Evidence of catalyzed oxidation of Li2O2 for rechargeable Li-air battery applications

The oxidation kinetics of Li(2)O(2) was studied in a carbonate-free electrolyte using electrodes consisting of non-catalyzed and catalyzed Vulcan carbon (VC) and chemically synthesized Li(2)O(2) particles. VC and Au nanoparticles supported on VC (Au/C) were fairly inactive for catalyzing the oxidation of Li(2)O(2), where oxidation currents greater than 10 mA g(carbon)(-1) were found only at voltages equal to and greater than 4.0 V vs. Li (V(Li)). Pt and Ru nanoparticles supported on VC (Pt/C and Ru/C) could significantly increase the kinetics of Li(2)O(2) oxidation, where Li(2)O(2) could be removed largely at voltages below 4 V(Li). In addition, Pt/C and Ru/C showed quick initiation of Li(2)O(2) oxidation in contrast to VC and Au/C.     

在TiO2上CO的光催化氧化

最近在“氧化的”TiO₂(即表面无氧空位和Ti³⁺)上进行的CO光催化氧化研究发现:室温下,以黑光灯(峰值λ=365nm)光照时,“氧化的”TiO₂无CO催化氧化的活性,但以杀菌灯(峰值λ=253.7nm)光照时,则对CO产生显著的催化活性.参照CO在过渡金属表面的催化氧化机理,对本现象进行了解释:黑光灯照时,O₂在TiO₂表面只生成O_2(a)^-,而O_2(a)^-不能使CO氧化,只有以杀菌灯照时,TiO₂表面产生O_(a)^-,CO氧化反应才能发生.     

Electrochemical oxidation of nitrite and the oxidation and reduction of NO2 in the room temperature ionic liquid [C2mim][NTf2

The electrochemical oxidation of potassium nitrite has been studied in the room temperature ionic liquid (RTIL) [C2mim][NTf2] by cyclic voltammetry at platinum electrodes. A chemically irreversible oxidation peak was observed, and a solubility of 7.5(+/-0.5) mM and diffusion coefficient of 2.0(+/-0.2)x10(-11) m2 s(-1) were calculated from potential step chronoamperometry on the microdisk electrode. A second, and sometimes third, oxidation peak was also observed when the anodic limit was extended, and these were provisionally assigned to the oxidation of nitrogen dioxide (NO2) and nitrate (NO3-), respectively. The electrochemical oxidation of nitrogen dioxide gas (NO2) was also studied by cyclic voltammetry in [C2mim][NTf2] on Pt electrodes of various size, giving a solubility of ca. 51(+/-0.2) mM and diffusion coefficient of 1.6(+/-0.05)x10(-10) m2 s(-1) (at 25 degrees C). It is likely that NO2 exists predominantly as its dimer, N2O4, at room temperature. The oxidation mechanism follows a CE process, which involves the initial dissociation of the dimer to the monomer, followed by a one-electron oxidation. A second, larger oxidation peak was observed at more positive potentials and is thought to be the direct oxidation of N2O4. In addition to understanding the mechanisms of NO2- and NO2 oxidations, this work has implications in the electrochemical detection of nitrite ions and of NO2 gas in RTIL media, the latter which may be of particular use in gas sensing.     

CO oxidation mechanism on CeO(2)-supported Au nanoparticles

Density functional theory was used to study the CO oxidation catalytic activity of CeO(2)-supported Au nanoparticles (NPs). Experimental observations on CeO(2) show that the surface of CeO(2) is enriched with oxygen vacancies. We compare CO oxidation by a Au(13) NP supported on stoichiometric CeO(2) (Au(13)@CeO(2)-STO) and partially reduced CeO(2) with three vacancies (Au(13)@CeO(2)-3VAC). The structure of the Au(13) NP was chosen to minimize structural rearrangement during CO oxidation. We suggest three CO oxidation mechanisms by Au(13)@CeO(2): CO oxidation by coadsorbed O(2), CO oxidation by a lattice oxygen in CeO(2), and CO oxidation by O(2) bound to a Au-Ce(3+) anchoring site. Oxygen vacancies are shown to open a new CO oxidation pathway by O(2) bound to a Au-Ce(3+) anchoring site. Our results provide a design strategy for CO oxidation on supported Au catalysts. We suggest lowering the vacancy formation energy of the supporting oxide, and using an easily reducible oxide to increase the concentration of reduced metal ions, which act as anchoring sites for O(2) molecules.     

Highly diastereoselective oxidation of 2-amino-2-deoxy-1-thio-beta-D-glucopyranosides: synthesis of imino sulfinylglycosides

A synthetic route to imino thioglycosides and to imino sulfinylglycosides has been developed. A detailed study on the diastereoselective oxidation of 2-amino-2-deoxy-1-thio-beta-D-glucopyranosides is reported. It has been shown that the stereochemical outcome of the oxidation is highly dependent on the protective group of the amine function. While the oxidation of iminothioglycosides is slightly diastereoselective (up to 30% de in favor of the R(S) sulfoxide), a single isomer is obtained in the case of tetrachlorophthalimido derivatives. The absolute configuration of the sulfinyl glycoside was ascertained by NMR analysis using our recent model on the basis of the exo-anomeric effect corroborated by X-ray crystallography.     

Oxidation mechanism of phenols by dicopper-dioxygen (Cu(2)/O(2)) complexes

The first systematic studies on the oxidation of neutral phenols (ArOH) by the mu-eta(2):eta(2)-peroxo)dicopper(II) complex (A) and the bis(mu-oxo)dicopper(III) complex (B) supported by the 2-(2-pyridyl)ethylamine tridentate and didentate ligands L(Py2) and L(Py1), respectively, have been carried out in order to get insight into the phenolic O-H bond activation mechanism by metal-oxo species. In both cases (A and B), the C-C coupling dimer was obtained as a solely isolable product in approximately 50% yield base on the dicopper-dioxygen (Cu(2)/O(2)) complexes, suggesting that both A and B act as electron-transfer oxidants for the phenol oxidation. The rate-dependence in the oxidation of phenols by the Cu(2)/O(2) complexes on the one-electron oxidation potentials of the phenol substrates as well as the kinetic deuterium isotope effects obtained using ArOD have indicated that the reaction involves a proton-coupled electron transfer (PCET) mechanism. The reactivity of phenols for net hydrogen atom transfer reactions to cumylperoxyl radical (C) has also been investigated to demonstrate that the rate-dependence of the reaction on the one-electron oxidation potentials of the phenols is significantly smaller than that of the reaction with the Cu(2)O(2) complexes, indicative of the direct hydrogen atom transfer mechanism (HAT). Thus, the results unambiguously confirmed that the oxidation of phenols by the Cu(2)O(2) complex proceeds via the PCET mechanism rather than the HAT mechanism involved in the cumylperoxyl radical system. The reactivity difference between A and B has also been discussed by taking account of the existed fast equilibrium between A and B.     

酸性溶液中NaH2PO2在铂电极上氧化的原位红外光谱研究

用SNIFTIRS和循环伏安法研究酸性溶液中次亚磷酸钠在多晶铂电极上的电氧化机理.分析了0.5mol/LH2SO4+0.1mol/LNaH2PO2溶液中原位红外反射谱图与电极电位的关系,发现在发生反应的电位下Pt电极上的吸附物种有氢原子和H2PO2,最终的氧化产物是H3PO4而不是H2PO3-,据此提出了酸性介质中次亚磷酸根离子在Pt上氧化的新机理.     

Evolution of H2O and CO2 during the copper-catalyzed oxidation of isotactic polypropylene

The kinetics and mechanism of H₂O and CO₂ evolution during uncatalyzed and copper(oxide)-catalyzed (Cu, CuO, CuO_0.67) oxidation of isotactic polypropylene have been investigated in detail for various catalysts over a range of temperatures (90–150°C). These volatiles were determined chromatographically; H₂O and CO₂ represent the main volatiles of the oxidation, comprising about 80 mol % of all volatiles. Uncatalyzed oxidation evolves ca. 1 mol of H₂O and 1 mol of CO₂ for each unit mole of polymer oxidized, while catalyzed oxidation produces 2 mol of H₂O and ca. 1.2 mol of CO₂ for each unit mole of polymer. These results indicate that secondary as well as tertiary H atoms on the polymer chains are involved in hydroperoxide formation and decay. The oxidation mechanism has been formulated and evaluated on this basis. It consists essentially of two parallel oxidation reactions involving tertiary and secondary groups (H atoms and hydroperoxides), respectively. The mechanism can be represented by first- and pseudo-first-order reactions in series: (1) oxygen absorption showing induction periods; (2) hydroperoxide formation and decay (plateaus are reached); (3) H₂O evolution from the decay of hydroperoxides; and (4) subsequent CO₂ production involving chain scission. Arrhenius parameters for all oxidation reactions (uncatalyzed and catalyzed) are also presented. It appears that CuO_0.67 is the most efficient catalyst of those investigated.     

二氧化钛薄膜上三氯乙烯光催化氧化反应机理

 研究了二氧化钛薄膜上三氯乙烯(TCE)气相光催化氧化的反应机理. 结果表明,TCE气相光催化氧化反应生成的氯气可引发TCE的连锁反应. 当添加氯气的浓度相同时TCE表面光催化反应的初速率约为光化学反应初速率的2倍,说明连锁反应主要发生在催化剂表面. 氯可吸附在催化剂表面,作为电子的接受体抑制空穴与电子复合,提高TiO2光催化剂的活性. 除了TCE与吸附在催化剂表面的·OH的相互作用及反应产物/中间产物二氯乙酰氯的光催化分解可生成氯气以外,光气在与氯气共存时的光分解也有利于氯的生成.     

Diffusion reaction of oxygen in HfO2/SiO2/Si stacks

We study the oxidation mechanism of silicon in the presence of a thin HfO2 layer. We performed a set of annealing in 18O2 atmosphere on HfO2/SiO2/Si stacks observing the 18O distribution in the SiO2 layer with time-of-flight secondary ion mass spectrometry (ToF-SIMS). The 18O distribution in HfO2/SiO2/Si stacks upon 18O2 annealing suggests that what is responsible for SiO2 growth is the molecular O2, whereas no contribution is found of the atomic oxygen to the oxidation. By studying the dependence of the oxidation velocity from oxygen partial pressure and annealing temperature, we demonstrate that the rate-determining step of the oxidation is the oxygen exchange at the HfO2/SiO2 interface. When moisture is chemisorbed in HfO2 films, the oxidation of the underlying silicon substrate becomes extremely fast and its kinetics can be described as a wet silicon oxidation process. The silicon oxidation during O2 annealing of the atomic layer deposited HfO2/Si is fast in its early stage due to chemisorbed moisture and becomes slow after the first 10 s.     

Propane oxidation with chemically bound oxygen on Pt/TiO2/Al2O3 and Pt/CeO2/Al2O3 catalysts

Possible mechanisms are suggested for propane oxidation on Pt/TiO₂/Al₂O₃ and Pt/CeO₂/Al₂O₃ catalysts in the cyclic reactant supply mode. As compared to the steady-state process, the process conducted as catalyst oxidation-reduction cycles results in a very different product composition: it is more selective toward partial oxidation products and yields much smaller amounts of complete oxidation products. It is established by isothermal and temperature-programmed oxygen desorption that, under the reaction conditions examined, the oxygen desorbed from the catalyst surface into the gas phase makes a negligible contribution to propane oxidation. It is proved by XPS that propane oxidation is due to the chemically bound oxygen of the catalyst. The hypothetical mechanism of the process includes propane activation on Pt followed by the transfer of the activated species to the oxygen-storing component (TiO₂ or CeO₂), where the intermediates are oxidized by chemically bound oxygen.     

Oxidation with the “O2−H2O2-vanadium complex-pyrazine-2-carboxylic acid” reagent

The oxidation of cyclohexene with hydrogen peroxide catalyzed by a vanadium complex and pyrazine-2-carboxylic acid (PCA) in air results in the formation of cyclohex-2-enyl hydroperoxide as the main product and cyclohex-2-enol, cyclohex-2-enone, cyclohex-3-enyl hydroperoxide, cyclohex-3-enol, cyclohexanol, cyclohexane, and 1,2-epoxycyclohexane in lesser amounts. The composition of the products of oxidation of decalin isomers with the system in question is similar to those obtained in the photochemical oxidation with hydrogen peroxide in air and in the oxidation with air in the presence of anthraquinone. A proposed mechanism for the oxidation includes the initiation by hydroxyl radicals generated from hydrogen peroxide under the action of the V-PCA system. For Part 8, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 253–258, February, 1998.     

Schiff碱配合物催化过氧化氢氧化苯酚的动力学研究

按照文献方法合成了钴(Ⅱ)和铁(Ⅱ)Schiff碱配合物,研究了它们作为模拟过氧化物酶在缓冲溶液中以及在三种不同的表面活性剂(CTAB,Brij35,LSS)胶束中催化过氧化氢氧化苯酚的反应,结果表明：过氧化氢／配合物物质的量比和胶束微环境对金属配合物催化过氧化氢氧化苯酚的反应有明显的影响;本文所提出的Schiff碱金属配合物催化苯酚氧化反应的机理和动力学数学模型是合理的。     

Diterpene Chemistry—VI : SeO2/H2O2 oxidations of exocyclic olefins

Unlike endocyclic olefins the major product from the SeO₂/H₂O₂ oxidation of exocyclic olefins is the same allylic alcohol as from the uncatalysed oxidation. Minor products derived from epoxide intermediates were investigated. The use of SeO₂ as an allylic oxidant for olefins has been extensively investigated, the functionality of the product being to a degree solvent dependent. Although the earlier mechanism of Guillemonat² is incorrect, his rules for the prediction of the position of oxidation still remain valid. A survey by Tratchenburg³ of the current position in SeO₂ oxidation postulates allylic oxidation as proceeding through the intermediacy of an oxaselenocyclobutane to a selenite ester which is solvated by competitive unimolecular (S_N1) and bimolecular (S_N2′) processes (Scheme 1).     

CO Preferential oxidation promoted by UV irradiation in the presence of H2 over Au/TiO2

The catalytic oxidation of CO was performed over Au/TiO(2) under UV irradiation in the presence of H(2) in different reaction systems. It was found that the introduction of H(2) enhanced the CO thermocatalytic oxidation in a CO pre-introduced system (CO/O(2)vs. CO/H(2)/O(2)), but suppressed that in an O(2) pre-introduced (O(2)/CO vs. O(2)/H(2)/CO) system. Although the CO oxidation in both CO/H(2)/O(2) and O(2)/H(2)/CO systems could be remarkably enhanced under UV irradiation, the oxidation of H(2) was suppressed under UV irradiation. It was proposed that the dissociative chemisorption H ([triple bond]Ti-H) at surface oxygen vacancy sites of TiO(2) could act as both the electron-acceptors for the photogeneration electrons and the electron-donors for the chemisorbed O(2) at TiO(2), and thus enhance the CO oxidation during the coinstantaneous process of thermocatalysis and photocatalysis. The suppression of H(2) thermocatalytic oxidation under UV irradiation might be ascribed to the electron transfer effect, i.e., the dissociative chemisorption H on Au (Au-H) could be desorbed at the H(2) molecule via accepting the photogenerated electrons from TiO(2).     

TiO2和ZnO表面CO光催化氧化活性研究

在TiO2和ZnO表面CO光催化氧化研究中发现,365 nm紫外光照下TiO2表面无活性,而ZnO表面却有明显的CO光催化氧化活性.研究表明,主要是由于紫外光照下,ZnO光分解而TiO2没有光分解,从而在表面产生不同吸附形态的氧所致.而且,ZnO表面CO光催化氧化反应活性可在27 h内保持稳定,暗示气相光催化反应中,ZnO不会因为光腐蚀而使其催化活性降低.     

V2O5/TiO2-ZrO2催化剂上甲醇选择氧化制甲缩醛

采用共沉淀法制备TiO2-ZrO2复合氧化物载体、等体积浸渍法制备V2O5/TiO2-ZrO2催化剂,对催化剂在温和条件下甲醇选择氧化生成甲缩醛(DMM)反应进行研究.结果表明,与单一氧化物载体TiO2或ZrO2负载的钒基催化剂相比,V2O5/TiO2-ZrO2对甲醇选择氧化具有较好的催化性能.XRD、NH3-TPD和...     

MoS2摩擦表面氧化与电子转移

利用电子自旋共振谱(ESR)和X射线光电子谱(XPS)研究了MoS2摩擦表面的氧化行为和摩擦表面氧化的电子转移,发现MoS2在摩擦失效过程中Mo4+与氧作用生成稳定的Mo6+终态氧化物,其间经过Mo5+过渡态。深入揭示了MoS2摩擦表面氧化过程的复杂性,指出Mo在摩擦表面氧化过程中以多种化学状态存在,Mo原子的氧化是Mo4d轨道上的单电子转移过程。     

Magnetically separable polyoxometalate catalyst for the oxidation of dibenzothiophene with H2O2

Two types of polyoxometalate-functionalized magnetic nanoparticles catalysts consisting of H(3)PW(12)O(40) supported on surface-modified Fe(3)O(4) magnetite nanoparticles were prepared using an easy synthetic route and successfully applied for the oxidation of dibenzothiophene. The magnetic catalysts showed a catalytic performance in the oxidation of dibenzothiophene in acetonitrile with hydrogen peroxide, and high conversions were obtained. The catalysts could be easily separated from the reaction solution by applying an external magnetic field and recycled several times.     

Oxidation of guanine in double-stranded DNA by [Ru(bpy)2dppz]Cl2 in cationic reverse micelles

DNA oxidation has been investigated in the medium of cationic reverse micelles (RMs). The oxidative chemistry is photochemically initiated using the DNA intercalator bis(bipyridine)dipyridophenazine ruthenium(II) chloride ([Ru(bpy)2dppz]Cl2) bound to duplex DNA in the RMs. High-resolution polyacrylamide gel electrophoresis (PAGE) is used to reveal and quantify guanine (G) oxidation products, including 8-oxo-7,8-dihydroguanine (8OG). In buffer solution, the addition of the oxidative quenchers potassium ferricyanide or pentaamminechlorocobalt(III) dichloride leads to an increase in the amount of piperidine-labile G oxidation products generated via one-electron oxidation. In RMs, however, the yield of oxidatively generated damage is attenuated. With or without ferricyanide quencher in the RMs, the yield of oxidatively generated products is approximately the same. Inclusion of the cationic quencher [CoCl(NH3)5]2+ in the RMs increases the amount of oxidation products generated but not to the extent that it does in buffer solution. Under anaerobic conditions, all of the samples in RMs, with or without added oxidative quenchers, show decreased levels of piperidine-labile oxidation products, suggesting that the primary oxidant in RMs is singlet oxygen. G oxidation is enhanced in D2O and deuterated heptane and is diminished in the presence of sodium azide in RMs, also supporting 1O2 as the main G oxidant in RMs. Isotopic labeling experiments show that the oxygen atom in 8OG produced in RMs is not from water. The observed change in the G oxidation mechanism from a one-electron process in buffer to mostly 1O2 in RMs illustrates the importance of both DNA structure and DNA environment on the chemistry of G oxidation.