{Ta12}/{Ta16} Cluster-Containing Polytantalotungstates with Remarkable Photocatalytic H2 Evolution Activity

详细信息    查看全文

• 作者：Shujun Li ; Shumei Liu ; Shuxia Liu ; Yiwei Liu ; Qun Tang ; Zhan Shi ; Shuxin Ouyang ; Jinhua Ye
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：December 5, 2012
• 年：2012
• 卷：134
• 期：48
• 页码：19716-19721
• 全文大小：294K
• 年卷期：v.134,no.48(December 5, 2012)
• ISSN：1520-5126

文摘

Four novel polytantalotungstates K₅Na₄[P₂W₁₅O₅₉(TaO₂)₃]路17H₂O (1), K₈Na₈H₄[P₈W₆₀Ta₁₂(H₂O)₄(OH)₈O₂₃₆]路42H₂O (2), Cs₃K_3.5H_0.5[SiW₉(TaO₂)₃O₃₇]路9H₂O (3), and Cs_10.5K₄H_5.5[Ta₄O₆(SiW₉Ta₃O₄₀)₄]路30H₂O (4) were synthesized. Compounds 1 and 3 are tris-(peroxotantalum)-substituted Dawson- and Keggin-type derivatives, whereas 2 and 4 are tetrameric oligomers containing respectively an unprecedented {Ta₁₂} and {Ta₁₆} cluster core. The photocatalytic activities of 2 and 4 for H₂ evolution from water were evaluated. The significantly enhanced performance against the control K₆[P₂W₁₈O₆₂] can be attributed to the modulation of the electronic structures of these novel POMs by Ta incorporation. The highest activity observed so far with the use of 2 can be further rationalized by the presence of distorted heptacoordinate Ta atoms in the form of TaO₇ pentagonal bipyramid.