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含钛簇金属有机框架的钠耦合电子转移反应活性：阳离子在氧化还原化学中的重要性。

Sodium-coupled electron transfer reactivity of metal-organic frameworks containing titanium clusters: the importance of cations in redox chemistry.

作者信息

Saouma Caroline T, Tsou Chih-Chin, Richard Sarah, Ameloot Rob, Vermoortele Frederik, Smolders Simon, Bueken Bart, DiPasquale Antonio G, Kaminsky Werner, Valdez Carolyn N, De Vos Dirk E, Mayer James M

机构信息

Department of Chemistry , University of Washington , Box 351700 , Seattle , Washington 98195-1700 , USA.

Department of Chemistry , University of Utah , 315 S 1400 E , Salt Lake City , Utah 84112-0850 , USA . Email:

出版信息

Chem Sci. 2018 Nov 19;10(5):1322-1331. doi: 10.1039/c8sc04138e. eCollection 2019 Feb 7.

DOI:10.1039/c8sc04138e
PMID:30809347
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6354900/
Abstract

Stoichiometric reduction reactions of two metal-organic frameworks (MOFs) by the solution reagents (M = Cr, Co) are described. The two MOFs contain clusters with TiO rings: TiO(OH)(bdc); bdc = terephthalate (MIL-125) and TiO(OH)(bdc-NH); bdc-NH = 2-aminoterephthalate (NH-MIL-125). The stoichiometry of the redox reactions was probed using solution NMR methods. The extent of reduction is greatly enhanced by the presence of Na, which is incorporated into the bulk of the material. The roughly 1 : 1 stoichiometry of electrons and cations indicates that the storage of e in the MOF is tightly coupled to a cation within the architecture, for charge balance.

摘要

描述了通过溶液试剂（M = Cr、Co）对两种金属有机框架（MOF）进行的化学计量还原反应。这两种MOF包含带有TiO环的簇：TiO(OH)(bdc)；bdc = 对苯二甲酸（MIL-125）和TiO(OH)(bdc-NH)；bdc-NH = 2-氨基对苯二甲酸（NH-MIL-125）。使用溶液核磁共振方法探究了氧化还原反应的化学计量。Na的存在极大地增强了还原程度，Na被掺入材料主体中。电子与阳离子大致1∶1的化学计量表明，MOF中电子的存储与结构内的阳离子紧密耦合，以实现电荷平衡。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45f8/6354900/7bb0585baa8a/c8sc04138e-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45f8/6354900/1a5160a3c40b/c8sc04138e-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45f8/6354900/7bb0585baa8a/c8sc04138e-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45f8/6354900/1a5160a3c40b/c8sc04138e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45f8/6354900/6b1339ccc09d/c8sc04138e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45f8/6354900/3b3276c7d960/c8sc04138e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45f8/6354900/890c9eed1864/c8sc04138e-f4.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/45f8/6354900/7bb0585baa8a/c8sc04138e-f6.jpg

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