Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Effect of Isomorphous Substitution on the Thermal Decomposition Mechanism of Hydrotalcites.

ABSTRACT: Hydrotalcites have many important applications in catalysis, wastewater treatment, gene delivery and polymer stabilization, all depending on preparation history and treatment scenarios. In catalysis and polymer stabilization, thermal decomposition is of great importance. Hydrotalcites form easily with atmospheric carbon dioxide and often interfere with the study of other anion containing systems, particularly if formed at room temperature. The dehydroxylation and decomposition of carbonate occurs simultaneously, making it difficult to distinguish the dehydroxylation mechanisms directly. To date, the majority of work on understanding the decomposition mechanism has utilized hydrotalcite precipitated at room temperature. In this study, evolved gas analysis combined with thermal analysis has been used to show that CO₂ contamination is problematic in materials being formed at RT that are poorly crystalline. This has led to some dispute as to the nature of the dehydroxylation mechanism. In this paper, data for the thermal decomposition of the chloride form of hydrotalcite are reported. In addition, carbonate-free hydrotalcites have been synthesized with different charge densities and at different growth temperatures. This combination of parameters has allowed a better understanding of the mechanism of dehydroxylation and the role that isomorphous substitution plays in these mechanisms to be delineated. In addition, the effect of anion type on thermal stability is also reported. A stepwise dehydroxylation model is proposed that is mediated by the level of aluminum substitution.

SUBMITTER: Crosby S

PROVIDER: S-EPMC5456014 | biostudies-other | 2014 Oct

REPOSITORIES: biostudies-other

ACCESS DATA

Json Xml

Similar Datasets

Selectivity and Mechanism of Thermal Decomposition of β-diketones on ZnO Powder.

Project description:The thermal chemistry of β-diketones underlies a number of catalytic processes related both to the catalytic reactions yielding commodity chemicals and to the production of supported transition metal catalysts themselves. The mechanisms of decomposition during thermal transformation of three β-diketones, acetylacetone (acacH), 1,1,1-trifluoroacetylacetone (tfacH), and 1,1,1,5,5,5-hexafluoroacetylacetone (hfacH), were studied on ZnO powder surface using Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and Density functional theory (DFT) computational investigation. The initial O-H dissociation leads to the formation of corresponding β-diketonates in all the cases investigated. These diketonates are important surface intermediates that can be generated in a controlled manner in these experiments. The presence on the C-CF3 entity determines the preferred thermal decomposition pathways, as the C-C bond in this group starts to react with a surface of ZnO around 400 K, followed by immediate decomposition of the resulting CF3 group. Above 600 K, the presence of the CF3-substituent leads to the formation of ketene-like structures observed by vibrational spectroscopy. The reaction mechanisms examined with the help of DFT calculations are correlated with vibrational signatures of the species produced and with the F-containing species recorded by XPS.

| S-EPMC4545501 | biostudies-literature

Effect of long-term ageing on graphene oxide: structure and thermal decomposition.

Project description:After long-term ageing, the structure of graphene oxide prepared by the modified Hummers method changed. Because of the desorption of oxygen-containing functional groups, the C/O ratio of graphene oxide increased from 1.96 to 2.76. However, the average interlayer distance decreased from 0.660 to 0.567 nm. The content of -CH- and -CH2- decreased; however, the type of oxygen-containing functional groups did not change. Moreover, I D/I G increased from 0.87 to 0.92, indicating that the defect density decreased because of desorbing oxygen functional groups after ageing. When the temperature exceeded 60°C, CO2 produced by decomposing graphene oxide was detected. The thermal decomposition changed after ageing. The decomposition peak temperature decreased from 216°C to 195°C. The CO2 amount produced remained almost unchanged; however, the amount of CO, SO2 and H2O decreased. After ageing, the apparent activation energy of graphene oxide decreased from 150 to 134 kJ mol-1.

| S-EPMC8652269 | biostudies-literature

Research on the Thermal Decomposition Reaction Kinetics and Mechanism of Pyridinol-Blocked Isophorone Diisocyanate.

Project description:A series of pyridinol-blocked isophorone isocyanates, based on pyridinol including 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine, was synthesized and characterized by ¹H-NMR, 13C-NMR, and FTIR spectra. The deblocking temperature of blocked isocyanates was established by thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), and the CO? evaluation method. The deblocking studies revealed that the deblocking temperature was increased with pyridinol nucleophilicity in this order: 3-hydroxypyridine > 4-hydroxypyridine > 2-hydroxypyridine. The thermal decomposition reaction of 4-hydroxypyridine blocked isophorone diisocyanate was studied by thermo-gravimetric analysis. The Friedman-Reich-Levi (FRL) equation, Flynn-Wall-Ozawa (FWO) equation, and Crane equation were utilized to analyze the thermal decomposition reaction kinetics. The activation energy calculated by FRL method and FWO method was 134.6 kJ·mol-1 and 126.2 kJ·mol-1, respectively. The most probable mechanism function calculated by the FWO method was the Jander equation. The reaction order was not an integer because of the complicated reactions of isocyanate.

| S-EPMC5456470 | biostudies-literature

Hydrolytic Decomposition of S-Aroylthiooximes: Effect of pH and N-Arylidene Substitution on Reaction Rate.

Project description:The hydrolytic decomposition of four peptides containing S-aroylthiooximes (SATOs) with variable N-arylidene substituents was investigated in 10 aqueous buffer solutions at pH values ranging from 6.0 to 10.9. UV-vis spectroscopy was employed to study the reaction kinetics, which revealed V-shaped pH-rate profiles for all peptides with a minimum near pH 8, suggesting a change from an acid-catalyzed to a base-activated reaction. Hammett plots showed positive ? values above pH 8 and negative ? values below pH 8, providing further evidence for a mechanism change. Based on these data, along with mass spectral evidence, we propose specific acid catalysis under mildly acidic and neutral conditions and multiple base-promoted decomposition reactions under mildly basic conditions.

| S-EPMC6294146 | biostudies-literature

Mechanism of thermal decomposition of carbamoyl phosphate and its stabilization by aspartate and ornithine transcarbamoylases.

Project description:Carbamoyl phosphate (CP) has a half-life for thermal decomposition of <2 s at 100 degrees C, yet this critical metabolic intermediate is found even in organisms that grow at 95-100 degrees C. We show here that the binding of CP to the enzymes aspartate and ornithine transcarbamoylase reduces the rate of thermal decomposition of CP by a factor of >5,000. Both of these transcarbamoylases use an ordered-binding mechanism in which CP binds first, allowing the formation of an enzyme.CP complex. To understand how the enzyme.CP complex is able to stabilize CP we investigated the mechanism of the thermal decomposition of CP in aqueous solution in the absence and presence of enzyme. By quantum mechanics/molecular mechanics calculations we show that the critical step in the thermal decomposition of CP in aqueous solution, in the absence of enzyme, involves the breaking of the C O bond facilitated by intramolecular proton transfer from the amine to the phosphate. Furthermore, we demonstrate that the binding of CP to the active sites of these enzymes significantly inhibits this process by restricting the accessible conformations of the bound ligand to those disfavoring the reactive geometry. These results not only provide insight into the reaction pathways for the thermal decomposition of free CP in an aqueous solution but also show why these reaction pathways are not accessible when the metabolite is bound to the active sites of these transcarbamoylases.

| S-EPMC2579353 | biostudies-literature

Thermal Decomposition of Nanostructured Bismuth Subcarbonate.

Project description:Nanostructured (BiO)2CO3 samples were prepared, and their thermal decomposition behaviors were investigated by thermogravimetric analysis under atmospheric conditions. The method of preparation and Ca2+ doping could affect the morphologies of products and quantity of defects, resulting in different thermal decomposition mechanisms. The (BiO)2CO3 nanoplates decomposed at 300-500 °C with an activation energy of 160-170 kJ/mol. Two temperature zones existed in the thermal decomposition of (BiO)2CO3 and Ca-(BiO)2CO3 nanowires. The first one was caused by the decomposition of (BiO)4(OH)2CO3 impurities and (BiO)2CO3 with surface defects, with an activation energy of 118-223 kJ/mol, whereas the second one was attributed to the decomposition of (BiO)2CO3 in the core of nanowires, with an activation energy of 230-270 kJ/mol for the core of (BiO)2CO3 nanowires and 210-223 kJ/mol for the core of Ca-(BiO)2CO3 nanowires. Introducing Ca2+ ions into (BiO)2CO3 nanowires improved their thermal stability and accelerated the decomposition of (BiO)2CO3 in the decomposition zone.

| S-EPMC7579297 | biostudies-literature

Mechanism of Two Typical Binders BR and F<sub>2604</sub> on Thermal Decomposition of HMX.

Project description:DSC-TG-FTIR-MS coupling technology was used to study the mechanism of two typical binders, that is, BR and F2604, on the thermal decomposition behavior of the HMX crystal. The results show that both BR and F2604 can induce premature decomposition of HMX and increase the activation energy of HMX. Especially in the case of HMX/BR particles, the decomposition temperature is the lowest, but the activation energy is the highest. Based on the results of DSC-TG-FTIR-MS, it is found that the rapid mechanism of binder and active intermediate products inhibits the reaction of relatively inert intermediate products and prolongs the continuous generation time of gas products in the composite particles, which delays the decomposition of HMX to a certain extent. This study is helpful for us to better understand the thermal decomposition behavior of HMX composite particles and provides reference for the application of high-energy composites.

| S-EPMC7841798 | biostudies-literature

Dissociative Ionization and Thermal Decomposition of Cyclopentanone.

Project description:Despite the growing use of renewable and sustainable biofuels in transportation, their combustion chemistry is poorly understood, limiting our efforts to reduce harmful emissions. Here we report on the (dissociative) ionization and the thermal decomposition mechanism of cyclopentanone, studied using imaging photoelectron photoion coincidence spectroscopy. The fragmentation of the ions is dominated by loss of CO, C2 H4 , and C2 H5 , leading to daughter ions at m/z 56 and 55. Exploring the C5 H8 O.+ potential energy surface reveals hydrogen tunneling to play an important role in low-energy decarbonylation and probably also in the ethene-loss processes, yielding 1-butene and methylketene cations, respectively. At higher energies, pathways without a reverse barrier open up to oxopropenyl and cyclopropanone cations by ethyl-radical loss and a second ethene-loss channel, respectively. A statistical Rice-Ramsperger-Kassel-Marcus model is employed to test the viability of this mechanism. The pyrolysis of cyclopentanone is studied at temperatures ranging from about 800 to 1100?K. Closed-shell pyrolysis products, namely 1,3-butadiene, ketene, propyne, allene, and ethene, are identified based on their photoion mass-selected threshold photoelectron spectrum. Furthermore, reactive radical species such as allyl, propargyl, and methyl are found. A reaction mechanism is derived incorporating both stable and reactive species, which were not predicted in prior computational studies.

| S-EPMC5639375 | biostudies-literature

Domain-selective thermal decomposition within supramolecular nanoribbons.

Project description:Self-assembly of small molecules in water provides a powerful route to nanostructures with pristine molecular organization and small dimensions (<10 nm). Such assemblies represent emerging high surface area nanomaterials, customizable for biomedical and energy applications. However, to exploit self-assembly, the constituent molecules must be sufficiently amphiphilic and satisfy prescribed packing criteria, dramatically limiting the range of surface chemistries achievable. Here, we design supramolecular nanoribbons that contain: (1) inert and stable internal domains, and (2) sacrificial surface groups that are thermally labile, and we demonstrate complete thermal decomposition of the nanoribbon surfaces. After heating, the remainder of each constituent molecule is kinetically trapped, nanoribbon morphology and internal organization are maintained, and the nanoribbons are fully hydrophobic. This approach represents a pathway to form nanostructures that circumvent amphiphilicity and packing parameter constraints and generates structures that are not achievable by self-assembly alone, nor top-down approaches, broadening the utility of molecular nanomaterials for new targets.

| S-EPMC8688471 | biostudies-literature

Thermal Decomposition of Maya Blue: Extraction of Indigo Thermal Decomposition Steps from a Multistep Heterogeneous Reaction Using a Kinetic Deconvolution Analysis.

Project description:Examining the kinetics of solids' thermal decomposition with multiple overlapping steps is of growing interest in many fields, including materials science and engineering. Despite the difficulty of describing the kinetics for complex reaction processes constrained by physico-geometrical features, the kinetic deconvolution analysis (KDA) based on a cumulative kinetic equation is one practical method of obtaining the fundamental information needed to interpret detailed kinetic features. This article reports the application of KDA to thermal decomposition of clay minerals and indigo-clay mineral hybrid compounds, known as Maya blue, from ancient Mayan civilization. Maya blue samples were prepared by heating solid mixtures of indigo and clay minerals (palygorskite and sepiolite), followed by purification. The multistep thermal decomposition processes of the clay minerals and Maya blue samples were analyzed kinetically in a stepwise manner through preliminary kinetic analyses based on a conventional isoconversional method and mathematical peak deconvolution to finally attain the KDA. By comparing the results of KDA for the thermal decomposition processes of the clay minerals and the Maya blue samples, information about the thermal decomposition steps of the indigo incorporated into the Maya blue samples was extracted. The thermal stability of Maya blue samples was interpreted through the kinetic characterization of the extracted indigo decomposition steps.

| S-EPMC6651835 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data