Non-oxidative dehydrogenation of ethane to ethylene over chromium catalysts prepared from layered double hydroxide precursors

Non-oxidative dehydrogenation of ethane into ethylene at 700 °C over reductively pretreated Cr–Mg–Al and Cr–Mg mixed oxide catalysts has been studied. The catalysts were prepared from layered double hydroxide (LDH) precursors that contained various species of chromium (i.e., cationic Cr(III), complex of Cr(III) with an anionic chelating agent, and chromate anion). Synthesized materials were characterized with powder X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy techniques. It was shown that the surface area of the LDH-derived mixed oxides, their catalytic performance, coking ability, and susceptibility to sintering were highly dependent on the method used for introducing chromium into the LDH precursors of the catalysts.     

Effects of Reducibility on Propane Oxidative Dehydrogenation over γ-Al2O3-Supported Chromium Oxide-Based Catalysts

Alumina-supported chromium oxide and binary mixed oxide catalysts of the form Cr–M oxide/-Al₂O₃ (where M is Ni, Co, Mo, W, Ho, La, Li, Cs or Bi) were found to catalyze the oxidative dehydrogenation of propane at 300-450 °C. The basic characters of the metals were found to determine partly the selectivity to propylene. Cr–Mo/-Al₂O₃ proved to be the most promising. It exhibited a propylene yield of 10.3% at 450 °C. The connections between the selectivity and reducibility of the catalyst were explored. TPR results showed that addition of molybdenum to chromium increased the temperature of reduction maxima. Thus the selectivity to propylene was improved by a decrease in the tendency of the catalyst to undergo a redox cycle. Further, an X-ray photoelectron spectroscopy study conducted on a sample of the catalysts showed that the basicity of the catalysts increased with increase in molybdenum. Catalysts with appropriate Cr/Mo ratios exhibited lower selectivity to over-oxidation product than those containing either chromium or molybdenum alone.     

Electrochemical synthesis of Cr(II) at carbon electrodes in acidic aqueous solutions

The electrochemical synthesis of Cr(II) has been investigated on a vitreous carbon rotating disc electrode and a graphite felt electrode using cyclic voltammetry, impedance spectroscopy and chronoamperometry. The results show that in 0.1 M Cr(III) + 0.5 M sulphuric acid and in 0.1 M Cr(III) + 1 M hydrochloric acid over an electrode potential range of –0.8 to 0.8 V vs SCE, the electrochemical reaction at carbon electrodes is essentially a surface process of proton adsorption and desorption, without significant hydrogen evolution and chromium(II) formation. At electrode potentials more negative than –0.8 V vs SCE, both hydrogen evolution and chromium(II) formation occurred simultaneously. At electrode potentials –0.8 to –1.2 V vs SCE, the electrochemical reduction of Cr(III) on carbon electrodes is controlled mainly by charge transfer rather than mass transport. Measurements on vitreous carbon and graphite felt electrodes in 1 M HCl, with and without 0.1 M CrCl₃, allowed the exchange current density and Tafel slope for hydrogen evolution, and for the reduction of Cr(III) to Cr(II), to be determined. The chromium(III) reduction on vitreous carbon and graphite electrodes can be predicted by the extended high field approximation of the Butler–Volmer equation, with a term reflecting the conversion rate of Cr(III) to Cr(II).     

Development of cobalt–copper nanoparticles as catalysts for higher alcohol synthesis from syngas

The synthesis of higher alcohols from syngas has been studied over different types of Cu-based catalysts. In order to provide control over the catalyst composition at the scale of a few nanometers, we have synthesized two sets of Co–Cu nanoparticles with novel structures by wet chemical methods, namely, (a) cobalt core–copper shell (Co@Cu) and (b) cobalt–copper mixed (synthesized by simultaneous reduction of metal precursors) nanoparticles. These catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The catalysts were tested for CO hydrogenation at temperatures ranging from 230 °C to 300 °C, 20 bar and 18,000 scc/(hr.gcat). It was observed that the Co–Cu mixed nanoparticles with higher Cu concentration exhibit a greater selectivity towards ethanol and C₂₊ oxygenates. The highest ethanol selectivity achieved was 11.4% with corresponding methane selectivity of 17.2% at 270 °C and 20 bar.     

Surface modification of Inconel-600 by growth of a hydrous oxide film

In this study, Inconel-600 (Ni–Cr–Fe alloy) was modified by repetitive potential cycling in 1M NaOH solution. This procedure induced the growth of a hydrous oxide film, following the same mechanism as previously reported for pure nickel in alkaline solution under similar experimental conditions. The electrode, modified by 30 repetitive potential cycles, exhibited about one order of magnitude lower current density in both the active and passive ranges of the anodic polarization curve. Selective dissolution of nickel and iron in acid solution was determined by rotating ring–disc electrode measurements. This process resulted in chromium enrichment as shown by use of X-ray electron spectroscopy. The proposed model for the enhanced stability of the modified electrode agrees with the percolation model of passivity of stainless steels and Fe–Cr alloys.     

CrOx/SiO2 catalysts prepared using chromium recovered from tanning sewage

Catalysts at different Cr loading (x, in the range 0.18–3.8 wt% Cr) were prepared by (i) impregnation of SiO₂ Aerosil directly with the waste water (SCx(I) samples); or (ii) mixing Aerosil with chromium oxo-hydroxides, precipitated from the waste water to eliminate the sulphate and sodium ions (SCx(II) and SCx(III) samples). Preparations (II) and (III) only differ for the accuracy in sulphate and sodium ions elimination. Catalyst surface characterization was performed by FT-IR spectroscopy using CO, adsorbed at room temperature, as test molecule, and by UV-Vis-NIR DR spectroscopy. Their activity towards ethylene polymerization were tested by FT-IR spectroscopy, monitoring the time dependence of the CH₂ stretching modes intensity. The obtained results were compared with those obtained for simplified Phillips catalysts with comparable chromium contents, SCx(R). SCx(I) catalysts were not active in the ethylene polymerization, while the SCx(II) and SCx(III) ones showed lower activity (1/10 at maximum) compared to that of simplified Phillips catalysts with comparable chromium contents. SCx(II) and SCx(III) catalysts were active in the isobutane dehydrogenation reaction and showed activity in the range of those of standard catalysts, while SCx(I) ones showed activity at 873 K, but very low at the usual temperatures (773–823 K).     

Supported chromium oxide catalysts using metal carboxylate complexes: dehydrogenation of propane

The present paper constitutes the first stage of a systematic study of the influence of precursor nature and structure on the catalyst behavior in dehydrogenation of propane, by varying the nature of the ligands and the nuclearity of the starting compounds at fixed net surface potentials. We show results obtained by the use of different Cr carboxylates to design the Cr₂O₃/γ-Al₂O₃ catalyst at low loadings and these results are compared with those obtained for chromic acid. The following short chain chromium compounds were selected as precursors: citrate (Cr(III)), dimer monohydrate acetate (Cr(II)), acetyl acetonate (Cr(III)) and hydroxyacetate (Cr(III)). An exhaustive characterization by means of BET surface, XPS, XRD, X-ray fluorescence, laser Raman spectroscopy, EPR and catalytic test in propane dehydrogenation enabled us to draw relevant conclusions. Low metal–support interaction might be the major cause of polymerization in Carbox. The interaction between the chromia phase and the support surface, which stabilizes different oxidation stages and coordinations of the chromia species, defines the surface architecture. Part of the Cr³⁺ is incorporated in the vacant octahedral sites of the spinel surface. The larger extension of this phenomenon in Cral might be responsible for surface inactive species that could cause a loss of catalytic activity. Deactivation between cycles might depend on the catalyst stabilization by the incorporation of Cr³⁺ into the support structure. The surface array of monomer species in a polymer species environment stabilizes the catalyst architecture and confers characteristics of high stability between cycles. The above considerations permit to infer that chromium carboxylates are interesting precursors for the control of surface species in chromia/Al₂O₃ catalysts.     

Chemical composition and structural transformations of amorphous chromium coatings electrodeposited from Cr(III) electrolytes

Amorphous chromium coatings were electrodeposited from Cr(III)-based solutions containing organic (HCOONa) or phosphorus-containing (NaH₂PO₂) additives. Their structure was studied by a combination of X-ray diffraction (XRD), valence-to-core X-ray emission spectroscopy (XES) and X-ray absorption spectroscopy (XAS) at the Cr K-edge. Metalloid atoms (C or P) incorporated in electroplates structure are chemically bonded to chromium (i.e. are located in the first coordination shell). Upon annealing at elevated temperatures in vacuum, these amorphous coatings crystallize into a mixture of phases containing metallic chromium and chromium carbides or chromium phosphides. Quantitative analysis of valence-to-core XES data demonstrates that the average local structure of chromium in the amorphous coatings does not change significantly during crystallization.     

A new route to synthesis of sulphonato-salen-chromium(III) hydrotalcites: Highly selective catalysts for oxidation of benzyl alcohol to benzaldehyde

The Mg–Al layered-double hydroxides (LDHs) intercalated by three kinds of sulphonato-salen-chromium(III) complexes were prepared and characterized by FTIR, UV–vis, XRD and elemental analysis. It was found that the homogeneous complexes were successfully intercalated into the LDH interlayer via the method of anion exchange followed by coordination with chromium(III) chloride. And the resulting LDH hosted chromium complexes were shown to be effective heterogeneous catalysts for the solvent-free oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) using 30% H₂O₂ as oxidant. Furthermore, owing to the different local environment of the central metal ion chromium(III), the catalyst with the backbone of o-C₆H₄ displayed the highest catalytic performance followed by the NH(CH₂CH₂)₂ with the (CH₂)₂ showing the lowest BzH yield. In addition, a tentative mechanism was also discussed.     

Preparation,characterization and testing of Cr/AlSBA-15 ethylene polymerization catalysts

Ethylene polymerization catalysts have been prepared by grafting chromium(III) acetylacetonate onto AlSBA-15 (Si/Al = ∞, 156, 86 and 30) mesoporous materials. A combination of XRD, nitrogen adsorption, TEM, ICP-atomic emission spectroscopy, H₂-TPR, TGA, UV–vis and FT-IR spectroscopy, were used to characterize the prepared Cr–AlSBA-15 catalysts. By reducing the Si/Al ratio of the AlSBA-15 supports increases the amount of chromium anchored, promotes the stabilization of chromium species as chromate and decreases the reduction temperature of Cr⁶⁺ ions determined by H₂-TPR. Attachment of Cr species onto AlSBA-15 surface results from the interaction of hydroxyl groups with the acetylacetonate ligands through H-bonds. On the contrary, a ligand exchange reaction may occur over siliceous SBA-15.The polymerization activity of Cr–AlSBA-15 catalysts is significantly improved by increasing aluminium content of the AlSBA-15 supports. Particularly, the chromium catalyst prepared with AlSBA-15 (Si/Al = 30) support is almost four times more active than a conventional Cr/SiO₂ Phillips catalyst. Polymers obtained with all the catalysts showed melting temperatures, bulk densities and high load melt indexes indicating the formation of linear high-density polyethylene.     

Preparation,characterization, and polymerization of chromium complexes‐grafted Al/SBA‐15 and Ti/SBA‐15 nanosupports

Ethylene polymerization catalysts have been prepared by grafting chromium (III) nitrate onto Al/SBA‐15 and Ti/SBA‐15 mesoporous materials. A combination of XRD, nitrogen adsorption, TEM, and inductively coupled plasma‐atomic emission spectroscopy (ICP‐AES), were used to characterize the catalysts. Polymerization activity of Cr/SBA‐15 catalyst is significantly improved by Al or Ti insertion to the supports. Particularly, the chromium catalyst prepared with Ti/SBA‐15 support is more active than Al/SBA‐15 catalyst. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Suzuki cross-coupling reaction over a palladium–pyridine complex immobilized on hydrotalcite

A catalyst consisting of a Pd(II) complex immobilized on the surface of a layered double hydroxide (LDH) was prepared. The Pd–LDH complex proved effective in the Suzuki cross-coupling reaction under very mild conditions (viz. a temperature of 55 °C and atmospheric pressure); in fact, it provided conversion and selectivity results surpassing those of existing heterogeneous phase catalysts and most homogeneous phase catalysts for the same purpose. The support and the active phase of the catalyst were characterized by using various instrumental techniques including X-ray diffraction and NMR spectroscopy. Of the inorganic bases used in combination with the catalyst, potassium carbonate was found to provide the best results in the reaction.     

Effects of the preparation methods on the performance of the Cu–Cr–Fe/γ-Al2O3 catalysts for the synthesis of 2-methylpiperazine

Co-precipitation, impregnation and ultrasonic sol–gel (USG) methods have been used to prepare Cu–Cr–Fe/γ-Al₂O₃ catalysts, which were further used to synthesize 2-methylpiperazine. The catalysts were characterized by XRD, XPS, TG/DSC, BET, TPR, AAS and TEM. It is found that preparation method can greatly impact the catalytic performance of the catalysts, the Cu–Cr–Fe/γ-Al₂O₃ catalyst prepared by the ultrasonic sol–gel method proved to be the most active and stable for this reaction. The dispersion and stabilization of Cu⁰ in the reduced catalysts are attributed to the existence of CuCr₂O₄ and Fe₂O₃. A surprising copper migration was detected by XPS analysis for the Cu–Cr–Fe/γ-Al₂O₃-USG catalyst after the calcination process, which may be crucial to the high activity and stability of this catalyst.     

Rutile-type Cr/Sb mixed oxides as heterogeneous catalysts for the ammoxidation of propane to acrylonitrile

Cr/Sb mixed oxides with a rutile-type structure were synthesized by calcining (700°C) a mixture of oxohydrates obtained by coprecipitation from an alcohol solution containing the required amount of the components. The samples were characterized using X-ray powder diffraction (XRD), FT-IR spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). In the Cr/Sb/O compound prepared with Cr/Sb 1/0.8 (atomic ratio), an almost stoichiometric CrSbO₄develops (no antimony or chromium oxides are found), which however is characterized by enrichment in Sb in outmost rutile atomic layers, and thus by a non-homogeneous intracrystalline distribution of the two components. For Cr/Sb ratios lower than 1, the amount of Sb in the rutile-type structure exceeds the stoichiometric value. The reactivity of Cr/Sb/O catalysts with increasing Sb contents (from Cr/Sb 1/0.8 to 1/2.8) is slightly affected by the Cr/Sb atomic ratio. In particular, the selectivity increases with increasing Sb content, while the catalytic activity is higher for the samples having higher Cr/Sb ratios. The Cr/Sb/O system presents considerable differences with respect to the V/Sb/O rutile system; these differences are discussed in reference to the properties of the transition metal components of the rutile mixed oxides.     

Alkoxylation reaction catalysed by layered double hydroxides

Layered double hydroxides (LDHs) are extensively studied as precursors for catalysts, following a calcination at high temperatures to yield mixed oxides. However, these materials are less used as layered materials, i.e., without undergoing thermal activation. We have focused in this work on the use of a series of as-synthesised LDHs for the catalytic preparation of glycol ethers, which is a reaction of primary commercial importance. Two main systems are considered, namely the [Cu–Cr] and [Mg–Al] LDHs. The [Cu–Cr–Cl] LDH is obtained by the coprecipitation method, then through the appropriate chimie douce exchange reactions the original chloride anions are replaced by a variety of oxo- and polyoxometallates, (CrO₄)²⁻, (Cr₂O₇)²⁻, (V₂O₇)²⁻, (V₁₀O₂₈)⁶⁻ and (Mo₇O₂₄)⁶⁻. On the other hand, the [Mg–Al] hydrotalcites, intercalated by (V₂O₇)²⁻, (V₁₀O₂₈)⁶⁻ and [Fe^III(CN)₆]³⁻ anions, are obtained by structure regeneration. This was done by rehydration of a commercial calcined material (Kyowa) in aqueous solutions containing the desired anion. The different materials have been fully characterised by conventional analytical techniques to evidence their lamellar properties and chemical nature. They were then tested in the catalytic reaction involving butan-1-ol and one or more units of ethylene oxide to make butyl-monoglycol ether (BMGE), di-glycol ether (BDGE), tri-glycol ether (BTGE), etc. The reactions were carried out between 80 and 120°C, temperature range in which no collapse of the lamellar structure is normally observed. In this paper it is shown that decavanadate exchanged LDHs proved to be very selective catalysts for the preparation of the monoglycol adduct, some samples achieving up to 100% selectivity in the screening tests.     

Chemical and electrochemical considerations on the removal process of hexavalent chromium from aqueous media

Two methods were used to remove Cr(VI) from industrial wastewater. Although both are based in the same general reaction: 3Fe(II)_(aq) + Cr(VI)_(aq) ; 3Fe(III)_(aq) + Cr(III)_(aq) the way in which the required amount of Fe(II) is added to the wastewater is different for each method. In the chemical method, Fe(II)_(aq) is supplied by dissolving FeSO₄ · 7(H₂O)_(s) into the wastewater, while in the electrochemical process Fe(II)_(aq) ions are formed directly in solution by anodic dissolution of an steel electrode. After this reduction process, the resulting Cr(III)_(aq) and Fe(III)_(aq) ions are precipitated as insoluble hydroxide species, in both cases, changing the pH (i.e., adding Ca(OH)_2(s)). Based on the chemical and thermodynamic characteristics of the systems Cr(VI)–Cr(III)–H₂O–e^– and Fe(III)–Fe(II)–H₂O–e^– both processes were optimized. However we show that the electrochemical option, apart from providing a better form of control, generates significantly less sludge as compared with the chemical process. Furthermore, it is also shown that sludge ageing promotes the formation of soluble polynuclear species of Cr(III). Therefore, it is recommended to separate the chromium and iron-bearing phases once they are formed. We propose the optimum hydraulic conditions for the continuous reduction of Cr(VI) present in the aqueous media treated in a plug-flow reactor.     

Direct synthesis of mesoporous M-SBA-15 (M = Al, Fe, B, Cr) and application to 1-hexene oligomerization

M-SBA-15 materials (M = Al, B, Cr, Fe) were prepared by different direct synthesis methods, characterized and tested catalytically in the 1-hexene oligomerization reaction at 125 °C. Al-SBA-15 were synthesized within the range Si/Al = 12–86 using aluminium isopropoxide as aluminium source. ²⁷Al MAS NMR spectra point out that the three Al-SBA-15 samples contain more tetrahedral aluminium than octahedral and the ratio tetrahedral/octahedral diminished with increasing aluminium contents. B-SBA-15 was prepared with a Si/B = 51–106 using two direct synthesis methods (sol–gel and hydrothermal) and three different boron sources (solid boric acid, aqueous boric acid and boron isopropoxide). The best results in terms of boron incorporation (Si/B = 51) were achieved with solid boric acid and the sol–gel method, although a lower degree of mesoscopic ordering was obtained compared to the hydrothermal procedure. ¹¹B MAS NMR showed that trigonal boron is the principal coordination state obtained after calcination. Cr-SBA-15 was also achieved by direct synthesis method at different pH (1.5, 3, 5) but the incorporation degree was low, at best Si/Cr = 240 at pH 5. UV–vis spectroscopy indicated that all Cr species were Cr⁶⁺ formed during the calcination step. Oligomerization of 1-hexene at 125 °C showed that the highest conversion (30%) was attained over Al-SBA-15 (Si/Al = 30) although Cr-SBA-15 material exhibited close conversion (21%) despite its low heteroatom content (Si/Cr = 240). Dimers were the major products over Al-SBA-15, Cr-SBA-15 and Fe-SBA-15 catalysts (selectivity ≥ 40%) while strikingly, sol–gel B-SBA-15 lead mostly to heavy oligomers (>60%), with less than 10% of dimers.     

Assessment of Cr doping on TiO2 thin films deposited by a wet chemical method

Undoped and Cr-doped TiO₂ thin films were synthesized by the dip-coating sol-gel process with titanium isopropoxide and chromium (III) chloride hexahydrate being used as the precursors. The chromium concentrations changed for different molar ratios, namely, 2, 4, and 8 wt.%. The samples, coated on glass substrates, were later annealed in air at 450 °C for 60 min. The influence of Cr doping on the structural, surface chemical, and optical properties of the samples was studied by several techniques, including EDS, Raman, UV–Vis, RT-PL, and XPS spectroscopies, as well as SEM and XRD. The diffraction patterns indicated that all the films displayed the anatase structure with the crystallite size decreasing with chromium doping. The same structure was confirmed by Raman spectroscopy measurements. UV–Vis absorption spectra of the samples showed a red shift of the fundamental absorption edge in the visible range following the increase of Cr doping concentration. In addition, the RT-PL study revealed that the dopant incorporation causes a decrease in the PL intensity. The EDS analysis revealed the presence of Ti, O, and Cr in the materials. Moreover, from high-resolution XPS Ti 2p spectra, titanium was found to be in the Ti⁴⁺ oxidation state evidencing the formation of TiO₂, while the Cr 2p fitting analysis showed that chromium is present in the Cr (III) and Cr-metal states.     

Ni-based supported catalysts from layered double hydroxides: Tunable microstructure and controlled property for the synthesis of carbon nanotubes

The carbon nanotubes (CNTs) with straight and helical nanostructures have been synthesized by catalytic chemical vapor deposition of acetylene over a series of Ni-based supported catalysts, which were formed from Ni–Mg–Al layered double hydroxide precursors (LDHs) synthesized through homogenous decomposition of urea under hydrothermal conditions. The materials were characterized by power X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), temperature-programmed reduction experiments (TPR), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results showed that the introduction of Mg into Ni-based supported catalysts could effectively improve the catalytic activities for the growth of CNTs, mainly proceeding from the inhibition effect of spinel phases formed in calcined LDHs on the agglomeration of metallic Ni particles. Furthermore, it is found interestingly that the addition of Mg also could induce the formation of helical structured CNTs with outer diameters of 20 nm and that the higher Mg content gave rise to the more helical nanotubes. The present work provides a simple and facile way to prepare metal-supported catalysts with a good dispersion of catalytically active metal particles for the growth of straight and helical CNTs.     

Methane oxidation on alumina supported palladium catalysts: Effect of Pd precursor and solvent

Palladium precursors and solvents were studied for their effects on the activities of alumina-based palladium catalysts in methane combustion and the resistance of the catalysts to thermal aging. The properties of the catalysts were compared with those of a commercial reference. The palladium precursors were Pd(propionate)₂, Pd(acetate)₂ and Pd(acetyl acetonate)₂ and the solvents were acetone, acetic acid, propionic acid and toluene. Catalysts were prepared by the wet impregnation method.Catalysts were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectroscopy (EDS). The surface areas were measured by Brunauer–Emmett–Teller method (BET). Acidity of the alumina support was measured by NH₃ desorption. Activities of the catalysts in methane oxidation were screened under lean burn conditions.In methane oxidation with fresh catalyst, the best performance was obtained with a combination of Pd(acetate)₂ and acetic or propionic acid. The light-off temperatures of the fresh catalysts (562 K and 557 K, respectively) were slightly lower than the light-off temperature (567 K) of the commercial reference. Differences between the light-off temperatures of the aged and fresh catalysts were least when the catalysts were prepared with Pd(acetyl acetonate)₂ as Pd precursor and in acetic or propionic acid as solvent: +12 K and +18 K, respectively. The corresponding value for the reference was +64 K. For several of the fresh catalysts, conversion in methane oxidation at 623 K was over 90%. A comparison of methane combustion and NH₃ desorption results indicated that acidity of the support material affects catalysts activity.