Selective oxidation of aromatic hydrocarbons by potassium and phosphorous-modified iron oxide–silica nanocomposite

Abstract  

Supported iron catalysts are active for hydrocarbon oxidation with H₂O₂, but the hydrogen peroxide dismutation is a shortcoming that may constrain their applications. Herein, we attempted to address this problem using potassium and phosphate-doped iron oxide–silica nanocomposite (KPFeSi) synthesized via sol–gel methods. The promoted silica–iron oxide nanocomposite has been characterized by elemental analyses, FTIR, X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface-size determination. The synthesized KPFeSi was an active catalyst in the low-temperature liquid phase oxidation of various alkyl aromatics with hydrogen peroxide in conversions of 31–78%. Furthermore, the direct oxidation of benzene into phenol using hydrogen peroxide has been achieved in the absence of any acid with this KPFeSi compound.     

New view on the oxidation mechanisms of crude oil through combined thermal analysis methods

In the previous study, the oxidation behavior of four Chinese crude oils (Oil 1 to 4) in the presence and absence of rock cuttings was investigated by thermogravimetry/derivative thermogravimetry (TG/DTG) techniques and oxidation tube experiments. The present work investigates the thermal behavior of these oils by combining DTG–DTA method. First, we conducted comparative analysis about mass loss rate from DTG curves and endothermic/exothermic phenomenon from DTA curves attempting to clarify the endothermic or exothermic mechanism in crude oil low-temperature oxidation. Finally, we combined the thermal analysis method with low-temperature oil oxidation tube experiment in porous media to ascertain, whether the two methods are consistent in the aspect of low-temperature oxidation mechanism of crude oil by O₂ consumption rate and CO₂ generating rate (carbon bond stripping reaction rate). Results show that crude oils undergo an endothermic oxidation behavior during low-temperature oxidation stage, suggesting the decomposition of hydrocarbon components. Clay can play a catalytic effect on low-temperature oil oxidation. The results of DTG–DTA tests can also better reflect oil oxidation mechanism under real conditions.     

金属次卟啉二甲酯对空气氧化环己烷的催化作用

在无任何外加溶剂及共还原剂的条件下, 将金属次卟啉二甲酯应用于催化空气氧化环己烷的氧化反应. 结果表明, 金属次卟啉二甲酯能够很好地催化环己烷的氧化反应, 与简单的金属四苯基卟啉相比, 金属次卟啉二甲酯催化剂具有更高的催化活性. 进而研究了络合金属对其催化性能的影响.     

Characterization and quantification of the hydrocarbons fraction of the subcutaneous fresh fat of Iberian pig by off-line combination of high performance liquid chromatography and gas chromatography

Hydrocarbons in fresh subcutaneous fat of Iberian pig have been analyzed by GC-MS after fractionation of the unsaponifiable fraction with a new off-line combination of HPLC and GC method. The new method proposed improves the recovery and simultaneous quantification of terpenic hydrocarbons in comparison to the traditional LC method. When necessary and for identification purposes, selective ion monitoring (SIM) was used as acquisition mode in GC-MS. To determine the position of the double bonds in the unsaturated hydrocarbon chain the dimethyl disulfide derivatives (DMDS) were obtained. To elucidate the structure of the branched 1-alkenes the hydrocarbon fraction was submitted to hydrogenation. Thirty-five compounds have been identified, including n-alkanes, n-alkenes, branched (n-1,n-2-dimethyl-1-alkenes) and terpenic hydrocarbons, being the most abundant n-alkenes and n-alkanes of even chain of n-C12-n-C26. Besides the hydrocarbons already described in bibliography, a new diterpenic hydrocarbon, ent-kaurene, have been identified for the first time. The compound reported as Neophytadiene by other authors, has been identified as a 20 atoms hydrocarbon with two double bonds, the 7,11,15-trimethyl-heptadeca-1,4-diene.     

Detailed product analysis during low- and intermediate-temperature oxidation of ethylcyclohexane

An experimental study of the oxidation of ethylcyclohexane has been performed in a jet-stirred reactor with online gas chromatography, under quasi-atmospheric pressure (800 Torr), at temperatures ranging from 500 to 1100 K (low- and intermediate-temperature zone including the negative temperature coefficient area), at a residence time of 2 s, and for three equivalence ratios (0.25, 1, and 2). Ethylcyclohexane displays important low-temperature reactivity with a well-marked negative temperature coefficient behavior. In addition to 47 products with a mass lower than ethylcyclohexane which have been quantified, many species with a C(8)H(14)O formula (molecular weight of 126) were detected by GC-MS and 7 of them were quantified. These molecules are cyclic ethers, ketones, and aldehydes with the same carbon skeleton as the reactant. Experiments were also carried on under the same conditions for two other C(8) hydrocarbons, n-octane and 1-octene, showing that the reactivity of ethylcyclohexane is close to that of the alkene and lower than that of the alkane. Simulations using a detailed kinetic model of the literature allow a good prediction of the global reactivity and of the main hydrocarbon products for temperatures above 800 K. The main reaction channels leading to the observed reaction products at both low (below 800 K) and intermediate temperature (above 800 K) are discussed.     

Modeling of Low-temperature oxidation and combustion of droplets

Key features of radiation extinguishing of spherical hot flame around a single droplet with its subsequent low-temperature oxidation and combustion under microgravity conditions—a phenomenon discovered in experiments onboard the International Space Station—have been reproduced using the mathematical model of droplet combustion and detailed kinetic mechanism of n-heptane oxidation and combustion. It has been demonstrated that experimentally observed repeated temperature flashes were blue flame flashes, and their duration was determined by the hydrogen peroxide decomposition time. In addition to this phenomenon, calculations predict the existence of new modes of low-temperature oxidation and combustion of droplets without the hot flame stage. In such modes, the basic reaction is concentrated very close to the droplet surface, and fuel vapor reacts in it only partially.     

Determination of 2,3-dihydro-6-[3-(2-hydroxymethyl)phenyl-2-propenyl]-5-benzofuranol in plasma using liquid chromatography with electrochemical detection

A reversed-phase column liquid chromatographic (LC) method with electrochemical detection (ED) is described for the quantification of 2,3-dihydro-6-[3-(2-hydroxymethyl)phenyl-2-propenyl]-5-benzofuranol (compound 1), a new locally active dual inhibitor of leukotriene and prostaglandin synthesis, in plasma. After a single liquid-liquid extraction of the biological specimen, the extract was analyzed using a liquid chromatograph with an amperometric detector set at an oxidation potential of +0.55 V. The resulting chromatograms are free from endogenous interference and the limit of detection is 0.2 ng/ml. Several other analogous dihydrobenzofuranols were shown to be electrochemically active, permitting their determination using LC with ED. The described analytical method has been fully validated in the concentration range 0.5-20 ng/ml of plasma and utilized in the analysis of plasma samples from human clinical studies. The analytical methodology has also been adapted for analysis of compound 1 in human skin blister fluid after topical administration of 1.     

Interaction of NO2 with hydrocarbon soot: focus on HONO yield, surface modification, and mechanism

Using a coated-wall flow tube connected to a mass spectrometer, the heterogeneous conversion of NO2 to HONO on dry hydrocarbon soot surfaces has been studied at room temperature and 243 K. Particular attention was given to the measurement of the HONO yield as a function of hydrocarbon fuel, NO2 partial pressure, extent of uptake, and surface oxidation state. In all cases, the yield is invariant of these parameters and close to unity, indicative of an irreversible oxidation mechanism by which the NO2 abstracts an H atom from the surface. XPS analysis shows that the surface N content does not measurably increase with NO2 exposure. There is minimal surface reactivity regeneration with time or via exposure to high relative humidity. A BET surface area measurement of the entire soot film exposed to NO2 was used to determine the amount of HONO that can be generated from the soot surface per unit surface area, prior to its deactivation. The reduction of NO2 to HONO on soot is unlikely to account for the observed nighttime buildup of HONO in polluted urban environments.     

Restructuring-induced activity of SiO(2)-supported large au nanoparticles in low-temperature CO oxidation

Large Au nanoparticles with an average size of approximately 10 nm supported on inert SiO(2) become active in low-temperature CO oxidation after the addition of NaNO(3). The catalyst structures have been characterized in detail by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and X-ray absorption spectroscopy. The NaNO(3) additive in Au/SiO(2) catalysts does not lead to the formation of fine Au nanoparticles, which are generally considered to be inevitable in low-temperature CO oxidation catalyzed by gold, nor does it alter the electronic structure of Au. The NaNO(3)-induced restructuring of large Au nanoparticles was proposed to create low-coordinated Au sites on the surface capable of catalyzing low-temperature CO oxidation. These results experimentally prove that the activity of supported Au nanoparticles in low-temperature CO oxidation could solely arise from their geometric structure, which greatly deepens the fundamental understandings of Au nanocatalysis.     

Structural and EPR study of the dependence on deuteration of the Jahn-Teller distortion in ammonium hexaaquacopper(II) sulfate, (NH4)

The variation of the EPR spectra with degree of deuteration of the partially deuterated Tutton salt ammonium hexaaquacopper(II) sulfate, (NH4)2[Cu(H2O)6](SO4)2, has been measured at 293 K. The measurements indicate that the structure changes quite abruptly from that of the pure hydrogenous salt to that of the fully deuterated salt at approximately 50% deuteration. The structure of a crystal in which approximately 42% of the hydrogen atoms were replaced by deuterium was elucidated at 15 K by single-crystal time-of-flight neutron diffraction. The hexaaquacopper(II) complex exhibits an orthorhombically distorted, tetragonally elongated octahedral coordination geometry (Cu-O bond distances of 2.281(1), 2.007(1), and 1.975(1) A). The structure is very similar to that reported for the undeuterated salt at 9.6 K, and markedly different from that of the fully deuterated compound at 15 K, which has similar Cu-O bond lengths but with the directions of the long and intermediate bonds interchanged. There is no evidence for disorder or partial switching of the Cu-O bond directions. This is consistent with the temperature dependence of the EPR spectrum of the approximately 42% deuterated compound, which indicates a thermal equilibrium between the two structural forms close to room temperature similar to that reported for the undeuterated compound, but complete reversion to the low-temperature phase on cooling to 5 K. The possible influence of deuteration upon the hydrogen-bonding distances and the bearing of this upon the structural modifications of the compound are discussed.     

The Cool Flames of Hydrocarbons

This review describes the properties of the cool-flame and two-stage ignition processes that characterize the gaseous oxidation of hydrocarbons and discusses the chemical reactions that are responsible for these phenomena. Cool flames result from a chainthermal acceleration of reaction rate. It is probable that the free-radical chain involved is propagated by the reaction of an alkyl radical with oxygen to give an alkyperoxy radical which isomerizes to a hydroperoxyalkyl radical. The decomposition of this radical produces a hydroxyl radical, which attacks the hydrocarbon rapidly and unselectively to regenerate an alkyl radical. Branching probably results from the pyrolysis of mono- and dihydroperoxides, from the oxidation of aldehydes, and from radical-molecule reactions. This reaction scheme explains the existence of a low-temperature ignition peninsula and the relation of the extent and shape of this peninsula to the molecular structure of the hydrocarbon. The chemical relevance of cool flames to abnormal combustion phenomena, such as knock, in gasoline engines is discussed.     

Prediction of a phase transition to a hydrogen bond ordered form of ice VI

Ice VI is a hydrogen bond disordered crystal over its known region of stability. In this work, we predict that ice VI will transform into a hydrogen bond ordered phase near 108 K, and have identified the likely low-temperature phase as ferroelectric (space group Cc) with an antiferroelectric structure (space group P2(1)2(1)2(1)) close by in energy. Electronic density functional theory calculations provide input to our calculations, which are extended to cells large enough for statistical simulations by using graph invariants. A significant decrease in the configurational entropy is predicted as hydrogen bonds exhibit partial order above the transition, provided that the hydrogen bonds can equilibrate on an experimental time scale. Conversely, partial disorder is predicted at temperatures below the transition. Although some evidence for ordering of ice VI has been observed in experiments, a low-temperature proton ordered phase has not been identified experimentally.     

Unusual geometries and questions of oxidation state in potential Sn(III) chemistry

A mixed-valence compound (Sn2I3(NPPh3)3) with nonequivalent Sn atoms in characteristic 2+ and 4+ Sn geometries, raised the idea of an average Sn3+ structure. The extended structures of Sr4Sn2Se9 and Sr4Sn2Se10 contain an unusual Sn2Se6 subunit, which has two equal Se-Sn-Se angles close to 160 degrees. This was suggestive of a Sn3+/Sn3+ compound, similar to the putative transition state for the valence state interchange in the molecular compound. These interesting geometrical features of two quite different molecules prompt a series of computations, a detective story of geometries and oxidation states, which concludes tentatively that the Sn with the abnormal angle in the extended structure is still likely to be formally Sn4+.     

Features of the initial stages of the oxidation of lignin by hydrogen peroxide

The kinetics of the initial stages of the oxidation of lignin and of several model compounds have been studied by the stopped-jet method. It has been shown that in the initial stage an intermediate compound is formed with an absorption spectrum close to that of phenoxyl radicals and with a lifetime of 0.013 sec. The high reactivity of the intermediate products leads to a branching of the oxidation process.Siberian Scientific-Research Institute of Pulp and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 516–518, July–August, 1983.     

A density functional study of O-O bond cleavage for a biomimetic non-heme iron complex demonstrating an Fe(v)-intermediate

Density functional theory using the B3LYP hybrid functional has been employed to investigate the reactivity of Fe(TPA) complexes (TPA = tris(2-pyridylmethyl)amine), which are known to catalyze stereospecific hydrocarbon oxidation when H(2)O(2) is used as oxidant. The reaction pathway leading to O-O bond heterolysis in the active catalytic species Fe(III)(TPA)-OOH has been explored, and it is shown that a high-valent iron-oxo intermediate is formed, where an Fe(V) oxidation state is attained, in agreement with previous suggestions based on experiments. In contrast to the analogous intermediate [(Por.)Fe(IV)=O](+1) in P450, the TPA ligand is not oxidized, and the electrons are extracted almost exclusively from the mononuclear iron center. The corresponding homolytic O-O bond cleavage, yielding the two oxidants Fe(IV)=O and the OH. radical, has also been considered, and it is shown that this pathway is inaccessible in the hydrocarbon oxidation reaction with Fe(TPA) and hydrogen peroxide. Investigations have also been performed for the O-O cleavage in the Fe(III)(TPA)-alkylperoxide species. In this case, the barrier for O-O homolysis is found to be slightly lower, leading to loss of stereospecificity and supporting the experimental conclusion that this is the preferred pathway for alkylperoxide oxidants. The difference between hydroperoxide and alkylperoxide as oxidant derives from the higher O-O bond strength for hydrogen peroxide (by 8.0 kcal/mol).     

Defects in divided zinc-copper aluminate spinels: structural features and optical absorption properties

Zn1-xCuxAl2O4 (0 < or = x < 0.30) compounds have been synthesized by polyesterification using metallic salts and annealing at low temperatures as well as by conventional solid state. XRD-powder data refinements (Rietveld method) have demonstrated that both compound series crystallize in the spinel structure (Fd3m) and exhibit similar inversion rates. This low-temperature route lead to metastable phases with crystallite sizes around 40 nm whereas particle sizes are larger than 1 moicrom in the case of solid-state route. This preparative method largely described in the literature allows stabilizing reduced copper states thanks to the presence of reductive organic species, which are decomposed below T = 700 degrees C. The absorption spectra of the x = 0.15 composition exhibit strong differences depending on the synthesis route. These differences can be explained by the occurrence of Cu2+/Cu+ mixed valencies in compounds prepared by the low-temperature route; 33% of monovalent copper has been identified in the x = 0.15 composition prepared by low-temperature process, whereas the solid-state compound contains only divalent copper. Reductive properties of polyesterification reaction implying citric acid and low annealing temperature (T = 700 degrees C) are mainly responsible of the occurrence of the Cu2+/Cu+ mixed valencies. Actually, the annealing under air at T = 1000 degrees C of divided zinc-copper aluminates prepared at low temperatures (T = 700 degrees C) leads to the oxidation reaction Cu+ --> Cu2+ + e- confirmed by the evolution of magnetic measurements, ESR spectra, and optical absorption properties. Defects such as oxygen vacancies in the anionic network leading to reduction in the cations coordination number could also explain the strong evolution of optical absorption spectra especially around lambda = 700 nm where intervalencies transfer (Cu+/Cu2+) as well as intra-atomic d-d transitions (Cu2+ in a 5-fold coordination) can occur. Finally the occurrence of monovalent and divalent copper at the surface of such divided oxides, probably in tetrahedral sites, has been demonstrated by FTIR spectroscopy using the co-adsorption of CO and NO as probe molecules.     

Mercapturic acids derived from toluene in rat urine samples: identification and measurement by gas chromatography–tandem mass spectrometry

Toluene is one of the most widely used CMR chemicals in industry. Worker exposure to this compound is regulated in France, but new, more sensitive methods are required to effectively monitor this exposure. A gas chromatography-tandem mass spectrometry (GC-MS/MS) method was developed and fully validated for the simultaneous determination of urinary toluene mercapturic acids derived from side chain and ring oxidation, i.e., benzylmercapturic acid and the three isomers o-, m- and p-toluylmercapturic acids, respectively. The method involves a simple and efficient two-step preparation procedure consisting of liquid-liquid extraction of the urinary acids followed by a microwave-assisted esterification of the isolated compounds using 2-propanol. The method meets all the required validation criteria: high selectivity, intra-day and inter-day precision ranges between 1.0?% and 12.4?%, with close to 100?% recovery. Linearity has been shown over the reduced concentration range 0.03-0.5?mg/L whereas a multiplicative model (ln-ln transformation) had to be used to describe the full range of concentrations 0.03-20?mg/L. The limits of detection for the four analytes, ranging from 2.8 to 5.5?μg/L, made the method suitable for their identification and quantification in urine from rats inhaling toluene in the 2 to 200?ppm concentration range. All urine samples from exposed rats contained measurable amounts of all metabolites. This is the first time that o- and m-toluylmercapturic acids have been shown to occur. Our results confirm the hypothesis that toluene mercapturic acids derived from ring oxidation exist in three forms.     

Catalytic oxidation of aliphatic alcohols in the tetraaquapalladium(ii) complex—iron(iii)—dioxygen system

The selective low-temperature (40—70 °C) catalytic oxidation of methanol, propan-1-ol, and propan-2-ol in the presence of the tetraaquapalladium(ii) complex and iron(iii) ions and/or molecular oxygen as cooxidants was studied. The corresponding carbonyl compound is the product of alcohol oxidation. The kinetic regularities of the reaction were established. In the reaction mechanism proposed, the key step is palladium(i) formation.     

Low-temperature aqueous phase oxidation of cyanide ions with the participation of nickel oxide system

The low-temperature oxidation of cyanide ions to CO₂ and N₂ in an aqueous phase in the presence of Ni-oxide system has been studied. The effect of pH, temperature and catalyst amount on the rate and selectivity of the oxidation process have been investigated. A kinetic model of the reaction studied is proposed based on the experimental results. It can be used to develop a catalytic method for purification of CN containing wastewaters.     

Role of O2 + QOOH in low-temperature ignition of propane. 1. Temperature and pressure dependent rate coefficients

The kinetics of the reaction of molecular oxygen with hydroperoxyalkyl radicals have been studied theoretically. These reactions, often referred to as second O(2) addition, or O(2) + QOOH reactions, are believed to be responsible for low-temperature chain branching in hydrocarbon oxidation. The O(2) + propyl system was chosen as a model system. High-level ab initio calculations of the C(3)H(7)O(2) and C(3)H(7)O(4) potential energy surfaces are coupled with RRKM master equation methods to compute the temperature and pressure dependence of the rate coefficients. Variable reaction coordinate transition-state theory is used to characterize the barrierless transition states for the O(2) + QOOH addition reactions as well as subsequent C(3)H(6)O(3) dissociation reactions. A simple kinetic mechanism is developed to illustrate the conditions under which the second O(2) addition increases the number of radicals. The sequential reactions O(2) + QOOH → OOQOOH → OH + keto-hydroperoxide → OH + OH + oxy-radical and the corresponding formally direct (or well skipping) reaction O(2) + QOOH → OH + OH + oxy-radical increase the total number of radicals. Chain branching through this reaction is maximized in the temperature range 600-900 K for pressures between 0.1 and 10 atm. The results confirm that n-propyl is the smallest alkyl radical to exhibit the low-temperature combustion properties of larger alkyl radicals, but n-butyl is perhaps a truer combustion archetype.