Effect of Cl− anions on photocatalytic decomposition of gaseous ozone over Au @ Ag/TiO2 catalyst

Au core Ag shell composite structure nanoparticles were prepared using a sol method. The Au core Ag shell composite nanoparticles were loaded on TiO₂ nanoparticles as support using a modified powder–sol method, enabling the generation of Au @ Ag/TiO₂ photocatalysts for photocatalytic decomposition and elimination of ozone. The sols were characterized by means of ultraviolet–visible light (UV–Vis) reflection spectrometry, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The activity of the Au @ Ag/TiO₂ photocatalysts for photocatalytic decomposition and elimination of ozone was evaluated and the effect of Cl^? anions on the photocatalytic activity of the catalysts was highlighted. Results showed that Au @ Ag/TiO₂ prepared via the modified powder–sol route in the presence of an appropriate amount of NaCl solid as demulsifier had better activity in the photocatalytic decomposition and elimination of ozone. At the same time, Au @ Ag/TiO₂ catalysts had better ability to resist poisonous Cl^? anions than conventional Au/TiO₂ catalyst. The reasons could be, first, that NaCl was capable of reducing the concentration of free Ag⁺ by adsorption on the surface of Ag particles forming AgCl and enhancing the formation of Au core Ag shell particles, leading to a better resistance to Cl^? anions of the catalysts, and, second, AgCl took part in the photocatalytic decomposition of ozone together with Au @ Ag/TiO₂ catalysts and had a synergistic effect on the latter, resulting in better photocatalytic activity of Au @ Ag/TiO₂ catalysts.     

Boosting Proton Conductivity in Highly Robust 3D Inorganic Cationic Extended Frameworks through Ion Exchange with Dihydrogen Phosphate Anions

The limited long‐term hydrolytic stability of rapidly emerging 3D‐extended framework materials (MOFs, COFs, MOPs, etc.) is still one of major barriers for their practical applications as new solid‐state electrolytes in fuel cells. To obtain hydrolytically stable materials, two H₂PO₄^?‐exchanged 3D inorganic cationic extended frameworks (CEFs) were successfully prepared by a facile anion‐exchange method. Both anion‐exchanged CEFs (YbO(OH)P and NDTBP) show significantly enhanced proton conductivity when compared with the original materials (YbO(OH)Cl and NDTB) with an increase of up to four orders‐of‐magnitude, reaching 2.36×10^?3 and 1.96×10^?2 S cm^?1 at 98 % RH and 85 °C for YbO(OH)P and NDTBP, respectively. These values are comparable to the most efficient proton‐conducting MOFs. In addition, these two anion‐exchanged materials are stable in boiling water, which originates from the strong electrostatic interaction between the H₂PO₄^? anion and the cationic host framework, showing a clear advance over all the acid‐impregnated materials (H₂SO₄@MIL‐101, H₃PO₄@MIL‐101, and H₃PO₄@Tp‐Azo) as practical solid‐state fuel‐cell electrolytes. This work offers a new general and efficient approach to functionalize 3D‐extended frameworks through an anion‐exchange process and achieves water‐stability with ultra‐high proton conductivity above 10^?2 S cm^?1.     

固相浸渍法制备NiO/CeO2催化剂及其在CO氧化反应中的应用

采用固相浸渍法制备了一系列NiO/CeO2催化剂,并通过与常规湿浸渍法比较,考察了制备方法对催化剂和CO氧化反应性能的影响.同时结合X射线衍射(XRD),N2吸附-脱附(BET),透射电镜(TEM),氢气-程序升温还原(H2-TPR),拉曼(Raman)光谱,X射线光电子能谱(XPS)等手段对催化剂的结构和表面物种分散状态进行了表征.CO氧化活性测试结果表明,当镍负载量相同时,固相浸渍法制备的催化剂相比于湿浸渍法表现出更好的催化性能.TEM、XPS、H2-TPR结果表明,固相浸渍法更有利于加强镍铈间的相互作用和得到高分散的镍物种,从而促进镍物种的还原.Raman结果表明固相浸渍法相比于湿浸渍法能产生更多氧空位,这有利于氧气在催化剂表面的活化,使得CO氧化反应更容易进行.     

Cation‐ and Anion‐Substituted Potassium Manganese Phosphate,KMnP3O9: Luminescence and Photocatalytic Studies

Phosphates as multifunctional materials were of vital importance in the environmental and energy fields. In the present work, a new cyclophosphate, potassium manganese phosphate (KMnP₃O₉) (hereafter KMPO), was prepared by solid state method. Cations (Ag⁺ and Cu²⁺) and anion (N^3?) were substituted into KMPO lattice via ion‐exchange and solid state methods, respectively. The as‐prepared materials were characterized by powder X–ray diffraction, SEM–EDS and UV–visible diffuse reflectance spectra. Rietveld refinement was carried out for parent material. All the prepared materials were found to crystallize in the hexagonal lattice and isomorphous with KCoP₃O₉. The nitrogen content in N^3?‐substituted KMPO was estimated by EDS and O‐N‐H analysis. The bandgap energy of the cation‐ and anion‐substituted samples was lower compared to that of pristine KMPO. Gouy method was employed to determine the magnetic susceptibility of KMPO. The photoluminescence property of Mn²⁺ in all the samples was studied, and the color coordinates were calculated using CIE 1931 chromaticity. The photocatalytic activity of visible light active material, N^3?‐substituted KMPO, was examined against the degradation of methylene blue and methyl violet at ambient conditions.     

From Waste Biomass to Solid Support: Lignosulfonate as a Cost‐Effective and Renewable Supporting Material for Catalysis

Lignosulfonate (LS) is an organic waste generated as a byproduct of the cooking process in sulfite pulping in the manufacture of paper. In this paper, LS was used as an anionic supporting material for immobilizing cationic species, which can then be used as heterogeneous catalysts in some organic transformations. With this strategy, three lignin‐supported catalysts were prepared including 1) lignin‐SO₃Sc(OTf)₂, 2) lignin‐SO₃Cu(OTf), and 3) lignin‐IL@NH₂ (IL=ionic liquid). These solid materials were then examined in many organic transformations. It was finally found that, compared with its homogeneous counterpart as well as some other solid catalysts that are prepared by using different supports with the same metal or catalytically active species, the lignin‐supported catalysts showed better performance in these reactions not only in terms of activity but also with regard to recyclability.     

Hexacoordinated spirocyclic germanium(IV) complex: Synthesis and structural characterization

The spiro‐dibenzogermocine [O(o‐C₆H₄S)₂]₂Ge ( 1 ) was prepared in a reaction between O(o‐C₆H₄SH)₂ and Ge(OⁱPr)₄, and its molecular structure was determined by X‐ray diffraction studies. In the solid state, 1 shows the existence of two weak O → Ge transannular interactions, resulting in a hexacoordinated germanium atom that displays the geometry of a distorted bicapped tetrahedron. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:45–49, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20510     

A Simple Electrochemical Approach Based on Inexpensive Wall‐Jet Screen‐Printed Ring Disk Electrode to Evaluate Oxygen Reduction Catalysts

A simple electrochemical approach to evaluate oxygen reduction catalysts using an inexpensive screen‐printed ring disk carbon electrode system, consisting of a ring electrode deposited with MnO₂ and a disk electrode modified with the catalysts for study, is developed in this study. The as‐prepared MnO₂ is selective and sensitive for H₂O₂ oxidation in the presence of O₂ and is crucial to the proposed approach. By coupling with a wall‐jet electrochemical cell, the product generated from the reduction reaction at the disk electrode can effectively be monitored at the MnO₂‐deposited ring electrode. Model catalysts of nano‐Au and nano‐Pd representing 2e^? reduction of O₂ to H₂O₂ and 4e^? reduction to H₂O, respectively, were evaluated as electrode materials in oxygen reduction reaction to demonstrate the applicability of the proposed method.     

Na3SbS4: A Solution Processable Sodium Superionic Conductor for All‐Solid‐State Sodium‐Ion Batteries

All‐solid‐state sodium‐ion batteries that operate at room temperature are attractive candidates for use in large‐scale energy storage systems. However, materials innovation in solid electrolytes is imperative to fulfill multiple requirements, including high conductivity, functional synthesis protocols for achieving intimate ionic contact with active materials, and air stability. A new, highly conductive (1.1 mS cm^?1 at 25 °C, E_a=0.20 eV) and dry air stable sodium superionic conductor, tetragonal Na₃SbS₄, is described. Importantly, Na₃SbS₄ can be prepared by scalable solution processes using methanol or water, and it exhibits high conductivities of 0.1–0.3 mS cm^?1. The solution‐processed, highly conductive solidified Na₃SbS₄ electrolyte coated on an active material (NaCrO₂) demonstrates dramatically improved electrochemical performance in all‐solid‐state batteries.     

Self‐assembled three‐dimensional flower‐like α‐Fe2O3 nanostructures and their application in catalysis

Three‐dimensional flower‐like α‐Fe₂O₃ nanostructures have been successfully synthesized by a simple surfactant‐free environmental friendly solvolthermal process. The as‐prepared products were investigated by X‐ray powder diffraction, transmission electron microscopy, and field emission scanning electron microscopy. By adjusting the synthetic parameters, the shape of the α‐Fe₂O₃ nanostructures can be controlled. The three‐dimensional flower‐like α‐Fe₂O₃ nanostructures were found to be highly active as catalysts for phenol alkylation. The effects of various parameters, such as reaction temperature, reaction time and the amount of catalyst, were studied. The catalyst was stable and could be reused three times in normal atmosphere without suffering appreciable loss in catalytic activity. Copyright © 2009 John Wiley & Sons, Ltd.     

Supported titanium‐magnesium catalysts for ethylene polymerization: A comparative study of catalysts containing isolated and clustered titanium ions in different oxidation states

Supported titanium–magnesium catalysts (TMC) comprising isolated and clustered titanium ions in different oxidation states, which are obtained using titanium compounds of different composition (TiCl₄, TiCl₃?nDBE (DBE – dibutyl ether), [η⁶–BenzeneTiAl₂Cl₈]), were synthesized and tested in ethylene polymerization. The state of titanium ions was studied by the ESR method both for the procatalysts and after their interaction with triisobutilaluminum. For identification of ESR‐silent Ti³⁺ ions and Ti²⁺ ions, special procedures of additional catalyst treatment with pyridine, water, and chloropentafluorobenzene were used to obtain Ti³⁺ ions that are observable in ESR spectra. In distinction to numerous earlier works performed with the TiCl₄/MgCl₂ catalyst comprising after the interaction with AlR₃ the Ti³⁺ surface compounds both as isolated ions and clusters (ESR‐silent), this work considers the [η⁶–BenzeneTiAl₂Cl₈]/MgCl₂ catalyst (TMC‐3) comprising mainly the isolated Ti²⁺ ions and a new catalyst TMC‐4 obtained by treating the TMC‐3 with chloropentafluorobenzene. This catalyst comprises only the isolated Ti³⁺ ions both before and after the interaction with triisobutylaluminum. It was shown that in spite of sharp distinctions between the catalysts under consideration concerning titanium oxidation state and the ratio of isolated Ti³⁺ ions to clustered ones, all these catalysts produce polyethylenes with similar molecular weights and molecular‐weight distributions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6362–6372, 2009     

Alternatively linking fullerene and conjugated polymers

The stereo‐electronic control over bisadditions of conjugated polymers to fullerene (C₆₀) is explored in the formation of alternating copolymers. The chemistry, resulting configuration, and properties of poly(3‐hexylthiophene)‐alt‐C₆₀ copolymers prepared by either classic pyrrolidine ring formation or an atom transfer radical addition are compared. Both routes result in controlled additions of polymers to C₆₀. Extensive macromolecular modeling through PM6 methods indicate that there is no conjugation between P3HT and C₆₀ in the systems studied. This along with 2D‐NMR, AFM, and photovoltaic characterizations of the materials indicate the importance of the structure of the modified C₆₀ and the nature of the linking group between C₆₀ and P3HT segments in determining the morphology of the copolymers in the solid state. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2304–2317, 2009     

Emulsion polymerization of ethylene from mesoporous silica nanoparticles with vinyl functionalized monolayers

Emulsion polymerization of ethylene from vinyl functionalized mesoporous silica nanoparticles (V‐MSNs) was reported. V‐MSNs were synthesized via deposition of vinyl monolayers on the pore walls, and the relative surface coverage of the vinyl monolayers was 74%. A fluorinated P‐O‐chelated nickel catalyst coordinated to the vinyl groups. These V‐MSNs hosting catalysts were full dispersed in water assisted by ultrasonic processor in the presence of surfactants. After addition of ethylene, polyethylene (PE) chains grew from the pores of V‐MSNs, formation of stable nanocomposite latices with solid content up to 17.3%. Our method made V‐MSNs well‐dispersed in the PE matrix. Especially, because of a strong interaction between PE and nanoparticles, a stable V‐MSNs core/PE shell structure was formed upon thermal treatment above melting temperature of the PE. Samples were analyzed by a number of techniques including TEM, N₂ adsorption‐desorption, FTIR, and solid state ²⁹Si NMR, DLS, ¹H NMR, GPC, and DSC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1393–1402, 2009     

Three‐in‐One Oxygen Vacancies: Whole Visible‐Spectrum Absorption,Efficient Charge Separation,and Surface Site Activation for Robust CO2 Photoreduction

A facile and controllable in situ reduction strategy is used to create surface oxygen vacancies (OVs) on Aurivillius‐phase Sr₂Bi₂Nb₂TiO₁₂ nanosheets, which were prepared by a mineralizer‐assisted soft‐chemical method. Introduction of OVs on the surface of Sr₂Bi₂Nb₂TiO₁₂ extends photoresponse to cover the whole visible region and also tremendously promotes separation of photoinduced charge carriers. Adsorption and activation of CO₂ molecules on the surface of the catalyst are greatly enhanced. In the gas‐solid reaction system without co‐catalysts or sacrificial agents, OVs‐abundant Sr₂Bi₂Nb₂TiO₁₂ nanosheets show outstanding CO₂ photoreduction activity, producing CO with a rate of 17.11 μmol g^?1 h^?1, about 58 times higher than that of the bulk counterpart, surpassing most previously reported state‐of‐the‐art photocatalysts. Our study provides a three‐in‐one integrated solution to advance the performance of photocatalysts for solar‐energy conversion and generation of renewable energy.     

The influence of CaCO3 filler component on thermal decomposition process of PP/LDPE/DAP ternary blend

Polypropylene‐low density polyethylene (PP‐LDPE) blends involving PP‐LDPE (90/10 wt%.) with (0.06 wt%) dialkyl peroxide (DAP) and different amounts (5, 10, 20 wt%) of calcium carbonate (CaCO₃) were prepared by melt‐blending with a single‐screw extruder. The effect of addition of CaCO₃ on thermal decomposition process and kinetic parameters, such as activation energy and pre‐exponential factor of PP‐LDPE blend with DAP matrix, was studied. The kinetics of the thermal degradation of composites was investigated by thermogravimetric analysis in dynamic nitrogen atmosphere at different heating rates. TG curves showed that the thermal decomposition of composites occurred in one weight‐loss stage. The apparent activation energies of thermal decomposition for composites, as determined by the Tang method (TM), the Kissinger–Akahira–Sunose method (KAS), the Flynn–Wall–Ozawa method (FWO), and the Coats–Redfern (CR) method were 156.6, 156.0, 159.8, and 167.7 kJ.mol^?1 for the thermal decomposition of composite with 5 wt% CaCO₃, 191.5, 190.8, 193.1, and 196.8 kJ.mol^?1 for the thermal decomposition of composite with 10 wt% CaCO₃, and 206.3, 206.1, 207.5, and 203.8 kJ mol^?1 for the thermal decomposition of composite with 20 wt% CaCO₃, respectively. The most likely decomposition process for weight‐loss stages of composites with CaCO₃ content 5 and 10 wt% was an A_n sigmoidal type. However, the most likely decomposition process for composite with CaCO₃ content 20 wt% was an R_n contracted geometry shape type in terms of the CR and master plots results. It was also found that the thermal stability, activation energy, and thermal decomposition process were changed with the increase in the CaCO₃ filler weight in composite structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Sodium Cobalt Metaphosphate as an Efficient Oxygen Evolution Reaction Catalyst in Alkaline Solution

Sodium cobalt metaphosphate [NaCo(PO₃)₃] has CoO octahedra (CoO₆) and shows superior oxygen evolution reaction (OER) activity in alkaline solution, comparable with the state‐of‐the‐art precious‐metal RuO₂ catalyst. OER catalysts of this metaphosphate are prepared by combustion (Cb) and solid‐state (SS) methods. The combustion‐assisted method offers a facile synthesis and one‐step carbon composite formation. Unusually high catalytic activity was observed in NCoM‐Cb‐Ar and could be due to chemical coupling effects between NaCo(PO₃)₃ and partially graphitized carbon. This novel electrocatalyst exhibits very small overpotential of 340 mV with high mass activity of 532 A g^?1. Good charge transfer abilities and chemical coupling between NaCo(PO₃)₃ and amorphous carbon gives the OER activity in NCoM‐Cb‐Ar.     

Three‐in‐One Oxygen Vacancies: Whole Visible‐Spectrum Absorption,Efficient Charge Separation,and Surface Site Activation for Robust CO2 Photoreduction

A facile and controllable in situ reduction strategy is used to create surface oxygen vacancies (OVs) on Aurivillius‐phase Sr₂Bi₂Nb₂TiO₁₂ nanosheets, which were prepared by a mineralizer‐assisted soft‐chemical method. Introduction of OVs on the surface of Sr₂Bi₂Nb₂TiO₁₂ extends photoresponse to cover the whole visible region and also tremendously promotes separation of photoinduced charge carriers. Adsorption and activation of CO₂ molecules on the surface of the catalyst are greatly enhanced. In the gas‐solid reaction system without co‐catalysts or sacrificial agents, OVs‐abundant Sr₂Bi₂Nb₂TiO₁₂ nanosheets show outstanding CO₂ photoreduction activity, producing CO with a rate of 17.11 μmol g^?1 h^?1, about 58 times higher than that of the bulk counterpart, surpassing most previously reported state‐of‐the‐art photocatalysts. Our study provides a three‐in‐one integrated solution to advance the performance of photocatalysts for solar‐energy conversion and generation of renewable energy.     

Ethylene polymerization over transition‐metal supported catalysts. II. Cr on zeolite,silica, and charcoal: Characterization and activity studies

Cr catalysts supported on silica, zeolite NaY, and charcoal were prepared with two different methods. They were characterized and examined in the polymerization of ethene. Cyclic voltammetry, electron spin resonance, X‐ray photoelectron spectroscopy and silicon‐29 magic‐angle spinning nuclear magnetic resonance spectroscopy were used to characterize them, demonstrating that Cr is not in a single oxidation state, that the distribution among the various oxidation states depends on the history of the sample, and that even for a single oxidation state a variety of different environments can occur. In the polymerization of ethene, the supported Cr catalysts exhibited activity values varying from 10³ to 10⁵ gPE · molCr^?1 · [M]^?1 · h^?1, depending on the choice of the support and on the method by which the Cr is placed on it. Silica seemed to be the most efficient support for Cr for this reaction. However, the zeolite‐supported catalysts also showed reasonable activity values (A_p ? 10⁴ units) and presented the advantage of having a strong interaction between the Cr and the support, which may prevent leaching of the cation into the surrounding environment. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3768–3780, 2003     

纯相和镍取代的Co_3O_4尖晶石催化剂用于N_2O直接分解(英文)

A series of NixCo1-xCo2O4(0 ≤ x ≤ 1) spinel catalysts were prepared by the co-precipitation method and used for direct N2O decomposition. The decomposition pathway of the parent precipitates was characterized by thermal analysis. The catalysts were calcined at 500 °C for 3 h and characterized by powder X-ray diffraction, Fourier transform infrared, and N2 adsorption-desorption. Nickel cobaltite spinel was formed in the solid state reaction between NiO and Co3O4. The N2O decomposition measurement revealed significant increase in the activity of Co3O4 spinel oxide catalyst with the partial replacement of Co2+ by Ni2+. The activity of this series of catalysts was controlled by the degree of Co2+ substitution by Ni2+, spinel crystallite size, catalyst surface area, presence of residual K+, and calcination temperature.     

The Hazardous Origin of Photocatalytic Activity of ZnCr2O4

The ZnCr₂O₄ catalysts are synthesized by thermal decomposition of (NH₄)₂[Zn(NH₃)₂(CrO₄)₂] and materials with high surface areas and particle sizes in the nano regime are obtained. A special structural feature of the materials are stacking faults with densities strongly depending on the synthesis temperature, i.e. the lower the temperature the larger the number of stacking faults. The catalyst prepared at the lowest decomposition temperature exhibiting the smallest particle size shows the highest catalytic activity in the photocatalytic degradation of y‐Eosin in a photo‐Fenton process. The results of different analytic methods demonstrate that the high catalytic activity is directly correlated with CrO₄^2– anions generated via photo‐oxidation of the catalyst. Therefore, ZnCr₂O₄ cannot be regarded as an environmental friendly catalyst for advanced photocatalytic oxidation processes.     

Ruthenium‐incorporated,metathesis‐active polyacetylene

Two olefin metathesis methods have been developed for the preparation of metal‐incorporated polyacetylene (MIPA) with high levels of covalently attached ruthenium complex. Treatment of freshly prepared, porous polyacetylene (PA) formed by polymerization of acetylene by the metathesis catalyst (H₂IMes)RuCl₂(?CHPh)(3‐bromopyridine)₂ ( G2B ) with additional G2B resulted in the incorporation of the ruthenium complex into the solid polymer in levels up to 75% by mass, giving two‐step MIPA (MIPA2). Alternatively, single‐step MIPA (MIPA1) samples with similar levels (up to 79% by mass) of ruthenium incorporation were obtained by polymerization of acetylene with highly concentrated solutions of G2B , and the resulting materials formed fine suspensions in CH₂Cl₂. A variety of experiments confirmed that both the methods give materials with ruthenium covalently attached to PA chains. Shiny, tough MIPA films were obtained by pressing the black powders obtained by either method. Some MIPA properties were dependent on the amount of metal incorporation, but even samples with high incorporation levels mimicked untreated PA in many respects. MIPA1, but not MIPA2, was made electrically conductive by doping with iodine. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1061–1072, 2009