不同浓度Sn4+离子掺杂TiO2的结构、性质和光催化活性

采用溶胶-凝胶法制备出纯TiO₂和不同浓度Sn⁴⁺离子掺杂的TiO₂光催化剂(TiO₂-Snx%, x%代表Sn⁴⁺离子掺杂的TiO₂样品中Sn⁴⁺离子摩尔分数). 利用X 射线衍射(XRD)、X 射线光电子能谱(XPS)和表面光电压谱(SPS)确定了TiO₂-Snx%催化剂的晶相结构和能带结构, 结果表明: 当Sn⁴⁺离子浓度较低时, Sn⁴⁺离子进入TiO₂晶格, 取代并占据Ti⁴⁺离子的位置, 形成取代式掺杂结构(Ti_1-xSn_xO₂), 其掺杂能级在导带下0.38 eV处; 当Sn⁴⁺离子浓度较高时, 掺入的Sn⁴⁺离子在TiO₂表面生成金红石SnO₂, 形成TiO₂和SnO₂复合结构(TiO₂/SnO₂), SnO₂的导带位于TiO₂导带下0.33 eV处. 利用瞬态光电压谱和荧光光谱研究了TiO₂-Snx%催化剂光生载流子的分离和复合的动力学过程, 结果表明, Sn⁴⁺离子掺杂能级和表面SnO₂能带存在促进光生载流子的分离, 有效地抑制了光生电子与空穴的复合; 然而, Sn⁴⁺离子掺杂能级能更有效地增加光生电子的分离寿命, 提高了光生载流子的分离效率, 从而揭示了TiO₂-Snx%催化剂的光催化机理.     

Synthesis, Structure, and Derivatives of endo-4-Aminomethyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene

Synthesis was performed and structure studied of endo-4-cyanotetracyclo[6.2.1.1^3,6.0^2,7]dodec-9-ene prepared by reaction of a stereochemically uniform endo-5-cyanobicyclo[2.2.1]hept-2-ene with cyclopentadiene. By analysis of potential energy surface (PES) for reactions of endo-5-cyanobicyclo[2.2.1]hept-2-ene and the respective exo-stereoisomer with cyclopentadiene (in B3LYP/6-31G(d) approximation) the endo,exo-junction and anti-orientation of the methylene bridges in the bicyclic fragments of the adducts were shown to be preferable. Reduction of the tetracyclic nitrile with lithium aluminum hydride yielded endo-4-aminomethyltetracyclo-[6.2.1.1^3,6.0^2,7]dodec-9-ene whose geometry and conformational characteristics were studied by means of molecular mechanics method. Products were obtained from reactions of the tetracyclic amine with p-toluene-, p-chloro-benzene-, p-nitrobenzenesulfonyl chlorides, p-nitrobenzoyl chloride, succinic anhydride, mesityl and p-toluene-sulfonyl isocyanates, phenyl, p-toluenesulfonyl, and benzoyl isothiocyanates, p-nitrophenyloxirane, and N-(2,3-epoxypropyl)carbazole. A series of the amine derivatives was epoxidized with perphtahlic acid. The structure of compounds synthesized was confirmed by analysis of their IR spectra, ¹H, ¹³C, and two-dimensional NMR spectra, and additionally by calculation of the chemical shifts in ¹H and ¹³C NMR spectra by procedures GIAO and CSGT in PBE1PBE/6-31G^## approximation.     

Thermal Decomposition of Chloromethylated Poly(styrene)-PAN Resin and Its Complexes with Some Transition Metal Ions

The complexes formed by the chemically modified chloromethylated poly(styrene)-PAN (CMPS-PAN) as a resin chelating ion exchanger were characterized by infrared and potentiometry. The thermal degradation of pure CMPS-PAN resin and its complexes with Au³⁺, Cr³⁺, Cu²⁺, Fe³⁺, Mn²⁺ and Pt⁴⁺ in air atmosphere has been studied using thermal gravimetry (TG) and derivative thermal gravimetry (DTG). The results showed that four different steps accompany the decomposition of CMPS-PAN resin and its complexes with the metal ions. These stages were affected by the presence of the investigated metal ions. The thermal degradation of CMPS-PAN resin in the presence of the ions showed different stability of the resin in the following decreasing order: Au³⁺>Pt⁴⁺>Mn²⁺>Cu²⁺>Cr³⁺>Fe³⁺. On the basis of the applicability of a non-isothermal kinetic equation, the decomposition process was a first-order reaction. The activation energy, Ea, the entropy change, ΔS ^*, the enthalpy change, ΔH ^* and the Gibbs free energy of activation, ΔG ^* were calculated by applying the theory of the reaction rates. The effect of the different central metal ions on the calculated thermodynamic activation parameters was discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Wet-air oxidation of p-nitrophenol

Summary Wet air oxidation rates of p-nitrophenol in the presence of excess oxygen, at different temperatures and oxygen pressures conditions were investigated. The experiments were carried out at between 120 and 200^oC and at 1.0-3.0 MPa partial pressures of oxygen, in a glass vessel inserted in a stainless steel reactor. Initial p-nitrophenol concentration was 3.59x10^-4 mol/L. Copper sulfate (CuSO₄.5H₂O) was used as a catalyst. Presence of Cu²⁺ ions in the reaction medium accelerated oxidation reaction slightly. Oxidation kinetics have also been investigated with respect to p-nitrophenol disappearance and TOC results.     

Luminescence properties of Eu2+, Sn2+, and Pb2+ in SrB6O10 and Sr1 − xMnxB6O10

The luminescence properties of Eu²⁺, Sn²⁺, and Pb²⁺ in SrB₆O₁₀ have been studied both at room-temperature and liquid-helium temperature and the decay times of Sn²⁺ and Pb²⁺ in this matrix have been measured and analyzed. According to the emission spectrum of Eu²⁺ there seems to be three different cation sites in SrB₆O₁₀. Europium, tin, and lead were also used as sensitizers for Mn²⁺ and the energy transfer processes were characterized. Eu²⁺-Mn²⁺ energy transfer was inefficient due to the transfer within different Eu²⁺ centers. The sensitization action of Sn²⁺ and Pb²⁺ on Mn²⁺ was different because lead-lead energy transfer occurs (even at 4.2 K) but tin-tin transfer can be neglected. A fast diffusion model for the Pb²⁺ system is suggested.     

Innovative Green Chemistry Approach to Synthesis of Sn2+-Metal Complex and Design of Polymer Composites with Small Optical Band Gaps

In this work, the green method was used to synthesize Sn²⁺-metal complex by polyphenols (PPHs) of black tea (BT). The formation of Sn²⁺-PPHs metal complex was confirmed through UV-Vis and FTIR methods. The FTIR method shows that BT contains NH and OH functional groups, conjugated double bonds, and PPHs which are important to create the Sn²⁺-metal complexes. The synthesized Sn²⁺-PPHs metal complex was used successfully to decrease the optical energy band gap of PVA polymer. XRD method showed that the amorphous phase increased with increasing the metal complexes. The FTIR and XRD analysis show the complex formation between Sn²⁺-PPHs metal complex and PVA polymer. The enhancement in the optical properties of PVA was evidenced via UV-visible spectroscopy method. When Sn²⁺-PPHs metal complex was loaded to PVA, the refractive index and dielectric constant were improved. In addition, the absorption edge was also decreased to lower photon. The optical energy band gap decreases from 6.4 to 1.8 eV for PVAloaded with 30% (v/v) Sn²⁺-PPHs metal complex. The variations of dielectric constant versus wavelength of photon are examined to measure localized charge density (N/m*) and high frequency dielectric constant. By increasing Sn²⁺-PPHs metal complex, the N/m* are improved from 3.65 × 10⁵⁵ to 13.38 × 10⁵⁵ m⁻³ Kg⁻¹. The oscillator dispersion energy (E_d) and average oscillator energy (E_o) are measured. The electronic transition natures in composite films are determined based on the Tauc’s method, whereas close examinations of the dielectric loss parameter are also held to measure the energy band gap.     

N,N'-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺的热分解动力学研究

以TG-DTG为手段, 研究了N,N'-二(5,5-二甲基-2-磷杂-2-硫代-1,3-二噁烷-2-基)乙二胺(DPTDEDA)在氮气气氛中的热分解动力学, 利用 Kissinger法、Flynn-Wall-Ozawa(FWO)法对DPTDEDA进行了动力学分析, 求出了该物质的热分解动力学参数, 同时利用Satava-Sestak法研究了该物质的热分解机理. 结果表明, Kissinger法所求得的表观活化能为137.37 kJ•mol^－1, 指前因子ln A＝28.00; Flynn-Wall-Ozawa法所求得的活化能为139.83 kJ•mol^－1. DPTDEDA的热分解机理为相边界反应, 其动力学方程为G(α)＝1－(1－α)⁴, 反应级数n＝4.     

Characteriztion of a novel feather-degrading Bacillus sp. strain

Feather waste is generated in large amounts as a byproduct of commercial poultry processing. This residue is almost pure keratin, which is not easily degradable by common proteolytic enzymes. A feather-degrading bacterium was isolated from poultry feathers in decomposition. The strain identified as kr16 showed important feather-degrading activity when grown on basal medium containing 10 g/L of native feather as the source of energy, carbon, and nitrogen. The isolate was characterized according to the phenotypical characteristics and biochemical profiling that belong to the Bacillus genus. Keratinolytic activity of this isolate was monitored during cultivation of the bacterium on raw feathers at different temperatures. Maximum growth and feather-degrading activity were observed at 30–37°C. The keratinolytic enzyme had a pH optimum ranging from 8.0 to 11.0 and a temperature optimum of 45–65°C. The keratinase was strongly inhibited by EDTA and the metal ions Hg²⁺ and Sn²⁺.     

P NMR study of the valence stability of tin in its 1-hydroxyethylene-diphosphonate (HEDP) and N,N′,N′-trimethylenephosphonate-polyethyleneimine (PEI-MP) complexes

The valence stability of tin in its complexes with 1-hydroxyethylene-diphosphonate (HEDP) and with N,N′,N′-trimethylenephosphonate-polyethyleneimine (PEI-MP) was investigated. With particular interest in the possible interconversion between Sn²⁺ and Sn⁴⁺, the complexes were monitored with the aid of ³¹P NMR spectroscopy. The extent of complex formation with both ligands was evaluated for systems with tin in their respective oxidation states. The Sn²⁺-complexes underwent initial, but limited oxidation upon preparation, and beyond which were rather stable, irrespective of pH or time. Both Sn²⁺- and Sn⁴⁺-complexes were found to exist in solution without change. Oxidation of Sn²⁺ was achieved by addition of hydrogen-peroxide and was partially reversed by the addition of glutathione (GSH). The amount of H₂O₂ needed for complete oxidation of the Sn²⁺- into Sn⁴⁺-complexes was determined for both ligands, as well as the time taken for that oxidation.     

Methylation of inorganic tin by decaying spartina alterniflora in estuarine water and by estuarine water

Methyltin compounds (MeSn) which do not originate from man–made pollution are common in estuaries and particularly in salt marshes containing the marsh grass Spartina alterniflora. This study reports the results of experiments in which estuarine water containing S. alterniflora leaves is spiked with inorganic tin, and estuarine water alone is spiked with inorganic tin and MeSn. When decaying leaves are present, inorganic tin concentrations in the water decrease and there is a 10-fold increase in inorganic tin concentration in the leaves. This biosorption follows pseudo–first–order kinetics. MeSn³⁺ and Me₂Sn²⁺ occur occasionally in the water. The Me₂Sn²⁺ concentration decreases with time and the Me₃Sn²⁺ concentration increases with time in S. alterniflora leaves. The results of estuarine water amended with inorganic tin and MeSn in the absence of leaves are quite different. The overall inorganic tin concentration decreases significantly during the experiment, the MeSn³⁺ concentration is approximately constant, and concentrations of Me₂Sn²⁺ and Me₃Sn⁺ increase. This means that net methylation of inorganic tin has occurred. We conclude that decaying S. alterniflora is likely to be important in the cycling of tin in salt marshes.     

Local structure and hyperfine interactions of Fe and Sn atoms in brownmillerite-like ferrite Sr2Fe1.98Sn0.02O5+x

Mössbauer spectroscopy has been applied for studying local environment of ⁵⁷Fe and ¹¹⁹Sn probe atoms within tin-doped Sr₂Fe_1.98Sn_0.02O_5+x (x?0.02) ferrite with the brownmillerite-type structure. ⁵⁷Fe Mössbauer spectra indicate no appreciable local distortions induced by the tin dopant atoms. The ¹¹⁹Sn spectra recorded below the magnetic ordering temperature (T_N) can be described as a superposition of two Zeeman sextets, which indicate that Sn⁴⁺ dopant ions are located in two non-equivalent crystallographic and magnetic sites. The observed hyperfine parameters were discussed supposing Sn⁴⁺ cations to replace iron cations in the octahedral (Sn_O) and tetrahedral (Sn_T) sublattices. It has been supposed that Sn⁴⁺ cations being stabilized in the tetrahedral sublattice complete their nearest anion surrounding up to the octahedral oxygen coordination “Sn_T⁴⁺”. Annealing of the Sr₂Fe_1.98Sn_0.02O_5+x in helium flux conditions at 950°C leads to formation of divalent Sn²⁺ cations with a simultaneous decrease of the contribution for the Sn_T⁴⁺ sub-spectrum. The parameters of combined electric and magnetic hyperfine interactions of the ¹¹⁹Sn²⁺ sub-spectrum underline that impurity atoms are stabilized in the sp³d-hybrid state in the oxygen distorted tetragonal pyramid. The analysis of the ¹¹⁹Sn spectra indicates a chemical reversibility of the processes Sn_T²⁺?Sn_T⁴⁺ within the tetrahedral sublattice of the brownmillerite-type ferrite.     

Non-isothermal Studies on Mechanism And Kinetics of Thermal Decomposition of Cobalt(II) Oxalate Dihydrate

Thermal decomposition of CoC₂O₄⋅2H₂O was studied using DTA, TG, QMS and XRD techniques. It was shown that decomposition generally occurs in two steps: dehydration to anhydrous oxalate and next decomposition to Co and to CoO in two parallel reactions. Two parallel reactions were distinguished using mass spectra data of gaseous products of decomposition. Both reactions run according toAvrami–Erofeev equation. For reaction going to metallic cobalt parameter n=2 and activation energy is 97±14 kJ mol^–1. It was found that decomposition to CoO proceeds in two stages. First stage (0.12<α_II<0.41) proceeds according to n=2, with activation energy 251±15 kJ mol^–1 and second stage (0.45<α_II<0.85) proceeds according to parameter n=1 and activation energy 203±21 kJ mol^–1. This revised version was published online in August 2006 with corrections to the Cover Date.     

DFT analysis of the linkage isomerism in penta(ammine)ruthenium(II/III) complexes of benzotriazole: Natural bond orbital method approach and a comprehensive energy decomposition analysis

Penta(ammine)ruthenium benzotriazole complexes [Ru^II/III(NH₃)₅bta]^+/2+ and [Ru^II/III(NH₃)₅btaH]^2+/3+ (bta and btaH are the deprotonated and neutral form of the triazole ligand, respectively) can exhibit two linkage isomers κN1 and κN2. This system was investigated by density functional theory natural bond orbitals analysis and Su-Li energy decomposition analysis. Steric, electrostatic, exchange, repulsion, polarization, and dispersion energy components of the total metal–ligand interaction were quantitatively evaluated, and revealed that the overall metal-triazole ligand is comprised of donor–acceptor interactions like σ-donation and π-back-donation, which favors a specific isomer depending on the oxidation state of the ruthenium and the charge of the ligand. Further, activation energies (ΔG^‡) for linkage isomerization reactions were calculated. Results were correlated with experimental chemical–electrochemical data and two plausible mechanisms are discussed. © 2019 Wiley Periodicals, Inc.     

Dehydration Kinetics of Zinc Phosphate Tetrahydrate α-Zn3（PO4）2·4H2O Nanoparticle

TG-DTG technique and Harcourt-Esson integrated equation were used to study the dehydration process of zinc phosphate tetrahydrate α-Zn3（PO4）2·4H2O nanoparticle and its thermal decomposition kinetics. The results show that there are three stages of dehydration between 300 and 800 K during the thermal decomposition of α-Zn3（PO4）2·4H2O nanoparticle. The first stage is controlled by chemical reaction with an activation energy of 69.48 kJ·mol^-1 and a pre-exponential factor of 1.77×10^6 s^-1. The second is controlled by nucleation and growth with an activation energy of 78.74 kJ·mol^-1 and a pre-exponential factor of 5.86×10^9 s^-1. The third is controlled by nucleation and growth with an activation energy of 141.5 kJ·mol^-1 and a pre-exponential factor of 1.01×10^12 s^-1. The kinetic compensative effects not only exist in Arrhenius equation but also in Harcourt-Esson equation. Activation energy E is dependent on both the decomposition fraction α and temperature T.     

Reactivity of Dicoordinated Stannylones (Sn0) versus Stannylenes (SnII): An Investigation Using DFT‐Based Reactivity Indices

The reactivity of dicoordinated Sn⁰ compounds, stannylones, is probed using density functional theory (DFT)‐based reactivity indices and compared with the reactivity of dicoordinated Sn^II compounds, stannylenes. For the former compounds, the influence of different types of electron‐donating ligands, such as cyclic and acyclic carbenes, stannylenes and phosphines, on the reactivity of the central Sn atom is analyzed in detail. Sn⁰ compounds are found to be relatively soft systems with a high nucleophilicity, and the plots of the Fukui function f^? for an electrophilic attack consistently predict the highest reactivity on the Sn atom. Next, complexes of dicoordinated Sn compounds with different Lewis acids of variable hardness are computed. In a first part, the double‐base character of stannylones is demonstrated in interactions with the hardest Lewis acid H⁺. Both the first and second proton affinities (PAs) are high and are well correlated with the atomic charge on the Sn atom, probing its local hardness. These observations are also in line with electrostatic potential plots that demonstrate that the tin atom in Sn⁰ compounds bears a higher negative charge in comparison to Sn^II compounds. Stannylones and stannylenes can be distinguished from each other by the partial charges at Sn and by various reactivity indices. It also becomes clear that there is a smooth transition between the two classes of compounds. We furthermore demonstrate both from DFT‐based reactivity indices and from energy decomposition analysis, combined with natural orbitals for chemical valence (EDA‐NOCV), that the monocomplexed stannylones are still nucleophilic and as reactive towards a second Lewis acid as towards the first one. The dominating interaction is a strong σ‐type interaction from the Sn atom towards the Lewis acid. The interaction energy is higher for complexes with the cation Ag⁺ than with the non‐charged electrophiles BH₃, BF₃, and AlCl₃.     

NMR-Spektroskopische Untersuchungen der kinetischen Limitierung der Kationenselektivität eines cadmiumselektiven Ionophors

NMR Studies of the Kinetic Limitation of Cation Selectivity of a Cadmium-Selective Ionophore The Cd²⁺-selective ionophore N,N,N′,N′-tetrabutyl-3, 6-dioxaoctanedithioamide (1) looses its capability to induce cation selectivity in solvent polymeric membranes if these are contacted with Cu²⁺, Pd²⁺, Pt²⁺, Ag⁺ and Hg²⁺. For systems with a free energy of activation of the ligand exchange reaction of more than about 65 kJ mol^?1 (in acetonitrile) the cation complexes of the ionophore act as anion exchangers (Pt²⁺, Pd²⁺). Below about 45 kJ mol^?1 cation permselectivity is observed (Zn²⁺, Cd²⁺). Ag⁺ and Hg²⁺ induce a decomposition of the ionophore.     

Sulfonic cation exchangers based on immobilized cis-Calix[4]resorcinolarenes

New sulfonic cation exchangers based on immobilized calix[4]resorcinolarenes were prepared. Their ion-exchange properties toward Na⁺, Cu²⁺, [Pd(NH₃)₄]²⁺, In³⁺, and Sn⁴⁺ ions were studied in a wide pH range, and their chemical stability was examined.     

Electron-exchange processes on simple columns of kel-f supporting tetrachlorohydroquinone

The preparation of simple electron-exchange columns is reported. An organic porous material (Kel-F powder) is used to support a water-insoluble redox reagent. Of the organic compounds tested, tetrachlorohydroquinone was best. Very stable columns were obtained with a sufficiently high redox capacity (1.59 $\text{meq}\text{g}$ dry material) and a satisfactory reaction rate.The following oxidation reactions were carried out: Fe²⁺→Fe³⁺, Cu⁺→Cu²⁺, Sn²⁺→Sn⁴⁺, I^-→I,ascorbic acid → dehydroascorbic acid, as well as the following reduction reactions: Fe³⁺→Fe²⁺, I→I^-, Ce⁴⁺→Ce³⁺, V⁵⁺→V⁴⁺, Cr⁶⁺→Cr³⁺. The effect of hydrogen ion concentration on the redox reactions was also studied.The Kel-F-tetrachlorohydroquinone columns can be used for indirect titration of redox systems and for selective oxidations or reductions, e.g. Fe³⁺ in presence of Fe²⁺ and vice versa, Cr⁶⁺ in presence of Fe³⁺, Ce⁴⁺ in presence of Ce³⁺, ascorbic acid in the presence of glucose, and Sn²⁺ in presence of Sn⁴⁺ or Fe²⁺.     

Study on the capacitance performance of Sn4+-doped V2O5

Sn⁴⁺-doped V₂O₅ cathode materials were prepared by a sol–gel method. The results showed that the modified cathode material was a mixture of V⁴⁺ and V⁵⁺. It was a kind of typical mesopore material with pores of 2–4 nm diameter. Symmetrical curves were obtained by cyclic voltammetry (CV) tests performed at different scanning rates and voltage ranges. In particular, the CV curve showed more obvious rectangle property and better redox properties when the scanning rate was 5 mV s^?1. At the current density of 200 mA g^?1, the maximum specific energy, specific power, and coulomb efficiency of the material were 27.25 mA h?g^?1, 494.87 W?kg^?1, and 97%, respectively. It was indicated that small amounts of Sn⁴⁺ doping would improve the surface morphology and electronic conductivity of V₂O₅. The Sn⁴⁺-doped V₂O₅ showed good capacitance characteristics.     

Crystal Growth and Structure Determination of Pigment Orange 82

The crystal structure of the important industrial orange pigment PO82, major part of the BASF Colors & Effects^® product Sicopal^® Orange K/L 2430, was solved from combined X‐ray single crystal, X‐ray and neutron powder diffraction, ¹¹⁹Sn Mössbauer spectroscopy, transmission electron microscopy, electron diffraction, and chemical analyses. The structure contains Keggin type clusters composed of four [M₃O₁₃] trimers consisting each of three MO₆ octahedra that share edges and one common oxygen atom connecting the trimers to the central ZnO₄ tetrahedron. The octahedrally coordinated metal atom position is mixed occupied by Ti⁴⁺, Sn⁴⁺, and Zn²⁺. Adjacent Keggin clusters share vertices and are further interconnected to four ZnO₄ tetrahedra. This framework of interconnected MO₆ octahedra and ZnO₄ tetrahedra contains channels along [110], in which the Sn²⁺ cations are located.