Oxygen evolution as a critical test of mechanism in the ferric-ion catalyzed decomposition of hydrogen peroxide

The stoichiometry of O₂ evolution in the Fe³ catalyzed decomposition of H₂O₂ in dilute HClO₄ at high [Fe³⁺]/[H₂O₂] ratios is 2H₂O₂ → 2H₂O + O₂ with no deficiency indicating accumulation of an intermediate complex. This and the observed kinetics are shown to be consistent with a “redox chain” but not a “complex” mechanism for the reaction.     

“Complex” versus “free radical” mechanism for the catalytic decomposition of H2O2 by ferric ions

Kinetic and spectrophotometric measurements made during the Fe³⁺ ion catalyzed decomposition of H₂O₂ have been analyzed using the computer simulation method. Improved values of the rate constants of the “complex scheme” and of the molar absorptivities ofthe intermediates were obtained: k₃/K_M = 4.94 M^?1 min^?1, k₄ = 193 M^?1 min^?1, ε_I/K_M = 52.3 M^?2 cm^?1, ε_II = 25.7 M^?1 cm^?1. The simulation revealed details of the reaction which were unavailable by other means and which explained several features of its kinetics. The total amount of O₂ evolved in the reaction using [H₂O₂] ～ 10^?2 M has been calculated and found to be nearly stoichiometric. O₂ evolution experiments in this region cannot, thus, distinguish between the “complex mechanism” predicting nearly stoichiometric evolution of O₂ and the “free radical mechanism” predicting exactly stoichiometricamounts of O₂. There are discrepancies within the “free radical scheme” with regard to the correct values of the rate constants to fit the reactions of H₂O₂ both with Fe²⁺ and Fe³⁺ ions, as well as other reactions assumed to proceed via free radicals.     

Kinetics of the Fe3+ ion–H2O2 reaction: Steady-state and terminal-state analysis

Computer calculations of the kinetics of the ferric ion catalyzed decomposition of H₂O₂ by Walling and Weil are not in contradiction to the “complex mechanism.” The examination of their results reveals that their simulations correspond to the terminal state of the system in which the secondary complex between Fe³⁺ and H₂O₂ becomes stabilized.     

钙钛矿氧化物H1.9K0.3La0.5Bi0.1Ta2O7和Pt/WO3组成的Z体系下完全光解水性能

以质子化层状钙钛矿氧化物H_1.9K_0.3La_0.5Bi_0.1Ta₂O₇ (HKLBT)作为产氢催化剂, Pt/WO₃作为产氧催化材料进行Z 型体系下完全分解水反应. 考察了不同载流子传递介质及不同载流子浓度对反应活性的影响. 结果表明, 以Fe²⁺/Fe³⁺为载流子传递介质时可以实现水的完全分解(H₂/O₂体积比为2:1), 8 mmol·L^-1的FeCl₃作为初始载流子传递介质时, 产氢、产氧活性分别为66.8和31.8 μmol·h^-1, 氢氧体积比为2.1:1. 受光催化材料对载流子传递介质氧化还原速度的限制, 过高的载流子传递介质浓度并不能提高光催化活性.     

Hemoglobin as a nitrite anhydrase: modeling methemoglobin-mediated N2O3 formation

Nitrite has recently been recognized as a storage form of NO in blood and as playing a key role in hypoxic vasodilation. The nitrite ion is readily reduced to NO by hemoglobin in red blood cells, which, as it happens, also presents a conundrum. Given NO’s enormous affinity for ferrous heme, a key question concerns how it escapes capture by hemoglobin as it diffuses out of the red cells and to the endothelium, where vasodilation takes place. Dinitrogen trioxide (N₂O₃) has been proposed as a vehicle that transports NO to the endothelium, where it dissociates to NO and NO₂. Although N₂O₃ formation might be readily explained by the reaction Hb‐Fe³⁺+NO₂^?+NO?Hb‐Fe²⁺+N₂O₃, the exact manner in which methemoglobin (Hb‐Fe³⁺), nitrite and NO interact with one another is unclear. Both an “Hb‐Fe³⁺‐NO₂^?+NO” pathway and an “Hb‐Fe³⁺‐NO+NO₂^?” pathway have been proposed. Neither pathway has been established experimentally. Nor has there been any attempt until now to theoretically model N₂O₃ formation, the so‐called nitrite anhydrase reaction. Both pathways have been examined here in a detailed density functional theory (DFT, B3LYP/TZP) study and both have been found to be feasible based on energetics criteria. Modeling the “Hb‐Fe³⁺‐NO₂^?+NO” pathway proved complex. Not only are multiple linkage‐isomeric (N‐ and O‐coordinated) structures conceivable for methemoglobin–nitrite, multiple isomeric forms are also possible for N₂O₃ (the lowest‐energy state has an N? N‐bonded nitronitrosyl structure, O₂N? NO). We considered multiple spin states of methemoglobin–nitrite as well as ferromagnetic and antiferromagnetic coupling of the Fe³⁺ and NO spins. Together, the isomerism and spin variables result in a diabolically complex combinatorial space of reaction pathways. Fortunately, transition states could be successfully calculated for the vast majority of these reaction channels, both M_S=0 and M_S=1. For a six‐coordinate Fe³⁺‐O‐nitrito starting geometry, which is plausible for methemoglobin–nitrite, we found that N₂O₃ formation entails barriers of about 17–20 kcal mol^?1, which is reasonable for a physiologically relevant reaction. For the “Hb‐Fe³⁺‐NO+NO₂^?” pathway, which was also found to be energetically reasonable, our calculations indicate a two‐step mechanism. The first step involves transfer of an electron from NO₂^? to the Fe³⁺–heme–NO center ({FeNO}⁶) , resulting in formation of nitrogen dioxide and an Fe²⁺–heme–NO center ({FeNO}⁷). Subsequent formation of N₂O₃ entails a barrier of only 8.1 kcal mol^?1. From an energetics point of view, the nitrite anhydrase reaction thus is a reasonable proposition. Although it is tempting to interpret our results as favoring the “{FeNO}⁶+NO₂^?” pathway over the “Fe³⁺‐nitrite+NO” pathway, both pathways should be considered energetically reasonable for a biological reaction and it seems inadvisable to favor a unique reaction channel based solely on quantum chemical modeling.     

Decomposition of a cation exchange resin with hydrogen peroxide

Ion exchange resins are widely used in the field of nuclear industry. The present work aimed at the development of a method for complete decomposition of cation exchange resins with H₂O₂ in the presence of Fe³⁺ ion. The decomposition reaction proceeded at ambient temperature and decomposition time was greatly shortened with increasing concentration of Fe³⁺ ion rather than that of H₂O₂. The catalytic action of Fe³⁺ ion was suppressed with increase of HNO₃ concentration. As much as 4 g of the air-dried resin could be decomposed with 8 ml of 30% H₂O₂, and the use of about 60 ml of 30% H₂O₂ resulted in the complete decomposition of organic carbon to CO₂. Absence of any orgnaic carbon in the residual solution will simplify the final disposal.     

Photo-Fenton and photo-Fenton-like processes for the degradation of methyl orange in aqueous medium: Influence of oxidation states of iron

Degradation of methyl orange (MO) was carried out by the photo-Fenton process (Fe²⁺/H₂O₂/UV) and photo-Fenton-like processes (Fe³⁺/H₂O₂/UV, Fe²⁺/S₂O₈²⁻/UV, and Fe³⁺/S₂O₈²⁻/UV) at the acidic pH of 3 using hydrogen peroxide and ammonium persulfate (APS) as oxidants. Oxidation state of iron had a significant influence on the efficiency of photo-Fenton/photo-Fenton-like processes. It was found that a process with a source of Fe³⁺ ions as the catalyst showed higher efficiency compared to a process with the Fe²⁺ ion as the catalyst. H₂O₂ served as a better oxidant for both oxidation states of iron compared to APS. The lower efficiency of APS is attributed to the generation of excess protons which scavenges the hydroxyl radicals necessary for degradation. Further, the sulfate ions produced from S₂O₈²⁻ form a complex with Fe²⁺/Fe³⁺ ions thereby reducing the concentration of free iron ions in the solution. This process can also reduce the concentration of hydroxyl radicals in the solution. Efficiency of the various MO degradation processes follows the order: Fe³⁺/H₂O₂/UV, Fe³⁺/APS/UV, Fe²⁺/H₂O₂/UV, Fe²⁺/APS/UV.     

57Fe 穆斯堡尔谱研究 Ir-Fe 催化剂用于 CO 选择氧化反应

 采用不同浸渍顺序制备了三种 Ir-Fe 催化剂, 其 CO 选择氧化 (PROX) 反应活性差别很大, 其中共浸渍的 Ir-Fe 催化剂活性最高. 吸附量热研究表明, 三种催化剂的 H2 和 CO 吸附存在差别. 通过对三种催化剂还原后、再氧化和反应后准原位 57Fe 穆斯堡尔谱的研究, 得到各种 Fe 物种信息. 结果表明, 三种制备方法影响催化剂中 Ir-Fe 相互作用强度, 导致催化剂中 Fe 物种的氧化还原性能不同. 催化剂中 Fe²⁺(a) 的含量与 CO 转化率呈正比关系, Fe²⁺(a) 是 PROX 反应过程中活化氧的活性中心. 浸渍顺序改变了 Ir-Fe 间相互作用强度, 从而改变 Fe²⁺(a) 物种含量, 影响 PROX 反应活性. Ir-Fe 间的相互作用可以稳定活化氧的 Fe²⁺(a) 物种, 为今后研究金属-金属间的相互作用提供借鉴.     

A S2O32−‐Enhanced Fluorogenic Chemosensor for Fe3+ in Aqueous Media Based on a Boron–Fluorine Derivative

A fluorescent “turn‐on” probe for Fe³⁺ was investigated in an aqueous system based on a boron 2‐(2′‐pyridyl) imidazole complex (BOPIM‐dma). BOPIM‐dma shows weak or no fluorescence in polar solvents due to twisted intramolecular charge transfer, but the addition of Fe³⁺ to BOPIM‐dma leads to fluorescence switch‐on responses. The binding is highly selective to Fe³⁺ over other metal ions, indicating that BOPIM‐dma is a chemodosimeter for Fe³⁺. Furthermore, the existence of S₂O₃²⁻ could much enhance and stabilize the emission significantly, indicating that the BOPIM‐dma/Fe³⁺/S₂O₃²⁻ complexes are a strong fluorescence system, and can be used as a sensitive detector for Fe³⁺, with the limit of detection of 6.0 × 10⁻⁷ mol L⁻¹.     

Conversion of Chromium(III) Propionate to Chromate/dichromate(VI) by the Advanced Oxidation Process. Pretreatment of a Biomimetic Complex for Metal Analysis

The use of H₂O₂ and UV irradiation to remove organic ligands in a chromium(III) complex for the subsequent chromium analysis is reported. The Advanced Oxidation Process (AOP) using a 5.5-W UV lamp, H₂O₂ and Fe²⁺/Fe³⁺ as catalyst (photo Fenton process) was found to give complete and quantitative Cr(III) → Cr(VI) conversion and removal of ligands in chromium(III) propionate [Cr₃O(O₂CCH₂CH₃)₆(H₂O)₃]NO₃, a biomimetic chromium species, as subsequent chromium analyses by the 1,5-diphenylcarbazide method and atomic absorption revealed. The current process eliminates the need for mineralization and/or dissolution of the matrix in order to remove the organic ligand, the traditional pretreatments of a sample for metal analysis. Studies to optimize the conditions for the oxidation processes, including the use of Fe²⁺/Fe³⁺ catalyst, length of UV irradiation, H₂O₂ concentration, pH, power of UV lamp, and reactor size, are reported.     

Charge dynamics of 57Fe probe atoms in La2Li0.5Cu0.5O4

The objective of this study is to characterize the electronic state and local surrounding of ⁵⁷Fe Mössbauer probe atoms within iron-doped layered perovskite La₂Li_0.5Cu_0.5O₄ containing transition metal in unusual formal oxidation states “+3”. An approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that a large amount of charge is transferred via Cu-O bonds from the O: 2p bands to the Cu: 3d orbitals and the ground state is dominated by the d⁹L configuration (“Cu²⁺-O^-” state). The dominant d⁹L ground state for the (CuO₆) sublattice induces in the environment of the ⁵⁷Fe probe cations a charge transfer Fe³⁺ + O⁻(L) → Fe⁴⁺ + O²⁻, which transforms “Fe³⁺” into “Fe⁴⁺” state. The experimental spectra in the entire temperature range 77–300 K were described with the use of the stochastic two-level model based on the assumption of dynamic equilibrium between two Fe³⁺↔Fe⁴⁺ valence states related to the iron atom in the [Fe(1)O₄]^4- center. The relaxation frequencies and activation energies of the corresponding charge fluctuations were estimated based on Mössbauer data. The results are discussed assuming a temperature-induced change in the electronic state of the [CuO₄]^5- clusters in the layered perovskite.     

Porous α-Fe_2O_3/SnO_2 nanoflower with enhanced sulfur selectivity and stability for H_2S selective oxidation

Being abundant and active,Fe_2O_3 is suitable for selective oxidation of H_2S.However,its practical application is limited due to the poor sulfur selectivity and rapid deactivation.Herein,we report a facile template-free hydrothermal method to fabricate porous α-Fe_2O_3/SnO_2 composites with hierarchical nanoflower that can obviously improve the catalytic performance of Fe_2O_3.It was disclosed that the synergistic effect between α-Fe_2O_3 and SnO_2 promotes the physico-chemical properties of α-Fe_2O_3/SnO_2 composites.Specifically,the electron transfer between the Fe~(2+)/Fe~(3+) and Sn~(2+)/Sn~(4+) redox couples enhances the reducibility of α-Fe_2O_3/SnO_2 composites.The number of oxygen vacancies is improved when the Fe cations incorporate into SnO_2 structure,which facilitates the adsorption and activation of oxygen species.Additionally,the porous structure improves the accessibility of H_2 S to active sites.Among the composites,Fe1 Sn1 exhibits complete H_2 S conversion with 100% sulfur selectivity at 220℃,better than those of pure α-Fe_2O_3 and SnO_2.Moreover,Fe1 Sn1 catalyst shows high stability and water resistance.     

Photoelectrolysis of water by irradiation of platinized n-type semiconducting metal oxides

The basic principles of semiconductor photoelectrochemistry as applied to light to chemical and/or electrical energy conversions are outlined. Special emphasis is on the photoelectrolysis of H₂O to H₂ and O₂. New results are presented which show that platinized n-type SrTiO₃ and KTaO₃ evolve H₂ and O₂ from alkaline aqueous solutions when irradiated with ultraviolet light. The irradiated portions of the metal oxide behave as the photoanode and the dark platinized portions behave as the cathode. The nonplatinized oxides are energetically capable of evolving H₂ and O₂ upon irradiation but the overvoltage for H₂ is too great. The general requirement for the “short-circuit” redox chemistry at the irradiated n-type semiconductor surface is that the dark cathodic reaction occur at a potential more positive than the anodic reaction upon irradiation. The role of the Pt coating is to reduce the H₂ overvoltage to meet this requirement. It is demonstrated that polished n-type TiO₂ and SrTiO₃ are both capable of oxidizing H₂O to evolve O₂ and reducing Cu²⁺ to plate out Cu upon irradiation in 0.5 M CuSO₄ (pH = 7). We discuss the importance of “short-circuit” redox chemistry and overvoltage in obtaining opencircuit photopotential in photoelectrochemical cells.     

Elucidation of methyl tert-butyl ether degradation with Fe/H2O2 by purge-and-trap gas chromatography-mass spectrometry

Degradation of methyl tert-butyl ether (MTBE) with Fe²⁺/H₂O₂ was studied by purge-and-trap gas chromatography-mass spectrometry. MTBE was degraded 99% within 120 min under optimum conditions. MTBE was firstly degraded rapidly based on a Fe²⁺/H₂O₂ reaction and then relatively slower based on a Fe³⁺/H₂O₂ reaction. The dissolved oxygen decreased rapidly in the Fe²⁺/H₂O₂ reaction stage, but showed a slow increase in the Fe³⁺/H₂O₂ reaction stage. tert-Butyl formate, tert-butyl alcohol, methyl acetate and acetone were identified as primary degradation products by mass spectrometry. A preliminary reaction mechanism involving two different pathways for the degradation of MTBE with Fe²⁺/H₂O₂ was proposed. This study suggests that degradation of MTBE can be achieved using the Fe²⁺/H₂O₂ process.     

Coherence assembly phenomenon in the typical structures of heteropolyniobates

Crystallographic analysis has provided evidence for single cation frameworks formed from preordered cation positions in the individual building blocks (modules) constituting the basis of structures. We propose to call this phenomenon coherence assembly. According to the mechanical wave concept of the crystalline state, coherence assembly dictates the rules of mutual packing of “rigid” structural fragments. This study investigates the typical structures of heteropolyniobates: Na₁₂[Ti₂O₂][SiNb₁₂O₄₀]·4H₂O (I), menezesite Ba₂MgZr₄[BaNb₁₂O₄₂]·12H₂O (II), and the menezesite-isostructural aspedamite □₁₂(Fe³⁺,Fe²⁺)₃Nb₄·[Th(Nb,Fe³⁺)₁₂O₄₂]·(H₂O,OH)₁₂ (III).     

Synthesis, characterization, infrared studies, and thermal analysis of Mn0.6Zn0.4Fe2(C4H2O4)3·6N2H4 and its decomposition product Mn0.6Zn0.4Fe2O4

Manganese zinc ferrous fumarato–hydrazinate precursor, Mn_0.6Zn_0.4Fe₂(C₄H₂O₄)₃·6N₂H₄ was synthesized for the first time and characterized by chemical analysis, infrared spectral studies, and thermal analysis. Infrared studies show band at 977 cm^?1 indicating bidentate bridging nature of the hydrazine in the complex. Thermogravimetric (TG) studies show two steps dehydrazination followed by two steps total decarboxylation. The precursor on touching with burning splinter undergoes self propagating autocatalytic decomposition yielding ultrafine Mn_0.6Zn_0.4Fe₂O₄. XRD studies confirms single phase formation as well as nanosize nature of “as prepared” Mn_0.6Zn_0.4Fe₂O₄. The saturation magnetization of the “as prepared” Mn_0.6Zn_0.4Fe₂O₄ was found to be 31.46 emu gm^?1, which is lower than the reported, confirms the ultrafine nature of the oxide.     

Catalytic Hydroxylation of Benzene to Phenol by Dioxygen with an NADH Analogue

Hydroxylation of benzene by molecular oxygen (O₂) occurs efficiently with 10‐methyl‐9,10‐dihydroacridine (AcrH₂) as an NADH analogue in the presence of a catalytic amount of Fe(ClO₄)₃ or Fe(ClO₄)₂ with excess trifluoroacetic acid in a solvent mixture of benzene and acetonitrile (1:1 v/v) to produce phenol, 10‐methylacridinium ion and hydrogen peroxide (H₂O₂) at 298 K. The catalytic oxidation of benzene by O₂ with AcrH₂ in the presence of a catalytic amount of Fe(ClO₄)₃ is started by the formation of H₂O₂ from AcrH₂, O₂, and H⁺. Hydroperoxyl radical (HO₂^.) is produced from H₂O₂ with the redox pair of Fe³⁺/Fe²⁺ by a Fenton type reaction. The rate‐determining step in the initiation is the proton‐coupled electron transfer from Fe²⁺ to H₂O₂ to produce HO^. and H₂O. HO^. abstracts hydrogen rapidly from H₂O₂ to produce HO₂^. and H₂O. The Fe³⁺ produced was reduced back to Fe²⁺ by H₂O₂. HO₂^. reacts with benzene to produce the radical adduct, which abstracts hydrogen from AcrH₂ to give the corresponding hydroperoxide, accompanied by generation of acridinyl radical (AcrH^.) to constitute the radical chain reaction. Hydroperoxyl radical (HO₂^.), which was detected by using the spin trap method with EPR analysis, acts as a chain carrier for the two radical chain pathways: one is the benzene hydroxylation with O₂ and the second is oxidation of an NADH analogue with O₂ to produce H₂O₂.     

Grafting onto cellulose. VIII. Graft copolymerization of poly(ethylacrylate) onto cellulose by use of redox initiators. Comparison of initiator reactivities

In an attempt to compare the relative reactivities of different redox systems in graft copolymerization of vinyl monomers onto cellulose, we studied grafting of ethylacrylate (EA) in aqueous medium by using the well-known redox intiator, ferrous ammonium sulfate–potassium persulfate (FAS–KPS) system, and its reactivity was compared with that of Fenton's reagent (Fe²⁺ ?H₂O₂) towards grafting of EA onto cellulose. Optimum conditions for affording maximum grafting were evaluated and percent grafting is expressed as functions of different reaction variables. Evidence of grafting was obtained from IR spectroscopic measurements, SEM, and TGA studies of the grafted and ungrafted cellulose. A plausible explanation for the observed reactivity pattern shown by (FAS–KPS) and (FAS–H₂O₂) redox systems is offered. Fenton's reagent (Fe²⁺ ?H₂O₂) was found to be several times more reactive than (FAS–KPS) redox system.     

Iron(II) sulfate oxidation with oxygen on a Pt/C catalyst: A kinetic study

The kinetics of iron(II) sulfate oxidation with molecular oxygen on the 2% Pt/Sibunit catalyst was studied by a volumetric method at atmospheric pressure, T = 303 K, pH 0.33–2.4, [FeSO₄] = 0.06?0.48 mol/l, and [Fe₂(SO₄)₃] = 0?0.36 mol/l in the absence of diffusion limitations. Relationships were established between the reaction rate and the concentrations of Fe²⁺, Fe³⁺, H⁺, and Cl^? ions in the reaction solution. The kinetic isotope effect caused by the replacement of H₂O with D₂O and of H⁺ with D⁺ was measured. The dependence of Fe²⁺ and Fe³⁺ adsorption on the catalyst pretreatment conditions was studied. A reaction scheme is suggested, which includes oxygen adsorption, the formation of a Fe(II) complex with surface oxygen, and the one-electron reduction of oxygen. The last step can proceed via two pathways, namely, electron transfer with H⁺ addition and hydrogen atom transfer from the coordination sphere of the iron(II) aqua complex. A kinetic equation providing a satisfactory fit to experimental data is set up. Numerical values are determined for the rate constants of the individual steps of the scheme suggested.     

On‐surface Fenton and Fenton‐like reactions appraised by paper spray ionization mass spectrometry

On‐surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe²⁺/H₂O₂) and Fenton‐like (Mⁿ⁺/H₂O₂; Mⁿ⁺ = Fe³⁺, Co²⁺, Cu²⁺, Mn²⁺) systems was investigated by using paper spray ionization mass spectrometry (PS‐MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS‐MS analyzes). The results indicated the following order in the rates of such reactions: Fe²⁺/H₂O₂ ≫ H₂O₂ ≫ Cu²⁺/H₂O₂ > Mⁿ⁺/H₂O₂ (Mⁿ⁺ = Fe³⁺, Co²⁺, Mn²⁺) ~ Mⁿ⁺ (Mⁿ⁺ = Fe²⁺, Fe³⁺, Co²⁺, Cu²⁺, Mn²). The superior capability of Fe²⁺/H₂O₂ in causing the degradation of sildenafil indicates that Fe²⁺ efficiently decomposes H₂O₂ to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H₂O₂ can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, ie, Fe³⁺, Co²⁺, Cu²⁺, and Mn²⁺. A unique oxidation by‐product was detected in the reaction between Fe²⁺/H₂O₂ with sildenafil, and a possible structure for it was proposed based on the MS/MS data. The on‐surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS‐MS shows to be a convenient platform to promptly monitor on‐surface oxidation reactions.