydrogenation of acetylene. The combined advantages of POMOF and single Pd atom provides an effective approach for the regulation of semi-hydrogenation selectivity.
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