Approach to De-NOx-ing photocatalysis. II excited state of copper ions supported on silica and photocatalytic activity for no decomposition

Cu²⁺ ions supported on SiO₂ (Cm²⁺ /SiO₂) prepared by an ion-exchange method are reduced to Cu⁺ when Cu²⁺/SiO₂ samples are evacuated at temperatures higher than 573 K Reduced Cu²⁺ ions on SiO₂ (Cu⁺/SiO₂ catalyst) decomposes NO molecules photocatalytically and stoichiometrically into N₂ and O₂ at 275 K. The physicochemical and photochemical properties of copper ions anchored onto SiO₂ have been investigated by means of ESR and dynamic photoluminescence spectroscopies, as well as the analysis of photoreaction products. These results indicate that the excited state of the copper ions (Cu⁺ species) plays a significant role in the photocatalytic decomposition of NO molecules and the photoreaction involves an electron transfer from the excited state of the Cu⁺ ion into an anti-bonding π orbital of NO molecule within the lifetime of its excited state. Thus, the present results obtained with the Cu⁺/SiO₂ catalysts imply the possibility of their utilization as a potentially promising type of photocatalysts in gas-solid systems.     

Catalytic performance of Ni-Al layered double hydroxides in CO purification processes

Ni-Al layered double hydroxides with Ni²⁺/Al³⁺ molar ratios of 1.5 and 3.0 have been synthesized by co-precipitation and studied as catalyst precursors for purification of CO-containing gas-mixtures by means of CO oxidation to CO₂ and conversion of CO by water vapor (water-gas shift reaction). The influence of the alkali additives (K⁺ ions) on the water-gas shift activity has been also examined. It was established that the catalytic activity of both reactions increases with the temperature and the nickel content. Hypothetic schemes are proposed about activation of the catalysts in the WGSR and CO oxidation including redox Ni²⁺ ? Ni³⁺ transition on the catalyst surface. The activity in WGSR is positively affected by the presence of potassium promoter, depending on its amount. The sample with higher nickel loading is the most effective catalyst as for CO oxidation as well as for WGSR at intermediate temperatures after potassium promotion.     

Investigation of the Cu-Zr-Y oxides activity in the carbon black catalytic oxidation by differential thermal analysis and temperature programmed reduction

Different copper/zirconium-yttrium catalysts have been tested in carbon black oxidation reaction. Supported mainly on differential thermal analysis and temperature programmed reduction, two different mechanisms have been proposed to explain the catalytic results. In the absence of copper, it has been shown that Zr³⁺ ions and associated anionic vacancies are responsible to the catalytic enhancement observed in the mixed oxides, oxygen species being activated on these sites. Among mixed zirconia-yttria solids, ZrO₂-5 mol%Y₂O₃ is the most active catalyst. Copper impregnation on these oxides leads to the formation of different copper species. Small particles of CuO in low interaction with the support, induce a catalytic improvement due to the highest reducibility of these species. Moreover, in order to be more efficient, CuO species should have some interactions with the support, since impregnated samples are more active than the simple mechanical mixtures.     

Influence of composition on corroding process of Na<Subscript>2</Subscript>O-K<Subscript>2</Subscript>O-CaO-ZrO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glasses

The corroding process of six glasses of the Na₂O-K₂O-CaO-ZrO₂-SiO₂ system with ZrO₂content 0–2.13 mass % by water was observed during static tests at 121°C and pressure of 0.25 MPa in steam sterilizer. Significant increase of Na⁺ and K⁺ content in leachates was observed after the addition of ZrO₂ into glass. Further increase of the content of ZrO₂ in glasses slowed down the rate of Na⁺ and K⁺ leaching. The leaching process of SiO₂ as well as Na⁺, K⁺, and Ca²⁺ ions was evaluated on the basis of comparison with model leaching processes. Variation of the concentrations of Na⁺, K⁺, Ca²⁺, and SiO₂ in leachates with time was described by empirical equation. Observed changes in the initial leaching rates of Na⁺, K⁺, Ca²⁺, and SiO₂ can be ascribed to the content of ZrO₂ in glasses. The presence of ZrO₂ in glasses reduced the overall rate of glass dissolution.     

Comparison of alkali-promoted ZrO2 catalysts towards carbon black oxidation

The effect of alkali metals deposition on zirconia has been studied in the oxidation of carbon black, considered as a model of diesel soot. The study of the influence of alkali content and alkali precursor was undertaken for K/ZrO₂, evidencing a better activity for a catalyst prepared with an atomic ratio K/Zr = 0.14 and from a nitrate precursor. Using the latter preparation conditions, alkali/ZrO₂ are found to be active in the oxidation of carbon black according the sequence ZrO₂ < Li/ZrO₂ < Na/ZrO₂ < K/ZrO₂ < Rb/ZrO₂ < Cs/ZrO₂. Alkali metals have an influence on the tetragonal–monoclinic crystalline modification. Alkali metals ions with low size tend to stabilize the tetragonal ZrO₂ phase whereas those with higher ionic radius favour the tetragonal–monoclinic modification. Fourier transform-infrared spectroscopy (FTIR) and temperature programmed reduction (TPR) measurements show that the catalytic activity partially depends on the presence of nitrate species stabilized in alkali/ZrO₂ even after calcination treatment at 600 °C. Nitrate species are more stable in the presence of alkali with high ionic radius than those of low size.     

Methane Oxidation over Cu2+/[CuOH]+ Pairs and Site-Specific Kinetics in Copper Mordenite Revealed by Operando Electron Paramagnetic Resonance and UV/Visible Spectroscopy

Cu-exchanged mordenite (MOR) is a promising material for partial CH₄ oxidation. The structural diversity of Cu species within MOR makes it difficult to identify the active Cu sites and to determine their redox and kinetic properties. In this study, the Cu speciation in Cu-MOR materials with different Cu loadings has been determined using operando electron paramagnetic resonance (EPR) and operando ultraviolet-visible (UV/Vis) spectroscopy as well as in situ photoluminescence (PL) and Fourier-transform infrared (FTIR) spectroscopy. A novel pathway for CH₄ oxidation involving paired [CuOH]⁺ and bare Cu²⁺ species has been identified. The reduction of bare Cu²⁺ ions facilitated by adjacent [CuOH]⁺ demonstrates that the frequently reported assumption of redox-inert Cu²⁺ centers does not generally apply. The measured site-specific reaction kinetics show that dimeric Cu species exhibit a faster reaction rate and a higher apparent activation energy than monomeric Cu²⁺ active sites highlighting their difference in the CH₄ oxidation potential.     

Structure and Catalytic Properties of a Cu2+-Containing Hydrogel of Zirconium Dioxide

The distribution of Cu²⁺ ions in ZrO₂ and sulfated ZrO₂ hydrogel phases was studied by EPR spectroscopy and voltammetry. The formation of the following three types of copper structures was observed: mononuclear Cu²⁺ complexes (A), magnetic associates (B), and Cu²⁺ compounds (C) that gave no EPR signals under the conditions used in the spectroscopic measurements. The specific catalytic activity of various Cu²⁺ compounds in the liquid-phase reaction of 2,3,5-trimethyl-1,4-hydroquinone oxidation was determined. The copper complexes C were found to exhibit the highest catalytic activity.     

State of the copper ions in the catalysts for oxidation of carbon monoxide to carbon dioxide

The state of the copper ions in the catalysts for the oxidation of carbon monoxide to carbon dioxide, prepared by dissolving an activated copper-containing aluminum alloy in water followed by calcination (method A) and by impregnation of the support produced by dissolving activated aluminum in water with copper nitrate solution (method B), was investigated by diffuse reflection electronic spectroscopy. It was established that the catalysts contain Cu ²⁺ ions stabilized in fields of octahedral symmetry. The concentration of these ions depends on the method of synthesis of the catalyst, its copper content, and the pretreatment temperature. It is higher in the samples produced by impregnation than in the samples produced by fusion; increase in the amount of copper leads to a decrease while increase in the calcination temperature leads to an increase in the concentration of the above-mentioned ions. Treatment of the oxide systems with the reaction mixture does not affect the state and concentration of Cu ²⁺. The catalytic activity of the samples depends on the method of preparation and increases with decrease in the amount of Cu ²⁺ (O_h) and with increase in the content of the CuO phase in the system.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 786–790, April, 1992.     

The structure of a potassium-copper complex with six-membered macrocyclic ethylsiloxanolate ligands

The structure of K₂{[EtSiO₂]₆K₂Cu₄[O₂SiEt]₆} · 4n-BuOH, a novel mixed sandwich-like complex of K⁺ and Cu²⁺ with two 6-membered macrocyclic ethylsiloxanolate ligands, was established by means of X-ray study. The ligands have an all-cis configuration and a crown conformation. Four Cu²⁺ and two K⁺ ions form a planar hexagon sandwiched between antiparallel coaxial macrocyclic ligands. The K⁺ ions occupy two opposite apices of the hexagon. The Cu²⁺ ions have square-planar coordination with four siloxanolate O_M atoms, while the K⁺ ions, are coordinated with two O atoms of the solvating butanol molecules, in addition to four O_M atoms. The electric neutrality of the whole complex is due to the two outer-sphere K⁺ counter-ions, each located over one of the two siloxanolate macrocycles, i.e., over the «decks» of the sandwich and coordinated with endocyclic siloxane O_Si atoms, as in crown-ether complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 752–756, April, 1993.     

Role of Pd(0) particles in oxidation of lower olefins in the catalytic system Fe(III)_Pd/ZrO<Subscript>2</Subscript>

Oxidation of metallic Pd(0) particles applied onto an oxide support with Fe(III) ions in a concentration not exceeding 0.06 M at 70°C was studied. In contrast to palladium black, with the supported catalyst Pd/ZrO₂ Pd(II) is formed in the solution in the concentration corresponding to the thermodynamic equilibrium. With an increase in the initial Fe(III) concentration, the equilibrium yield of Pd(II) increases. The initial reaction rate grows with an increase in the weight of the initial Pd-containing catalyst and in the initial Fe(III) concentration. The revealed kinetic relationships of the dissolution of Pd(0) in the reaction with Fe(III) aqua ions allow a conclusion that, in oxidation of lower olefins C₂-C₄ in the catalytic system Fe(III)_Pd/ZrO₂ in aqueous solution, Pd(II) is regenerated in the catalytic cycle by oxidation of Pd(I) species, rather than of Pd(0), with Fe(III) aqua ions.     

Applications of Macrocyclic Polyethers in Analytical Sensors and Ion Separation

Artificial macrocyclic polyethers were synthesized and applied as neutral carriers for ion-selective PVC membrane electrodes, ion-chromatographic packing materials, extractants and adsorbents for ion separation, coating materials for piezoeletrical membrane sensors for organic species, and ion-transport carriers through liquid membranes. Ion-selective electrodes such as those for K⁺ Na⁺, UO₂²⁺, Cs⁺, Pb²⁺, Fe³⁺, Hg²⁺ and Ag⁺ ions based on crown ether-phosphotungstic acid (PW) precipitates and dithio crown ethers respectively were prepared and showed good sensitivity and selectivity. Crown ether-PW precipitates were applied as adsorbents of rare-earth ions and some common heavy-metal ions. Some rare-earth ions were easily extracted with crown ethers, especially 15-crown-5. Poly(stytene/divinyl benzene) cryptand-22 resin was synthesized and applied as a bifunctional stationary phase of ion chromatography to separate bom cations and anions, even some organic carboxylate geometric isomers. Crown ethers such as mono-benzo-15-crown-5 was successfully applied as a coating material on piezoelectric quartz membrane sensors for some organic species. The oscillation frequency of the crown-ether quartz-membrane sensor was sensitive to organic vapours such as amines and alcohols. Upon adsorption of organic species on the crown-ether quartz membrane, the oscillation frequency of the sensor decreased obviously. Special crown ether such as dibenzo-16-crown-5-oxyacetic acid, decyl-cryptand-22 and 1, 4-dihydro-pyridine-18-crown-5 were synthesized and successfully applied as ion-transport carriers (ionophores) for transport of Na⁺ K⁺ and Mg²⁺ ions through liquid membranes.     

Selective catalytic reduction of nitrogen monoxide with propene over CuCl/MCM-41 catalysts

Selective catalytic reduction of nitrogen monoxide with propene over two kinds of CuCl/MCM-41 catalysts prepared by a dispersion method has been studied. It was found that CuCl/AlMCM-41 exhibits substantially higher activity over CuCl/SiMCM-41. Characterization of these samples by H₂-TPR, IR and XRD showed that the active copper species were mainly related to Cu²⁺ and Cu⁺ ions in CuCl/AlMCM-41 catalyst.     

A Colorimetric and Fluorimetric Chemodosimeter for Copper Ion Based on the Conversion of Dihydropyrazine to Pyrazine

In this research, we successfully synthesized and fully characterized the new compound 5,8,13,16,21,24‐hex‐(triisopropylsilyl)ethynyl)‐6,23‐dihydro‐6,7,14,15,22,23‐hexaza‐trianthrylene ( HHATA , brown color in a mixed solvent of CH₂Cl₂/CH₃CN 1:1, v/v, weakly blue fluorescent), which can be easily oxidized to 5,8,13,16,21,24‐hex‐(triisopropylsilyl)ethynyl)‐6,7,14,15,22,23‐hexazatrianthrylene ( HATA ) (yellow color in CH₂Cl₂/CH₃CN 1:1, v/v), red fluorescent) by Cu²⁺ ions. This reaction only proceeds efficiently in the presence of Cu²⁺ ions when compared with other common metal ions such as Fe³⁺, Co²⁺, Mn²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Ag⁺, Mg²⁺, Ca²⁺, K⁺, Na⁺, and Li⁺. Our result suggests that this reaction can be developed as an effective method for the detection of Cu²⁺ ions.     

Pd-Cu-Clx/Al2O3催化剂对CO氧化的稳定性

CO催化氧化广泛应用于空气净化、机动车尾气治理和CO气体传感器中.在CO氧化催化剂设计与制备过程中,催化剂与使用环境密切相关.例如工业和机动车尾气净化需要在高温(200–600°C)下进行,而对于半密闭空间(隧道或者地下停车场)空气净化需要在室温和高相对湿度下进行.频繁冷启动导致半密闭空间CO浓度累积而超过排放控制标准,因此制备室温、高相对湿度下CO氧化催化剂是面临的重要问题之一.负载型Wacker催化剂对于CO低温催化氧化的研究一直受到广泛关注.环境中少量水的存在会促进负载型Wacker催化剂对CO的低温氧化性能,但随着水沉积量的增加,活性位点将被覆盖,并且Pd和Cu活性组分之间的紧密结构被破坏,从而导致催化剂的失活,即催化剂的稳定性变差.因此,为了提高催化剂在高相对湿度下的稳定性,利用二乙氧基二甲基硅烷对Al2O3载体进行硅烷化处理,以增加载体的疏水性,考察载体疏水改性对CO低温氧化过程中催化剂稳定性的影响.催化剂的稳定性测试结果表明,在0°C,100%相对湿度条件下,未改性催化剂在约20 h内CO转化率由81%下降到50%;载体硅烷化后制备的催化剂在反应进行150 h后,CO转化率仍保持在78%,即反应活性未见降低.由此表明催化剂载体经有机硅烷改性后,可显著增强催化剂在低温、高相对湿度下的稳定性.N2吸附/脱附和水吸附实验结果表明,载体硅烷化改性并未对催化剂的比表面积产生影响,但显著降低了催化剂上水沉积速度和沉积量,未改性催化剂的初始吸水速度是改性后催化剂的4倍,但改性后催化剂的饱和吸水率仅占未改性催化剂的1/3.X射线衍射结果表明,载体预处理后活性物种Cu2(OH)3Cl晶粒尺寸有所增加.氢气程序升温还原、X射线光电子能谱结果表明,载体硅烷化预处理改善了催化剂中Cu和Pd物种的化学分布及接触状态,增加了与Pd物种紧密接触的Cu物种的量,从而促进了Cu物种的还原.与此同时,载体硅烷化显著降低了催化剂表面Cl离子的浓度,从而影响到对CO吸附.为了进一步研究水与催化剂稳定性之间的关系,采用原位红外漫反射(In situ DRIFT)对催化剂进行表征.负载型Wacker催化剂对CO氧化反应机理为:Pd是CO氧化反应的活性中心,通过Pd和Cu物种之间的氧化还原循环来实现CO氧化,且Pd+比Pd2+具有更高的CO氧化性能.反应气氛中水的存在,有利于CO在Pd+上氧化、以及金属态Pd被Cu2+物种再氧化的过程,同时水也显著促进了催化剂表面碳酸盐的生成以及抑制了活性物种Pd+生成.与表面碳酸盐累积相比,水对于活性物种Pd+生成的抑制作用是导致催化剂活性降低的主要原因.     

Synthesis and characterization of graphene oxide‐based hybrid ligand and its metal complexes: Highly efficient sensor and catalytic properties

A new graphene oxide‐based hybrid material (HL) and its Co(II), Cu(II) and Ni(II) metal complexes were prepared. Firstly, graphene oxide and (3‐aminopropyl)trimethoxysilane were reacted to give graphene oxide–3‐(aminopropyl)trimethoxysilane (GO‐APTMS) hybrid material. After that, hybrid material HL was synthesized from the reaction of GO‐APTMS and 2,6‐diformyl‐4‐methylphenol. Finally, Co(II), Cu(II) and Ni(II) complexes of HL were obtained. All the materials were characterized using various techniques. The chemosensor properties of HL were investigated against Na⁺, K⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Ni²⁺, Zn²⁺, Al³⁺, Cr³⁺, Fe³⁺ and Mn³⁺ ions and it was found that HL has selective chemosensing to Fe³⁺ ion. All the graphene oxide‐supported complexes were used as heterogeneous catalysts in the oxidation of 2‐methylnaphthalene (2MN) to 2‐methyl‐1,4‐naphthoquinone (vitamin K₃, menadione) in the presence of hydrogen peroxide, acetic acid and sulfuric acid. The Cu(II) complex showed good catalytic properties compared to the literature. The selectivity of 2MN to vitamin K₃ was 60.23% with 99.75% conversion using the Cu(II) complex.     

Cuprous complexes and dioxygen. IX. Formation of a unique trimeric species Cu3L and Ligand Oxidation (L  cis,cis-1, 3, 5-cyclohexanetriamine)

The complexation of Cu⁺ by the potentially tripod like ligand cis, cis-1, 3, 5 cyclohexanetriamine (chta) has been studied potentiometrically in aqueous acetonitrile (an). The expected tetracoordinated species Cu (chta) ? (an)⁺ was formed only at rather high pH with log K (Cu (an)⁺ + chta ? Cu (chta) · (an)⁺) = 6.94. Quite unexpectedly the most stable complex in neutral solution was the trimetric species Cu³ (chta) with log K (3 Cu⁺ + 2 chta ? Cu³ (chta)) = 31.75. In addition, the ternary complexes Cu (LH²) · (an)³⁺ and Cu (LH) · (an)²⁺ (L = chta) are formed at low pH. From model considerations, Cu³ (chta) must contain two ligand molecules with all amino groups in equatorial position, linked by three linearly coordinated Cu⁺-ions. Cu₃ (chta)³⁺₂ shows no measurable reactivity towards dioxygen. At pH values above 9, very rapid O₂-uptake due to Cu (chta) · (an)⁺ is observed. In this reaction, Cu⁺-autoxidation is stoichiometrically coupled to ligand oxidation, followed by a much slower Cu-catalyzed secondary reaction of the primary oxidation product of chta. Hydrogen peroxide and likely also superoxide, are involved in the coupled Cu⁺/ligand oxidation.     

Controlling carbon monoxide emissions from automobile vehicle exhaust using copper oxide catalysts in a catalytic converter

Carbon monoxide (CO) is a very poisonous gas present in the atmosphere. It has significant effects on human beings, animals, plants and the climate. Automobile vehicle exhaust contributes 64% of the CO pollution in urban areas. To control this exhaust pollution, various types of catalysts in catalytic converters have been investigated. Increasing costs of noble metals as a catalyst in automobile vehicles motivates the investigation of material that can be substituted for noble metals. Among the non-noble metals, copper (Cu) is found to be the most capable and highly active catalyst for CO oxidation, compared to precious metal catalysts. Lower cost, easy availability and advance preparation conditions with stabilizers, promoters and so on, make Cu a good choice as an auto exhaust purification catalyst. The oxidation of CO proceeds very quickly over Cu°, followed by Cu⁺ and Cu²⁺. The Cu₂O catalyst is more active in an O₂-rich atmosphere than in O₂-lean conditions. The reduced species of copper (Cu⁰, Cu⁺) are essential for better CO oxidation but smaller Cu particles could be less active than the higher ones. There is a great deal of research available on the Cu catalyst for CO oxidation, but there is a gap in the literature for a review article individually applied to the Cu catalyst for CO oxidation. To fill this gap, the present review updates information on Cu catalysts in the purification of exhaust gases.     

Effect of Ligands on Formation of Photosensitive Oxide Layers on Copper Electrode*

Photosensitive oxide layers are found to develop on copper electrode exposed to solutions containing Cu(II), different ligands, and K₂SO₄ as a supporting electrolyte. Two mechanisms of Cu₂O formation are discussed: corrosion of copper in naturally aerated Cu(II)-free solutions, and interaction between Cu and Cu²⁺ yielding intermediate Cu⁺ ions. Oxide layers formed in the supporting electrolyte at pH 5 and 7 exhibit n-type conduction; the n–p transition is observed at pH 10. An addition of ligands suppresses the oxide formation. The correlation between the photoelectrochemical effects and the stability of Cu(II) complexes is revealed: the higher the complexation degree, the lower the level of photoresponse. A model of nonuniform Cu₂O-containing layer with predominant n- and p-type properties at copper/oxide and oxide/solution interfaces, respectively, is discussed.     

KCl对Cu-K-La/γ-Al2O3催化剂上HCl氧化反应性能的影响

采用等体积浸渍法制备了Cu-K-La/γ-Al₂O₃催化剂,考察了KCl对该催化剂催化HCl氧化制Cl₂反应性能的影响. 当KCl的负载量为5 wt%时,Cu-K-La/γ-Al₂O₃催化剂表现出较好的催化活性和稳定性,可在较大的原料气空速变化范围内使用. 在0.1 MPa,360 ℃,空速450 L/（kg-cat·h）和HCl/O₂摩尔比为2：1的反应条件下,Cu-K-La/γ-Al₂O₃催化剂上HCl转化率在100 h内保持85%以上. 表征结果表明,Cu,K和La物种均高度分散于γ-Al₂O₃载体表面;一定量KCl的加入可降低Cu²⁺ → Cu⁺的还原温度,从而提高Cu²⁺活性中心的催化活性.     

Copper-cerium oxide catalysts for the selective oxidation of carbon monoxide in hydrogen-containing mixtures: II. Physicochemical characterization of the catalysts

The copper-cerium oxide catalysts were characterized using a set of physicochemical techniques including in situ FTIR spectroscopy, XPS, and XRD. It was found that copper segregated on the surface of cerium oxide and its states were labile and dependent on catalyst pretreatment conditions. Copper in a dispersed state was responsible for the reaction of CO oxidation in the presence of H₂ on the copper-cerium oxide catalysts. It is likely that this state of copper was composed of two-dimensional or three-dimensional surface clusters containing Cu⁺ ions.