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固载于联吡啶-介孔有机硅上的铱配合物的水氧化多相催化作用。

Heterogeneous Catalysis for Water Oxidation by an Iridium Complex Immobilized on Bipyridine-Periodic Mesoporous Organosilica.

机构信息

Toyota Central R&D Laboratories, Inc., Nagakute, Aichi, 480-1192, Japan.

Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China.

出版信息

Angew Chem Int Ed Engl. 2016 Jul 4;55(28):7943-7. doi: 10.1002/anie.201601453. Epub 2016 May 11.

Abstract

Heterogenization of metal-complex catalysts for water oxidation without loss of their catalytic activity is important for the development of devices simulating photosynthesis. In this study, efficient heterogeneous iridium complexes for water oxidation were prepared using bipyridine-bridged periodic mesoporous organosilica (BPy-PMO) as a solid chelating ligand. The BPy-PMO-based iridium catalysts (Ir-BPy-PMO) were prepared by postsynthetic metalation of BPy-PMO and characterized through physicochemical analyses. The Ir-BPy-PMOs showed high catalytic activity for water oxidation. The turnover frequency (TOF) values for Ir-BPy-PMOs were one order of magnitude higher than those of conventional heterogeneous iridium catalysts. The reusability and stability of Ir-BPy-PMO were also examined, and detailed characterization was conducted using powder X-ray diffraction, nitrogen adsorption, (13) C DD MAS NMR spectroscopy, TEM, and XAFS methods.

摘要

金属配合物催化剂的异质化对于开发模拟光合作用的设备非常重要,因为这样可以避免其催化活性的损失。在这项研究中,我们使用联吡啶桥联的周期性介孔有机硅(BPy-PMO)作为固体螯合配体,制备了用于水氧化的高效非均相铱配合物催化剂。通过 BPy-PMO 的后合成金属化制备了基于 BPy-PMO 的铱催化剂(Ir-BPy-PMO),并通过物理化学分析对其进行了表征。Ir-BPy-PMO 对水氧化表现出高催化活性。Ir-BPy-PMO 的周转频率(TOF)值比传统的非均相铱催化剂高一个数量级。还对 Ir-BPy-PMO 的可重复使用性和稳定性进行了考察,并使用粉末 X 射线衍射、氮气吸附、(13)C DD MAS NMR 光谱、TEM 和 XAFS 方法进行了详细的表征。

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