Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.

Sulfonated Schiff base copper(ii) complexes as efficient and selective catalysts in alcohol oxidation: syntheses and crystal structures

The reaction between 2-aminobenzenesulfonic acid and 2-hydroxy-3-methoxybenzaldehyde produces the acyclic Schiff base 2-[(2-hydroxy-3-methoxyphenyl) methylideneamino] benzenesulfonic acid (H2L center dot 3H(2)O) (1). In situ reactions of this compound with Cu(II) salts and, eventually, in the presence of pyridine (py) or 2,2'-bipyridine (2,2'-bipy) lead to the formation of the mononuclear complexes [CuL(H2O)(2)] (2) and [CuL(2,2'-bipy)]center dot DMF center dot H2O (3) and the diphenoxo-bridged dicopper compounds [CuL(py)](2) (4) and [CuL(EtOH)](2)center dot 2H(2)O (5). In 2-5 the L-2-ligand acts as a tridentate chelating species by means of one of the O-sulfonate atoms, the O-phenoxo and the N-atoms. The remaining coordination sites are then occupied by H2O (in 2), 2,2'-bipyridine (in 3), pyridine (in 4) or EtOH (in 5). Hydrogen bond interactions resulted in R-2(2) (14) and in R-4(4)(12) graph sets leading to dimeric species (in 2 and 3, respectively), 1D chain associations (in 2 and 5) or a 2D network (1). Complexes 2-5 are applied as selective catalysts for the homogeneous peroxidative (with tert-butylhydroperoxide, TBHP) oxidation of primary and secondary alcohols, under solvent-and additive-free conditions and under low power microwave (MW) irradiation. A quantitative yield of acetophenone was obtained by oxidation of 1-phenylethanol with compound 4 [TOFs up to 7.6 x 10(3) h(-1)] after 20 min of MW irradiation, whereas the oxidation of benzyl alcohol to benzaldehyde is less effective (TOF 992 h(-1)). The selectivity of 4 to oxidize the alcohol relative to the ene function is demonstrated when using cinnamyl alcohol as substrate.

Copper-cobalt foams as active and stable catalysts for hydrogen release by hydrolysis of sodium borohydride

The progress of hydrogen generation by sodium borohydride hydrolysis depends highly on the development of efficient catalysts based on non-noble metals such as cobalt. However, such catalysts undergo extensive deactivation which has a detrimental effect on their stability. Herein, highly porous copper and cobalt-based bimetallic foams, CuxCo100-x (x = 0-100 at%), produced by electrodeposition using the dynamic hydrogen bubble template are reported. The chemical composition of the foams was optimized in order to enhance specific surface area and improve their catalytic activity and stability as heterogeneous catalysts for sodium borohydride hydrolysis. Among the tested catalysts, copper-rich samples like Cu85Co15 are slightly more active than Co-100 and above all, they are less sensitive to deactivation by borates adsorption. Porous copper-rich foams were found to be an alternative to cobalt as low-cost, active and stable heterogeneous catalysts for hydrogen generation by hydrolysis of sodium borohydride. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Aroylhydrazone Cu(II) complexes in keto form: structural characterization and catalytic cctivity towards cyclohexane oxidation

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with a copper(II) salt of a base of a strong acid, i.e., nitrate, chloride or sulphate, yielded the mononuclear complexes [Cu(H2L)(NO3)(H2O)] (1), [Cu(H2L)Cl]center dot 2MeOH (2) and the binuclear complex [{Cu(H2L)}(2)(mu-SO4)]center dot 2MeOH (3), respectively, with H2L- in the keto form. Compounds 1-3 were characterized by elemental analysis, Infrared (IR) spectroscopy, Electrospray Ionisation-Mass Spectrometry (ESI-MS) and single crystal X-ray crystallography. All compounds act as efficient catalysts towards the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, under mild conditions. In the presence of an acid promoter, overall yields (based on the alkane) up to 25% and a turnover number (TON) of 250 (TOF of 42 h(-1)) after 6 h, were achieved.

Scorpionate complexes as catalysts for alkane functionalization

A survey of the scorpionate tris(pyrazolyl)methane complexes synthesized by our group is presented, as well as their structural features and catalytic applications toward the funtionalization of linear and cyclic light alkanes.

n-Hexane hydroisomerisation over bifunctional Pt/MCM-22 catalysts. Influence of the mode of Pt introduction

Three different methods were used to introduce 1.0 wt.% of Pt in bifunctional Pt/MCM-22 zeolite catalysts: ion exchange with Pt(NH3)(4)(2+), incipient wetness impregnation with PtCl6H2 and mechanical mixture with Pt/Al2O3. The Pt dispersion was estimated by transmission electron microscopy and the hydrogenating activity with toluene hydrogenation at 110 degrees C. From these experiments, it can be concluded that with the ion exchanged sample, platinum was located within the inner micropores and on the outer surface, whereas with the impregnated one, platinum was essentially on the outer surface under the form of large particles. With all the samples there is a fast initial decrease in the activity for n-hexane hydroisomerisation at 250 degrees C. With exchanged and impregnated samples, this decrease is followed by a plateau, the activity value being then higher with impregnated sample. For the sample prepared by mechanical mixture a continuous decrease in activity can be observed. All these differences can be related with the distinct locations of Pt.

New heterogeneous catalysts for trans-esterification of triglycerides

This paper describes preliminary work done towards the development of new metallic heterogeneous catalysts to be used in the transesterification reaction of triglycerides, which is of considerable interest in the production of biodiesel. Biodiesel, is a mixture of mono-alkyl esters of fatty acids, and is currently manufactured by transesterification of triglycerides with methanol using NaOH or KOH as liquid base catalyst. Catalysts as such are corrosive to the equipment, and as these catalysts are in liquid phase must be neutralized after the completion of the reaction, typically using HCl, thus producing salt streams. Moreover, due to the presence of free fatty acids it reacts to form soaps as unwanted by-products, hence requiring more expensive separation processes. Therefore, there is a great need on the development of industrial processes for biodiesel production using solid acid catalysts. The key benefit of using solid acid catalysts is that no polluting by-products are formed and the catalysts do not have to be removed since they do not mix with the biodiesel product.

Advances on the development of novel heterogeneous catalysts for transesterification of triglycerides in biodiesel

This paper describes experimental work done towards the search for more profitable and sustainable alternatives regarding biodiesel production, using heterogeneous catalysts instead of the conventional homogenous alkaline catalysts, such as NaOH, KOH or sodium methoxide, for the methanolysis reaction. This experimental work is a first stage on the development and optimization of new solid catalysts, able to produce biodiesel from vegetable oils. The heterogeneous catalytic process has many differences from the currently used in industry homogeneous process. The main advantage is that, it requires lower investment costs, since no need for separation steps of methanol/catalyst, biodiesel/catalyst and glycerine/catalyst. This work resulted in the selection of CaO and CaO modified with Li catalysts, which showed very good catalytic performances with high activity and stability. In fact FAME yields higher than 92% were observed in two consecutive reaction batches without expensive intermediate reactivation procedures. Therefore, those catalysts appear to be suitable for biodiesel production.

Hydroisomerization of n-decane over SAPO-11 catalysts synthesized with methylamine as co-template

The present work deals with preliminary studies concerning a new synthesis approach to prepare SAPO materials with AEL structure and evaluate their catalytic behavior in the hydroisomerization of long paraffins. The new SAPO-11 catalysts were synthesized with the help of a small amine (methylamine, MA) added during the preparation of the initial gel. As MA incorporates into the structure of the final materials, it contributes, together with DPA (dipropylamine), to an increase in Si incorporation as isolated species, which results in Bronsted acid sites. Thus, this new and original synthesis strategy allows to obtain materials with enhanced Bronsted acidity when compared with free MA materials. The catalysts were tested in n-decane hydroisomerization (n-decane was used as a model molecule) and confirmed the effect of MA on the acidic properties of the catalysts. The samples synthesized with MA present a higher number of acid sites that increase the catalytic conversion but have a negative effect in the isomerization selectivity, i.e. a more significant amount of cracking products is formed.

Novel Scorpionate and Pyrazole Dioxovanadium Complexes, Catalysts for Carboxylation and Peroxidative Oxidation of Alkanes

The dioxovanadium(V) complexes [VO2(3,5-Me(2)Hpz)(3)][BF4] (1) (pz = pyrazolyl), [VO2{SO3C(pz)(3)}] (2), [VO2{HB(3,5-Me(2)pz)(3)}] (3) and [VO2{HC(pz)(3)}][BF4] (4), bearing pyrazole or scorpionate ligands, were obtained by reaction of triethyl vanadate [VO(OEt)(3)] with hydrotris(3,5-dimethyl-1-pyrazolyl)methane [HC(3,5-Me(2)pz)(3)] or 3,5-dimethylpyrazole (3,5-Me(2)Hpz; 1), lithium tris(1-pyrazolyl)methanesulfonate {Li[SO3C(pz)(3)], 2}, potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate {K[HB(3,5-Me(2)pz)(3)], 3} and hydrotris(1-pyrazolyl)methane [HC(pz)(3), 4], respectively. Treatment of [VO(OEt)(3)] with potassium hydrotris(1-pyrazolyl)borate {K[HB(pz)(3)]} led to the mixed eta(3)-tris(pyrazolyl)borate and eta(2)-bis(pyrazolyl)borate oxovanadium(IV) complex [VO{HB(pz)(3)}{H2B(pz)(2)}, 5]. The compounds were characterized by elemental analyses, IR, NMR and EPR spectroscopy, FAB and ESI mass spectrometry, cyclic voltammetry and, for 5, also by single crystal X-ray diffraction analysis. All complexes exhibit catalytic activity in the single-pot carboxylation [in trifluoroacetic acid/potassium peroxodisulfate (CF3COOH/K2S2O8)] of gaseous alkanes (methane and ethane) to carboxylic acids (yields up to 40%. TONs up to 157) and in the peroxidative oxidation [in water/acetonitrile (H2O/NCMe)] of liquid alkanes (cyclohexane and cyclopentane) to the corresponding alcohols and ketones (yields up to 24%, TONs up to 117), under mild conditions.

Structural and optical studies of Au doped titanium oxide films

Thin films of TiO2 were doped with Au by ion implantation and in situ during the deposition. The films were grown by reactive magnetron sputtering and deposited in silicon and glass substrates at a temperature around 150 degrees C. The undoped films were implanted with Au fiuences in the range of 5 x 10(15) Au/cm(2)-1 x 10(17) Au/cm(2) with a energy of 150 keV. At a fluence of 5 x 10(16) Au/cm(2) the formation of Au nanoclusters in the films is observed during the implantation at room temperature. The clustering process starts to occur during the implantation where XRD estimates the presence of 3-5 nm precipitates. After annealing in a reducing atmosphere, the small precipitates coalesce into larger ones following an Ostwald ripening mechanism. In situ XRD studies reveal that Au atoms start to coalesce at 350 degrees C, reaching the precipitates dimensions larger than 40 nm at 600 degrees C. Annealing above 700 degrees C promotes drastic changes in the Au profile of in situ doped films with the formation of two Au rich regions at the interface and surface respectively. The optical properties reveal the presence of a broad band centered at 550 nm related to the plasmon resonance of gold particles visible in AFM maps. (C) 2011 Elsevier B.V. All rights reserved.

Copper Bis(oxazoline) Encapsulated in Zeolites and Its Application as Heterogeneous Catalysts for the Cyclopropanation of Styrene

A copper C(2)-symmetric bis(oxazoline), CuBox, was introduced in two forms of commercial Y zeolite: a sodium form (NaY) and an ultrastable form (NaUSY). CuBox was introduced by first partially exchanging the sodium cations of both zeolites for copper and then by refluxing the obtained materials with a solution of bis(oxazoline) (Box). Two different loadings were prepared for each form of zeolite. The materials were characterized by copper ICP-AES, elemental analysis, XPS, FTIR, TG, and nitrogen adsorption isotherms at -196 degrees C. Evidence for Box ligand location in the supercages of NaY and NaUSY zeolites and its coordination to the exchanged copper(II) was obtained by the several techniques used. The materials were all active in the cyclopropanation of styrene with ethyldiazoacetate at room temperature and diastereoselective toward trans cydopropanes. Although the materials containing Box showed low enantioselectivities, their catalytic activities were higher than the parent copper exchanged zeolites, and did not decrease with reuse, at least during three consecutive cycles.

Study of Pt/MCM-22 based catalysts in the transformation of n-hexane: effect of rare earth elements and mode of platinum introduction

The bifunctional transformation of n-hexane was carried out over Pt/MCM-22 based catalysts. MCM-22 was synthesized and submitted to ion exchange with rare earth nitrate solutions of La, Nd and Yb, followed by Pt introduction. Three different methods were used to introduce about 1 wt% of Pt in the zeolite: ion exchange, incipient wetness impregnation and mechanical mixture with Pt/Al(2)O(3). The bifunctional catalysts were characterized by transmission electron microscopy and by the model reaction of toluene hydrogenation. These experiments showed that, in the ion exchanged sample, Pt is located both within the inner micropores and on the outer surface, whereas in the impregnated one, the metal is essentially located on the outer surface under the form of large particles. The presence of RE elements increases the hydrogenating activity of Pt/MCM-22 since the location of these species at the vicinity of metal particles causes modification on its electronic properties. Whatever the mode of Pt introduction, a fast initial decrease in conversion is observed for n-hexane transformation, followed by a plateau related to the occurrence of the catalytic transformations at the hemicages located at the outer surface of the crystals. The effect of rare earth elements on the hydrogenating function leads to a lower selectivity in dibranched isomers and increased amounts of light products.

Study on the use of MgAl hydrotalcites as solid heterogeneous catalysts for biodiesel production

This paper, reports experimental work on the use of new heterogeneous solid basic catalysts for biodiesel production: double oxides of Mg and Al, produced by calcination, at high temperature, of MgAl lamellar structures, the hydrotalcites (HT). The most suitable catalyst system studied are hydrotalcite Mg:Al 2:1 calcinated at 507 degrees C and 700 degrees C, leading to higher values of FAME also in the second reaction stage. One of the prepared catalysts resulted in 97.1% Fatty acids methyl esters (FAME) in the 1st reaction step, 92.2% FAME in the 2nd reaction step and 34% FAME in the 3rd reaction step. The biodiesel obtained in the transesterification reaction showed composition and quality parameters within the limits specified by the European Standard EN 14214. 2.5% wt catalyst/oil and a molar ratio methanol:oil of 9:1 or 12:1 at 60 -65 degrees C and 4 h of reaction time are the best operating conditions achieved in this study. This study showed the potential of Mg/Al hydrotalcites as heterogeneous catalysts for biodiesel production. (C) 2011 Elsevier Ltd. All rights reserved.

Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions

The oxovanadium(IV) complexes [VO(acac)(2)(Hpz)].HC(pz)(3) 1.HC(pz)(3) (acac= acetylacetonate, Hpz = pyrazole, pz = pyrazoly1) and [VOCl2{HOCH2C(pz)(3)}] 2 were obtained from reaction of [VO(acac)(2)] with hydrotris(1-pyrazolyl)methane or of VCl(3)with 2,2,2-tris(1-pyrazolyl)ethanol. The compounds were characterized by elemental analysis, IR, Far-IR and EPR spectroscopies, FAB or ESI mass-spectrometry and, for 1, by single crystal X-ray diffraction analysis. 1 and 2 exhibit catalytic activity for the oxidation of cyclohexane to the cyclohexanol and cyclohexanone mixture in homogeneous system (TONS up to 1100) under mild conditions (NCMe, 24h, room temperature) using benzoyl peroxide (BPO), tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide or the urea-hydrogen peroxide adduct (UHP) as oxidants. 1 and 2 were also immobilized on a polydimethylsiloxane membrane (1-PDMS or 2-PDMS) and the systems acted as supported catalysts for the cyclohexane oxidation using the above oxidants (TONs up to 620). The best results were obtained with mCPBA or BP0 as oxidant. The effects of various parameters, such as the amount of catalyst, nitric acid, reaction time, type of oxidant and oxidant-to-catalyst molar ratio, were investigated, for both homogeneous and supported systems. (C) 2012 Elsevier B.V. All rights reserved.