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Self‐Assembly of a Phosphate‐Centered Polyoxo‐Titanium Cluster: Discovery of the Heteroatom Keggin Family
Author(s) -
Li Ning,
Liu Jiang,
Liu JingJing,
Dong LongZhang,
Li ShunLi,
Dong BaoXia,
Kan YuHe,
Lan YaQian
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201910491
Subject(s) - heteroatom , cluster (spacecraft) , chemistry , titanium , crystallography , self assembly , keggin structure , polyoxometalate , inorganic chemistry , materials science , catalysis , organic chemistry , ring (chemistry) , computer science , programming language
Over the past 200 years, the most famous and important heteroatom Keggin architecture in polyoxometalates has only been synthesized with Mo, W, V, or Nb. Now, the self‐assembly of two phosphate (PO 4 3− )‐centered polyoxo‐titanium clusters (PTCs) is presented, PTi 16 and PTi 12 , which display classic heteroatom Keggin and its trivacant structures, respectively. Because Ti IV has lower oxidate state and larger ionic radius than Mo VI , W VI , V V , and Nb V , additional Ti IV centres in these PTCs are used to stabilize the resultant heteroatom Keggin structures, as demonstrated by the cooresponding theoretical calculation results. These photoactive PTCs can be utilized as efficient photocatalysts for highly selective CO 2 ‐to‐HCOOH conversion. This new discovery indicates that the classic heteroatom Keggin family can be assembled with Ti, thus opening a research avenue for the development of PTC chemistry.