Decolorization of synthetic dyes by hydrogen peroxide with heterogeneous catalysis by mixed iron oxides

Heterogeneous catalysts based on magnetic mixed iron oxides (MO·Fe₂O₃; M: Fe, Co, Cu, Mn) were used for the decolorization of several synthetic dyes (Bromophenol Blue, Chicago Sky Blue, Cu Phthalocyanine, Eosin Yellowish, Evans Blue, Naphthol Blue Black, Phenol Red, Poly B-411, and Reactive Orange 16). All the catalysts decomposed H₂O₂ yielding highly reactive hydroxyl radicals, and were able to decolorize the synthetic dyes. The most effective catalyst FeO·Fe₂O₃ (25 mg mL⁻¹ with 100 mmol L⁻¹ H₂O₂) produced more than 90% decolorization of 50 mg L⁻¹ Bromophenol Blue, Chicago Sky Blue, Evans Blue and Naphthol Blue Black within 24 h. The fastest decomposition proceeded during the first hour of the reaction. In addition to dye decolorization, all the catalysts also caused a significant decrease of chemical oxygen demand (COD). Individual catalysts were active in the pH range 2–10 depending on their structure and were able to perform sequential catalytic cycles with low metal leaching.     

Transmission electron microscopy of supported molybdenum and vanadium oxides

Transmission electron microscopy has been used to characterize dispersions of molybdena and vanadia on titania and silica supports. When silica spheres of controlled morphology were used as support, the dispersed monolayer phase of both oxides could be imaged due to characteristic changes in contrast. In addition to the dispersed phase, we could detect three-dimensional crystallites of V₂O₅ but in the case of MoO₃ only two-dimensional islands were seen. On Degussa P-25 titania, there was no observable contrast change due to the presence of a monolayer of these dispersed oxides. However, exposure to the electron beam caused dramatic changes in the surface texture of the support. Such changes were not seen when blank TiO₂ was similarly irradiated. These e-beam induced changes were more pronounced in the vanadia/titania catalysts leading to formation of 1–3 nm clusters of reduced VO _x . However, on the MoO₃/TiO₂ sample, e-beam exposure caused only a pronounced change in texture but no well defined clusters could be detected.     

Preparation and characterisation of vanadium catalysts supported over alumina-pillared clays

Supported vanadium-containing catalysts were prepared by impregnation of Al-pillared clays with NaVO₃ precursor aqueous solutions. A montmorillonite and a saponite, both natural as well as previously pillared with Al₁₃-Keggin polycations, were used as supports, being impregnated with solutions of the precursor by means of the incipient wetness technique. The layered structure of the supports is maintained after impregnation, and even after calcination of the impregnated solids at 500 °C, although with a significant worsening of the textural properties of the solids, in particular, a loss of specific surface area. Three crystalline vanadium-containing phases were identified in the impregnated solids, namely, NaV₃O₈, AlVO₄ and V₂O₅ (shcherbinaite). The reduction of these phases to V³⁺ species was observed as wide processes in the 450–750 °C range, all of them centred at ca. 600 °C.     

Electrochemical promotion of heterogeneous catalysis

The catalytic activity and selectivity of metals interfaced with solid electrolytes can be altered dramatically and reversibly via potential application. The increase in catalytic rate can be several orders of magnitude higher than that anticipated from Faraday's Law. This new phenomenon of electrochemical promotion is of considerable theoretical and potentially practical importance in heterogeneous catalysis. In this paper the main phenomenological features of electrochemical promotion (or NEMCA effect) are surveyed and the origin of the effect is discussed in view of recent surface spectroscopic and quantum mechanical studies.     

Environmentally friendly, heterogeneous acid and base catalysis for the methylation of catechol: Chances for the control of chemo-selectivity

The properties of catalysts with (i) Brønsted-type acidity (H-mordenite and Al/P mixed oxide), (ii) Lewis-type acidity (Al trifluoride) or (iii) basic characteristics (Mg/Fe mixed oxide) were investigated in the gas-phase methylation of catechol. When methanol was used as the methylating agent, H-mordenite and AlF₃ gave high selectivities to guaiacol (the product of O-methylation) under mild reaction conditions, that is at very low catechol conversions. An increase in temperature led to the transformation of guaiacol to phenol and cresols, and to considerable catalyst deactivation. The basic catalyst Mg/Fe/O also favored an extensive degradation of guaiacol to phenol. On the mildly acidic catalyst Al/P mixed oxide a stable catalytic performance and a high selectivity to guaiacol at 40% catechol conversion were obtained. When methylformate, a more reactive methylating agent, was used with AlF₃ and Mg/Fe mixed oxide as catalysts, higher catechol conversions and slower deactivation rates could be achieved under mild reaction conditions, with a low extent of guaiacol degradation. However, methylformate rapidly decomposed when temperatures above 350 °C were used. Finally, tests were made by reacting catechol and diethoxymethane with acid catalysts, with the aim of synthesizing methylenedioxybenzene. The latter product was obtained with high selectivity, but with very low yield, due to both catalyst deactivation and decomposition of diethoxymethane.     

One step liquid phase heterogeneous synthesis of phenytoin over MgAl calcined hydrotalcites

Heterogeneous liquid phase synthesis of phenytoin (5,5-diphenylhydantoin) was carried out over MgAl calcined hydrotalcites for the first time under environmental friendly conditions. The catalytic activity results showed very high conversion (80–95%) and selectivity (90–95%) of the desired product phenytoin over MgAl calcined hydrotalcites. The calcined hydrotalcites can be recycled without further loss in the activity and the possible mechanism of the reaction is also proposed.     

Gas-phase selective oxidation of toluene on TiO2–sepiolite supported vanadium oxides: Influence of vanadium loading on conversion and product selectivities

Gas-phase selective oxidation of toluene has been carried out on vanadium oxide systems (5–20 wt.% of V₂O₅, equivalent to 0.4–1.7 theoretical monolayers) supported on TiO₂–sepiolite (with titania loading around the theoretical monolayer, 12 wt.%) and on sepiolite. A study has been made on both the influence of vanadia loading and of the support on the catalytic behaviour of the supported vanadium systems. The reducibility by H₂ TPR was also studied as well as the acid and basic/redox sites from the results of conversion of the 2-propanol test reaction of the solids. Benzaldehyde, benzoic acid and several coupling products were the main ones detected, attaining over 50% selectivity towards the benzaldehyde and benzoic acid products at a total conversion around 10%. The activity and selectivity to the selective products exhibited by vanadium systems supported on mixed support were superior to those exhibited by the systems supported on sepiolite and increased notably in both series with the increase in vanadium loading. The best catalytic behaviour exhibited by the vanadium systems supported on mixed support, which also exhibited the highest density of sites capable of being reduced (as well as their reducibility) and of those responsible for propanone formation, could be attributed not only to the different balance of the vanadia species existing in the two supports (monomeric + oligomeric/polymeric), but also to such other factors as the nature of the support and, concretely, its chemical composition.     

Multifactorial analysis in the study of hydroformylation of oct-1-ene using supported aqueous phase catalysis

The influence of the hydration and the surface characteristics of five supports in the hydroformylation of oct-1-ene by supported aqueous phase catalysis (SAPC) using [Rh₂(μ-S^tBu)₂(CO)₂(TPPTS)₂] as catalyst was studied. The results confirm that the size of the pores and the amounts of water were found to be the determining factors contributing to the SAPC. According to the size of pores there is a critical value for which the SAPC takes place either in the classical model or in conditions where the pores are filled. When the pores are fully filled the SAPC can operate efficiently onto the external surface, stabilising the conversion in a relatively wide range of support hydration.     

Investigation of factors influencing sodium sulfide oxidation in the presence of polymeric heterogeneous catalysts of transition metal oxides

The activity of heterogeneous catalysts of transition metal oxides and their mixtures deposited on the polymeric matrix in the oxidation of sodium sulfide was investigated. It is shown that mixtures of manganese oxide and other transition metal oxides have high catalytic activity. It was evident that the positive synergistic effect occurred in the combined action of two or more catalytically active transition metal oxides, and the maximum effect was observed in the mixture of three catalytic agents of transition metal oxides. Catalytic mechanism of transition metal oxides for sulfide oxidation was studied. The kinetics of formation of products of sodium sulfide oxidation was studied in the presence of heterogeneous catalysts based on phthalocyanine cobalt and transition metal oxides. The dependence of the rate of formation of products of sodium sulfide oxidation on alkali concentration was investigated. Some factors influencing the oxidation rate such as sulfide, oxygen and alkaline concentrations, antioxidant and oxidation products were investigated.     

The role of V in rutile-type Sn/V/Nb/Sb mixed oxides, catalysts for propane ammoxidation to acrylonitrile

Rutile-type Sn/V/Nb/Sb mixed oxides of composition Sn/V/Nb/Sb 1/x/1/3 (atomic ratios) were prepared by co-precipitation from an alcoholic medium, characterized and tested as catalysts for the ammoxidation of propane to acrylonitrile. Vanadium had a relevant effect on chemical–physical and reactivity properties of catalysts. The latter consisted of Sn oxide incorporating Sb and Nb cations, of defective rutile-type V/Nb/Sb mixed oxide and of Sb oxide. Increasing amounts of V in samples caused an increase of the crystallinity and a corresponding decrease of the specific surface area. However, a relevant enhancement of the catalyst activity (rate of propane conversion per unit surface area) was observed. This was attributed to the generation of cationic vacancies, formed in the rutile-type V/Nb/Sb mixed oxide, that enhanced the intrinsic activity of V ions in the activation of the alkane. On the other hand, the selectivity to acrylonitrile declined considerably when the content of V in samples was increased, whereas the selectivity to carbon monoxide and that to cyanhydric acid increased.     

Oxidative dehydrogenation of ethane with carbon dioxide over silica molecular sieves supported chromium oxides:Pore size effect

SBA-15 with varied pore size from 4 to 8 nm were synthesized by tuning the temperature of hydrothermal treat-ment,the supports were then used to load the active phase CrOx through a conventional impregnation method.The resulting catalysts were characterized by small/wide angle XRD,N2 adsorption/desorption,FT-IR,TEM-EDX,XPS,TPR and CO2-TPD to study the feature of structure,surface chemical state,redox and basicity.It was found from these results that the metal species could be well dispersed on catalysts with larger pore size.Cr6+species could enter into the framework by substituting the Si atoms of SBA-15,and Cr3+mainly exist on extra frame-work Pore size had profound effects on reducibility,surface composition and basicity.Cr6+species were neces-sary to activate the C-H bonds of alkanes,while the basicity played an important role in activating C-O bonds of CO2.The best performances were achieved over the sample Cr supported on SBA-15 with a pore diameter of 7 nm in oxidative dehydrogenation of ethane in the presence of CO2.     

Bridging the gap between homogeneous and heterogeneous gold catalysis: supported gold nanoparticles as heterogeneous catalysts for the benzannulation reaction

Gold nanoparticles supported on metal oxides and activated carbon are able to catalyze the benzannulation reaction of o-(phenylethynyl)benzaldehyde and phenylacetylene to 1-benzoyl-2-phenylnaphtalene with high selectivity at 99% conversion. Benzannulation of ortho-alkynyl benzaldehydes is a reaction typically catalyzed by soluble AuCl₃ and, now, we have found that it can also be catalyzed by heterogeneous gold supported catalysts. The heterogeneous catalytic system can be reused several times without loss of activity or selectivities.     

Low temperature SCR of NO with NH3 over carbon nanotubes supported vanadium oxides

A novel multiwalled carbon nanotube (CNTs) supported vanadium catalyst was prepared. The structure of catalyst prepared was characterized by TEM, BET, FTIR, XRD and temperature-programmed desorption (TPD) methods. The results indicated that vanadium particles were highly dispersed on the wall of carbon nanotubes. The V₂O₅/CNT catalysts showed good activities in the SCR of NO with a temperature range of 373–523 K. The Lewis acid sites on the surface of V₂O₅/CNT are the active sites for the selective catalytic reduction (SCR) of NO with NH₃ at low temperatures. It was suggested that the reaction path might involve the adsorbed NH₃ species reacted with NO from gaseous phase and as well as the adsorbed NO₂ species. The diameter of CNTs showed positive effect on the activities of the catalysts. Under the reaction conditions of 463 K, 0.1 Mpa, NH₃/NO = 1, GHSV = 35,000 h⁻¹, and V₂O₅ loading of 2.35 wt%, the outer diameter of CNTs of 60–100 nm, the NO conversion was 92%.     

Spinel-type cobalt-manganese oxide catalyst for degradation of Orange II using a novel heterogeneous photo-chemical catalysis system

A spinel-type Co-Mn oxide was designed and synthesized through a two-step oxidation-precipitation method at modest temperatures. The Co-Mn oxide was applied as the catalyst in the presence of NaHSO₃ under visible light irradiation in order to establish the superiority of heterogeneous photo-chemical catalysis system. In the above system, the Co-Mn catalyst exhibited much better catalytic capability than that in either single photocatalysis or chemocatalysis system, implying that the Co-Mn catalyst could well combine photocatalysis and chemocatalysis to obtain the highest degradation efficiency of up to 94% within 40?min when using Orange II as the target pollutant. Recycling experiments results showed that the as-obtained catalyst has excellent stability and recyclability. Powder X-ray diffraction (XRD) analysis showed that the as-obtained Co-Mn catalyst had a cubic MnCo₂O_4.5 spinel structure. Because of relatively low temperature (180?℃) synthesis, the catalyst was formed with nanoparticles (25–65?nm) and high specific surface area as confirmed by SEM and BET analyses. XPS indicated the presence of both manganese and cobalt species that serve as reactive sites for the catalytic oxidation reactions. Rational degradation mechanisms responsible for superior catalytic activity and durability were proposed based on a series of experimental results. The active species such as Mn(III), holes and sulfate and hydroxyl radicals were proposed to be responsible for the outstanding degradation results.     

碳材料在多相催化过程中的应用

碳是自然界中存在最为广泛的元素,具有丰富的结构和形态。碳材料不仅可以作为理想的催化剂载体,其本身也表现出对多种催化过程的优异性能。综述了碳材料在化学品制造、环境催化与能源催化等领域的最近研究进展,并总结了碳材料在这些过程中的催化作用机理。     

Metal oxides as heterogeneous catalysts for esterification of fatty acids obtained from soybean oil

The growing demand for renewable energy sources stimulates the development of new technologies for biofuel production. Biodiesel synthesis by esterification of fatty acids is a favorable route, because, differently from transesterification, it does not produce glycerin and uses cheaper raw materials. In this work the study of metal oxides and their performance as Lewis acid catalysts in the esterification of fatty acids obtained from soybean oil presented promising results in heterogeneous catalysis, with reaction yields as high as 89%. The influence of variables such as temperature, reaction time and the amount of catalyst in the reaction yield was also evaluated. The possibility of recycling tin oxide was also studied, showing that it was possible to reuse the catalyst up to ten times without significant losses in its catalytic activity.     

Gas-phase dehydrochlorination of 1, 1, 2, 2-tetrachloroethane over the non-metal supported ionic liquid catalyst

Developing of non-metallic catalyst to replace metal catalyst is a meaningful and challenging direction. In this work, the non-metallic catalyst was synthetized successfully by loading ionic liquid onto the silica surface, which was applied for the gas-phase dehydrochlorination of 1, 1, 2, 2-tetrachloroethane. The 12%TPPC/SiO₂ (wt%) showed the best results with the conversion of 1, 1, 2, 2-tetrachloroethane reaching 100%. The selectivity of 1, 1, 2-trichloroethylene was 100%, and no deactivation was found during the evaluation period. The catalytic mechanism was investigated and possible reaction route was given, which was a reference for fabricating and design of solid base catalyst.     

MoOx-based catalysts for the oxidative dehydrogenation (ODH) of ethane to ethylene: Influence of vanadium and phosphorus on physicochemical and catalytic properties

The influence of vanadium and phosphorus on the physicochemical properties of the MoO_x oxide and on its catalytic properties in the oxidation of ethane to ethylene is examined. A series of MoO_x, MoVO_x (Mo/V = 11) and MoVPO_x (Mo/V = 11, V/P = 1) catalysts were prepared, characterized by several techniques (BET, XRD, XPS, LRS and ATG) and studied in the oxidative dehydrogenation of ethane to ethene at atmospheric pressure and at the temperature of reaction of 550 °C. Their structural properties, during reduction and re-oxidation, were examined by in situ X-ray diffraction and by X-ray photoelectron spectroscopy after pre-treatment. The sample containing phosphorus is the most active (conversion 14%) and selective to ethylene (SC₂H₄ = 67%). The formation of [PMo₁₁VO₄₀]⁴⁻ is assumed during preparation, and its decomposition during calcination leads to well dispersed phosphate groups and improved interactions between Mo and V species. During the catalytic reaction Mo^VI is stabilised by means of solid solutions of V in Mo₅O₁₄ and in MoO₃ (V_xMo_1−xO_3−x/2). A synergetic effect between these two phases could be responsible for the best performance of Mo₁₁VPO_x as compared to those of MoO_x and Mo₁₁VO_x.     

Baeyer–Villiger-oxidation of cyclopentanone with aqueous hydrogen peroxide by acid heterogeneous catalysis

Using aqueous hydrogen peroxide containing 30% H₂O₂, solid acid catalysts were compared in their performance as catalysts for the transformation of cyclopentanone to δ-valerolactone. It could be shown that organic ion exchange resins with sulphonic acid groups providing acid functionality are promising catalysts for this reaction. The variation of several reaction parameters was studied in more detail. The obtained results were compared to investigations of zeolites and Nafion^® composite materials.     

Oxidation of 5-hydroxymethylfurfural over supported Pt, Pd and Au catalysts

Supported Pt, Pd, and Au catalysts were evaluated in the aqueous-phase oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) at 295 K and high pH in a semibatch reactor. The intermediate reaction product 5-hydroxymethyl-2-furancarboxylic acid (HFCA) was formed in high yield over Au/C and Au/TiO₂ at 690 kPa O₂, 0.15 M HMF and 0.3 M NaOH, but did not continue to react substantially to FDCA at the specified O₂ pressure and base concentration. In contrast, the final reaction product FDCA was formed over Pt/C and Pd/C under identical conditions. The initial turnover frequency of HMF conversion was an order of magnitude greater on Au catalysts compared to either Pt or Pd. Increasing the O₂ pressure and NaOH concentration facilitated the conversion of HFCA to FDCA over the supported Au. The significant influence of base concentration on the product distribution indicates an important role of OH⁻ in the activation, oxidation and degradation of HMF.