Self‐Assembly of a Phosphate‐Centered Polyoxo‐Titanium Cluster: Discovery of the Heteroatom Keggin Family. Issue 48 (16th October 2019)

• Record Type: Journal Article
• Authors: Li, Ning; Liu, Jiang; Liu, Jing‐Jing; Dong, Long‐Zhang; Li, Shun‐Li; Dong, Bao‐Xia; Kan, Yu‐He; Lan, Ya‐Qian
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 48(2019)
• Page Start: 17260
• Page End: 17264
• Publication Date: 2019-10-16
• Subjects: CO2 photoreduction -- Keggin structures -- polyoxo-titanium cluster; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201910491
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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 (PO4 3− )‐centered polyoxo‐titanium clusters (PTCs) is presented, PTi16 and PTi12, 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 CO2 ‐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. Abstract : One of the family : A Ti IV ‐based heteroatom Keggin and its trivacant lacunary architectures were structurally synthesized as a polyoxo‐titanium cluster. They exhibited a very high selectivity and activity for photocatalytic CO2 ‐to‐HCOOH conversion.