Self-Assembly of a Phosphate-Centered Polyoxo-Titanium Cluster: Discovery of the Heteroatom Keggin Family.,Angewandte Chemie International Edition

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Self-Assembly of a Phosphate-Centered Polyoxo-Titanium Cluster: Discovery of the Heteroatom Keggin Family.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2019-10-16 , DOI: 10.1002/anie.201910491
Ning Li _{1,

2} , Jiang Liu ₁ , Jing-Jing Liu ₁ , Long-Zhang Dong ₁ , Shun-Li Li ₁ , Bao-Xia Dong ₂ , Yu-He Kan ₃ , Ya-Qian Lan ₁

Affiliation

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 TiIV has lower oxidate state and larger ionic radius than MoVI , WVI , VV , and NbV , additional TiIV 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.

中文翻译：

以磷酸盐为中心的多氧钛簇的自组装：杂原子Keggin家族的发现。

在过去的200年中，多金属氧酸盐中最著名和最重要的杂原子Keggin结构仅由Mo，W，V或Nb合成。现在，介绍了两个以磷酸盐（PO4 3-）为中心的多氧钛簇（PTC）的自组装，分别为PTi16和PTi12，它们分别显示了经典的杂原子Keggin及其三价结构。由于TiIV具有比MoVI，WVI，VV和NbV更低的氧化态和更大的离子半径，因此这些PTC中的其他TiIV中心可用于稳定所得的杂原子Keggin结构，如相应的理论计算结果所示。这些光敏性PTC可用作有效的光催化剂，用于高选择性的CO2-HCOOH转化。这一新发现表明经典的杂原子Keggin家族可以与Ti组装在一起，

更新日期：2019-10-17

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