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Polyoxometalate‐Based Metal–Organic Framework as Molecular Sieve for Highly Selective Semi‐Hydrogenation of Acetylene on Isolated Single Pd Atom Sites
Author(s) -
Liu Yiwei,
Wang Bingxue,
Fu Qiang,
Liu Wei,
Wang Yu,
Gu Lin,
Wang Dingsheng,
Li Yadong
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202109538
Subject(s) - acetylene , ethylene , photochemistry , selectivity , molecular sieve , catalysis , chemistry , hydrogen , adsorption , metal organic framework , inorganic chemistry , organic chemistry
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 SiW 12 O 40 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.