Exploring the mechanism of in situ formation of oxalic acid for producing mixed fumarato-oxalato lanthanide (Eu, Tb and Gd) frameworks

被引：9

作者：

Oliveira, Cristiane K. ^{[1
]}

de Menezes Vicenti, Juliano R. ^{[2
]}

Burrow, Robert A. ^{[2
]}

Alves, Severino, Jr. ^{[1
]}

Longo, Ricardo L. ^{[1
]}

Malvestiti, Ivani ^{[1
]}

机构：

[1] Univ Fed Pernambuco, Dept Quim Fundamental, BR-50740560 Recife, PE, Brazil

[2] Univ Fed Santa Maria, Dept Quim, BR-97105900 Santa Maria, RS, Brazil

来源：

INORGANIC CHEMISTRY COMMUNICATIONS | 2012年 / 22卷

关键词：

In situ reaction; Hydrothermal treatment; Lanthanide; MOF; Reaction mechanism; COORDINATION POLYMERS; CRYSTAL-STRUCTURES; CARBON-DIOXIDE; HYDROTHERMAL SYNTHESIS; OXIDATION; NETWORKS; H2O; PDC; SM; LN;

D O I：

10.1016/j.inoche.2012.04.036

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Mixed fumarato-oxalato ligands lanthanide metal-organic frameworks (MOFs) [Ln(2)(fum)(2)(ox)(H2O)(4)]center dot 4H(2)O (Ln = Eu, Gd, and Tb) were obtained from hydrothermal treatment of aqueous acid solutions of trivalent lanthanide ions and fumaric acid with nitrate or sodium hypochlorite as oxidants. The crystal structure for [Gd-2(fum)(2)(Ox)(H2O)(4)]center dot 4H(2)O was determined. Other oxidants (H2O2 and NaSO4) or conditions (NaOCl at room temperature and atmospheric pressure) yielded other MOFs or products. Oxalic acid was formed in situ and mechanisms based on the hydration of fumaric acid mediated by Ln(3+) followed by oxidation and decarboxylation steps were proposed. The mechanisms were able explain the dual role of Ln(3+) ions and the nature of the oxidant in forming the frameworks. (C) 2012 Elsevier B.V. All rights reserved.

引用

页码：54 / 59

页数：6

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