The role of temperature in the synthesis of hybrid inorganic–organic materials: the example of cobalt succinates

Forster, Paul M.; Burbank, Andrea R.; Livage, Carine; Férey, Gérard; Cheetham, Anthony K.

doi:10.1039/b311156c

Cited by 395 publications

(207 citation statements)

References 10 publications

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“…This is in accordance with the results of a series of experiments in which cobalt(II) hydroxide was treated with succinic acid in 1:1 molar ratio at five temperatures between 60 and 250 8C. [20] Five cobalt succinates were obtained, which became more dense and less hydrated with increasing temperature. To further support our results, four single experiments in conventional autoclaves were carried out for the molar ratio Cd 2+ /H 5 L/NaOH = 1:1:1.…”

Section: Sebastian Bauer and Norbert Stock*supporting

confidence: 86%

Implementation of a Temperature‐Gradient Reactor System for High‐Throughput Investigation of Phosphonate‐Based Inorganic–Organic Hybrid Compounds

Bauer

Stock

2007

Angew Chem Int Ed

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High-throughput (HT) methods applied to materials science are a powerful technique for the rapid investigation of large parameter spaces in a short time, and they give rise to the accelerated discovery of new materials and the optimization of synthesis parameters.[1] The resulting information density contributes to a better understanding of the role of compositional and process parameters. After the pioneering work of Schultz et al. based on thin-film methods [2] several approaches for the HT investigation of the hydrothermal synthesis of zeolitic microporous materials have been reported. [3] In a recent HT study, the influence of pH, temperature, concentration, and time on the synthesis of hybrid inorganicorganic materials was investigated in detail.[4] It was shown that acid/base ratio, time, concentration, and, most importantly, temperature play a role in determining which structure forms. Due to the application of HT methods, these systematic investigations involving 383 individual reactions could be carried out in only three weeks. The method allows automated dispensing of reagents, identical treatment under hydrothermal conditions for up to 48 reaction mixtures, parallel workup, and automated characterization without manipulation of individual samples.[5] Although this setup is ideal for the isothermal study of compositional parameters, parallel screening of temperature in a single HT experiment was not possible. However, since temperature often has a profound impact on product formation, a HT method that allows parallel investigation of the influence of temperature on identical reaction mixtures in one HT experiment would be of great benefit for systematic investigations of solvothermal reactions.Whenever a well-established HT methodology is expanded, new tools must be integrated in the workflow in order to avoid bottlenecks. We successfully integrated a thermocycler (also known as PCR machine) with a gradient function in our HT methodology and thus extended the HT investigation of parameter spaces from only composition to a further dimension, temperature. This allows us to efficiently screen the role of temperature in solvothermal synthesis, since all experiments are carried out in parallel. The thermal block with a maximum gradient of 40 K allows the investigation of six different compositions at eight different temperatures and therefore 48 individual reactions at a time.Whereas in zeolite chemistry the influence of compositional (e.g., Si/Al ratio, pH, concentration) and process parameters (e.g., reaction time, temperature, homogenization) is well understood, [6] similar studies on inorganicorganic hybrid compounds are quite rare.[7] Apart from reticular chemistry, which allows the tailoring of functionalized carboxylate-based hybrid materials (metal-organic frameworks, MOFs), in phosphonate chemistry many parameters for directing the structure remain unexplored. Nevertheless, metal phosphonates are promising candidates for sorbents, ion-exchange materials, and catalysts. [8] In our ongoing stud...

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Section: Sebastian Bauer and Norbert Stock*supporting

confidence: 86%

Implementation of a Temperature‐Gradient Reactor System for High‐Throughput Investigation of Phosphonate‐Based Inorganic–Organic Hybrid Compounds

Bauer

Stock

2007

Angew Chem Int Ed

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“…However several other synthetic parameters (e.g., pressure, solvent, pH, reaction time and temperature) and approaches must also be taken into account. 7,18,36,37 Depending on the final purpose, multidimensional MOFs may be prepared employing several and distinct synthetic methodologies: some of them are faster and with low energy consumption, being more attractive for industrial purposes. The possibility to prepare the desired materials as large single-crystals is, very often, a difficult but important task, which influences which method is ultimately selected.…”

Section: -Synthesismentioning

confidence: 99%

Multifunctional metal–organic frameworks: from academia to industrial applications

et al. 2015

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“…Indeed, an increasing degree of condensation of the inorganic nodes in MOFs has previously been associated with the formation of thermodynamically more stable phases at increasing temperatures. 2,37 When comparing UTSA-74 and MOF-74(Zn), the conversion of discrete Zn 2+ dimers into onedimensional infinite chains leads to an increase in the number of Zn 2+ -linker bonds from four to five, achieving a hydrolytically more stable coordination environment. This is reminiscent of the water-induced transformation of MOF-5(Zn) to MOF69c, 38,39 where conversion of discrete [Zn4O(COO)6] clusters to infinite chains is also accompanied by an increase in average Zn 2+ coordination number, from 4 to 4.67.…”

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confidence: 99%

An in situ investigation of the water-induced phase transformation of UTSA-74 to MOF-74(Zn)

et al. 2017

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We report the water-induced transformation of the [Zn2(dobdc)] (dobdc = 2,5-dioxidobenzene-1,4-dicarboxylate) metal-organic framework UTSA-74 to its polymorph MOF-74(Zn), contrary to a previous report on the stability of UTSA-74 under such conditions. This dissolution-recrystallization process was investigated using time-resolved in situ X-ray diffraction and kinetically analyzed using the Gualtieri crystallization model.

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The role of temperature in the synthesis of hybrid inorganic–organic materials: the example of cobalt succinates

Abstract: Five different cobalt succinate materials synthesized from an identical starting mixture using temperature as the only independent variable show increasing condensation and density at higher synthesis temperatures.

Cited by 395 publications

References 10 publications

Implementation of a Temperature‐Gradient Reactor System for High‐Throughput Investigation of Phosphonate‐Based Inorganic–Organic Hybrid Compounds

Implementation of a Temperature‐Gradient Reactor System for High‐Throughput Investigation of Phosphonate‐Based Inorganic–Organic Hybrid Compounds

Multifunctional metal–organic frameworks: from academia to industrial applications

An in situ investigation of the water-induced phase transformation of UTSA-74 to MOF-74(Zn)

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