Ni–Al hydrotalcite-like material as the catalyst precursors for the dry reforming of methane at low temperature

Nickel–aluminium and magnesium–aluminium hydrotalcites were prepared by co-precipitation and subsequently submitted to calcination. The mixed oxides obtained from the thermal decomposition of the synthesized materials were characterized by XRD, H₂-TPR, N₂ sorption and elemental analysis and subsequently tested in the reaction of methane dry reforming (DRM) in the presence of excess of methane (CH₄/CO₂/Ar = 2/1/7). DMR in the presence of the nickel-containing hydrotalcite-derived material showed CH₄ and CO₂ conversions of ca. 50% at 550 °C. The high values of the H₂/CO molar ratio indicate that at 550 °C methane decomposition was strongly influencing the DRM process. The sample reduced at 900 °C showed better catalytic performance than the sample activated at 550 °C. The catalytic performance in isothermal conditions from 550 °C to 750 °C was also determined.     

Separation of hydrogen from steam using a SiC-based membrane formed by chemical vapor deposition of triisopropylsilane

A silicon carbide-based membrane was formed in the macropores of an α-alumina support tube by chemical vapor deposition of triisopropylsilane at 700–800°C with a forced cross-flow through the porous wall. The membrane permeated gases except H₂O mainly by the Knudsen diffusion mechanism at permeation temperatures of 50–400°C. The H₂/H₂O selectivity was near or below unity because of the hydrophilic nature of the membrane. After a heat-treatment in Ar at 1000°C for 1 h, however, the membrane formed at a final evacuation pressure of 1 kPa exhibited a H₂/H₂O selectivity of 3–5, for a mixed feed of H₂–H₂O–HBr system, associated in a thermochemical water-splitting process. The H₂ permeance was (5–6)×10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 50–400°C. The membrane maintained the H₂/H₂O selectivity for more than 100 h in the H₂–H₂O–HBr mixture at 400°C.     

Investigation of the evolved gases from Sulcis coal during pyrolysis under N2 and H2 atmospheres

The evolution of gases and volatiles during Sulcis coal pyrolysis under different atmospheres (N₂ and H₂) was investigated to obtaining a clean feedstock of combustion/gasification for electric power generation. Raw coal samples were slowly heated in temperature programmed mode up to 800 °C at ambient pressure using a laboratory-scale quartz furnace coupled to a Fourier transform infrared spectrometer (FTIR) for evolved gas analysis. Under both pyrolysis and hydropyrolysis conditions the evolution of gases started at temperature as low as 100 °C and was mainly composed by CO and CO₂ as gaseous products. With increasing temperature SO₂, COS, and light aliphatic gases (CH₄ and C₂H₄) were also released. The release of SO₂ took place up to 300 °C regardless of the pyrolysis atmosphere, whilst the COS emissions were affected by the surrounding environment. Carbon oxide, CO₂, and CH₄ continuously evolved up to 800 °C, showing similar release pathways in both N₂ and H₂ atmospheres. Trace of HCNO was detected at low pyrolysis temperature solely in pure H₂ stream. Finally, the solid residues of pyrolysis (chars) were subjected to reaction with H₂ to produce CH₄ at 800 °C under 5.0 MPa pressure. The chars reactivity was found to be dependent on pyrolysis atmosphere, being the carbon conversions of 36% and 16% for charN₂ and charH₂, respectively.     

Natural gas permeation in polyimide membranes

Polyimide membranes derived from 6FDA-DAM:DABA and 6FDA-6FpDA:DABA copolymers have been used to separate 50/50 CO₂/CH₄ mixtures and multicomponent synthetic natural gas mixtures at 35 °C and feed pressures up to 55 atm. For 6FDA-DAM:DABA 2:1 membranes the effects of thermal annealing and covalent crosslinking are decoupled with respect to effects on permeabilities and selectivity. Crosslinking at 295 °C with 1,4-butylene glycol and 1,4-cyclohexanedimethanol increases CO₂ permeabilities by factors of 4.1 and 2.4, respectively, at 20 atm feed pressure, without a loss in selectivity, relative to crosslinking at 220 °C. Thermal annealing and crosslinking also reduce CO₂ plasticization effects. Crosslinking of DABA-containing copolymers, therefore, can produce membranes with tunable transport properties that offer significantly higher performance with better plasticization-resistance than that reported in the literature for the commercial polymers Matrimid^® and cellulose acetate for CO₂ removal from natural gas mixtures. Separation of complex mixtures containing CO₂, CH₄, C₂H₆, C₃H₈, and C₄H₁₀ or toluene results in a significant decrease of the CO₂ permeability, but only a moderate decrease in the CO₂/CH₄ selectivity.     

One-pot synthesis of 2,5-disubstituted-1,3,4-thiadiazoles under ultrasonic irradiation

A facile one-pot synthesis of 2,5-disubstituted-1,3,4-thiadiazoles was achieved by ultrasonic irradiation of a mixture of 1- naphthylacetyl chloride,NH_4CNS,CH_2Cl_2 and PEG-400 for 1.5 h at 10-20℃and subsequent irradiation for 1.5h in the presence of N-arylglycine hydrazides.This method requires short time and gives thiadiazoles in high yields.     

Synthesis,structure and magnetic properties of {Mn5(OC(O)CH3)6(OC(O)C6H5)4}∞

The ligand exchange reaction between Mn(OC(O)CH₃)₂ and benzoic acid under solvothermal conditions in toluene at 110 °C yields colorless crystals of {Mn₅(OC(O)CH₃)₆(OC(O)C₆H₅)₄}_∞ (1). The asymmetric unit of this complex is Mn_2.5(OC(O)CH₃)₃(OC(O)C₆H₅)₂ with each of the three different Mn(II) atoms in 6-fold coordination and one of the benzoate ligands exhibiting the rare μ₃-symmetric bridging mode (O–Mn–O angle = 57°). The structure consists of edge-shared Mn₁₂ loops arranged in a honeycomb-like 2D sheet with the acetate ligands displaced slightly out of the plane. The sheets are spaced at 12 Å and linked into a 3D network via weak intersheet interactions. Magnetic susceptibility characterization of 1 indicates antiferromagnetic exchange with a Weiss constant of −165 K and a transition toward ferromagnetic exchange below 10 K corroborated with a finite imaginary component in the variable temperature susceptibility data.     

Assembly of succinic acid and isoxazolidine motifs in a single entity to mitigate CO2 corrosion of mild steel in saline media

Inhibition of CO₂ corrosion of mild steel in 0.5 M NaCl under atmospheric pressure at 40 °C as well as high pressure (10 bar) at 120 °C by 2-[2-methyl-4(or 5)-alkylisoxazolidin-5(or 4)-yl)methyl]succinic acids, a new class of molecules having inhibitive motifs of succinic acid, isoxazolidine and hydrophobic alkyl chain assembled in a single entity, has been examined by gravimetric and electrochemical methods. Inhibitor molecule containing CH₃(CH₂)₈ outperformed its counterpart with a shorter hydrophobe CH₃(CH₂)₄ and two other commercial imidazoline-based inhibitors. The effectiveness of these new inhibitors was also evaluated by electrochemical impedance spectroscopy. The inhibition efficiency by EIS was found to be 75%, 91% and 98% in the presence of 1, 5 and 20 ppm, respectively, at 40 °C. The potentiodynamic polarization studies indicated that the new inhibitors act as anodic inhibitors. The adsorption of the synthesized inhibitors follows Temkin adsorption isotherm model with favorable high values of –ΔG°_ads and −ΔH°_ads pointing the inhibitors adsorbed on the metal surface by chemisorption process. The XPS study confirmed the adsorption of the inhibitors on the metal surface.     

Increasing the efficiency of silicon and aluminum extraction from Volclay by a water iteration treatment for the synthesis of MCM-41 nanomaterials

This work aims to reduce the prices of a wide range of nanomaterials which are unreachable in the industry by using natural sources as silicon and aluminum precursors. In a previous work, silicon and aluminum have been extracted from Volclay after applying the alkaline fusion process at 550 °C, and a water treatment of this fused clay by adopting a weight ratio (1:4, fusion mass:H₂O) to synthesize Al-MCM-41 nanomaterials. In this study, the weight ratio of fusion mass:H₂O was increased to 1:8 to synthesize a highly structurally ordered MCM-41 under the same reaction conditions. The Al-MCM-41 nanomaterials are investigated by inductively coupled plasma optical emission spectrometry (ICP–OES), powder X-ray diffraction (XRD), N₂ adsorption–desorption measurements and scanning electron microscopy (ESEM). As a result, the increase in the weight ratio fusion mass:H₂O generates more silica and aluminum, which allows the formation of well-ordered MCM-41 nanomaterials with high pore volume (0.70 cm³/g), high surface area (1044 m²/g), and uniform mesoporous diameter (3.67 nm); as a consequence, the increase in the weight ratio fusion mass:H₂O leads to an increase in the mass of Al-MCM-41 (9.3 g for 1:8 compared to 5 g for 1:4), whereas the yield of production of mesoporous materials increases to 86%.     

Synthesis of a PEBAX-1074/ZnO nanocomposite membrane with improved CO_2 separation performance

In this investigation, polymeric nanocomposite membranes(PNMs) were prepared via incorporating zinc oxide(ZnO) into poly(ether-block-amide)(PEBAX-1074) polymer matrix with different loadings. The neat membrane and nanocomposite membranes were prepared via solution casting and solution blending methods, respectively. The fabricated membranes were characterized by field emission scanning electron microscopy(FESEM) to survey cross-sectional morphologies and thermal gravimetric analysis(TGA)to study thermal stability. Fourier transform infrared(FT-IR) and X-ray diffraction(XRD) analyses were also employed to identify variations of the chemical bonds and crystal structure of the membranes, respectively. Permeation of pure gases, CO_2, CH_4 and N_2 through the prepared neat and nanocomposite membranes was studied at pressures of 3–18 bar and temperature of 25 °C. The obtained results showed that the fabricated nanocomposite membranes exhibit better separation performance compared to the neat PEBAX membrane in terms of both permeability and selectivity. As an example, at temperature of 25 °C and pressure of 3 bar, CO_2 permeability, ideal CO_2/CH_4 and CO_2/N_2 selectivity values for the neat PEBAX membrane are 110.67 Barrer, 11.09 and 50.08, respectively, while those values are 152.27 Barrer,13.52 and 62.15 for PEBAX/ZnO nanocomposite membrane containing 8 wt% ZnO.     

Expedient one-pot organometallics-free synthesis of tris(2-pyridyl)phosphine from 2-bromopyridine and elemental phosphorus

2-Bromopyridine reacts with elemental phosphorus (red or white) in a superbasic KOH/DMSO(H₂O) suspension at 100 °C (for red phosphorus) and 75 °C (for white phosphorus) over 3 h to afford tris(2-pyridyl)phosphine in a 62% yield (from red phosphorus) and a 50% yield (from white phosphorus). Under microwave assistance, the reaction with red phosphorus takes just 20 min to produce tris(2-pyridyl)phosphine in 53% yield. A hitherto unknown complex, [Pd(PPy₃)₂Cl₂]·CH₂Cl₂, synthesized from tris(2-pyridyl)phosphine and PdCl₂, has the cis-configuration; this is unusual for bis(phosphino)palladium dichloride complexes.     

Author index

The triplet potential energy surface for the reaction of ethylene with molecular oxygen in the ground state has been calculated at the QCISD(T, full)/6-311++G(3df,2p)//MP2(full)/6-311G(d,p) level of theory. Four intermediates and 17 transition states are located along the minimum energy reaction path. Six major radical product channels are revealed, namely, C₂H₃ + HO₂, O(³P) + C₂H₄O, H + C₂H₃O₂, OH + C₂H₃O, OH + CH₃CO, and O(³P) + CH₃CHO. In view of reaction barrier heights, the dominant channels are predicted to be C₂H₃ + HO₂, O(³P) + C₂H₄O, H + C₂H₃O₂, and C₂H₄O₂(³A″). The calculated rate constants for the abstraction reaction path are in good agreement with the available experimental data. The implication of the current results in the initiation of the combustion of ethylene is discussed.     

Thermal behaviour of malonic acid,sodium malonate and its compounds with some bivalent transition metal ions

Characterization, thermal stability and thermal decomposition of transition metal malonates, MCH₂C₂O₄·nH₂O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as, the thermal behaviour of malonic acid (C₃H₄O₄) and its sodium salt (Na₂CH₂C₂O₄·H₂O) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, TG-FTIR system, elemental analysis and complexometry. The dehydration, as well as, the thermal decomposition of the anhydrous compounds occurs in a single step. For the sodium malonate the final residue up to 700 °C is sodium carbonate, while the transition metal malonates the final residue up to 335 °C (Mn), 400 °C (Fe), 340 °C (Co), 350 °C (Ni), 520 °C (Cu) and 450 °C (Zn) is Mn₃O₄, Fe₂O₃, Co₃O₄, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity, thermal behaviour and identification of some gaseous products evolved during the thermal decomposition of these compounds.     

Highly stable and selective Ru/NiFe_2O_4 catalysts for transfer hydrogenation of biomass-derived furfural to 2-methylfuran

Spinel ferrites NiFe_2O_4 supported Ru catalysts have been prepared via a simple sol–gel route and applied for converting biomass-derived furfural to 2-methylfuran. The as-prepared catalysts were characterized by thermogravimetric analysis(TG), N_2 adsorption–desorption, X-ray diffraction(XRD), scanning electronic microscopy(SEM), and X-ray photoelectron spectroscopy(XPS). Results showed that the catalysts had well-dispersed Ru active sites and large surface area for calcination temperature ranging from 300 to 500 ℃. The conversion of biomass-derived furfural into 2-methylfuran was conducted over Ru/NiFe_2O_4 through catalytic transfer hydrogenation in liquid-phase with 2-propanol as the hydrogen source. A significantly enhanced activity and increased 2-methylfuran yield have been achieved in this study. Under mild conditions(180 ℃ and 2.1 MPa N_2), the conversion of furfural exceeds 97% and 2-methylfuran yield was up to 83% over the catalyst containing 8 wt% Ru. After five repeated uses, the catalytic activity and the corresponding product yield remained almost unchanged. The excellent catalytic activity and recycling performance provide a broad prospects for various practical applications.     

Phase transfer catalysis: Synthesis of monodispersed FePt nanoparticles and its electrocatalytic activity

Using dibenzo-24-crown-8-ether (DB24C8) as phase transfer catalyst, the monodispersed iron–platinum (FePt) alloy nanoparticles with size of ∼17 nm were synthesized by reduction of H₂PtCl₆·6H₂O and FeCl₂·4H₂O in the solvothermal system. The structure, magnetic property and electrocatalytic activity of FePt nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction system (XRD), vibration sample magnetometer (VSM) and CHI 820 electrochemical analyser (three electrodes system, the reference electrode is saturated calomel electrode (SCE), the counter electrode is platinum electrode and the glassy carbon electrode is used as working electrode (GCE)), respectively. The results show that the as-synthesized FePt nanoparticles have a chemically disordered fcc structure and can be transformed into chemically ordered fct structure after annealing treatment above 400 °C, simultaneously accompanying with the coercivity changed from 5 to 2400 Oe. CVs of 0.5 M H₂SO₄/0.5 M CH₃OH on GCE modified with FePt nanoparticles monolayer illustrate that the as-synthesized FePt nanoparticles have strong electrocatalytic activity toward the oxidation of CH₃OH in aqueous solution.     

Conformational and stereoelectronic investigation of chloromethyl methyl sulfide and its sulfinyl and sulfonyl analogs

Three compounds based on polyoxometalate building blocks, [Cu(en)₂]{[Cu(en)₂]₂[Mo^VI₅Mo^V₃V^IV₈O₄₀(PO₄)]} · 4H₂O (1), [Co(en)₂]{[Co(en)₂]₂[HMo^VI₄Mo^V₄V^IV₈O₄₀(PO₄)]} · 5H₂O (2) and [Ni(en)₂]{[Ni(en)₂]₂[Mo^VI₅Mo^V₃V^IV₈O₄₀(VO₄)]} · 2H₂O (3) (en = ethylenediamine), have been synthesized and characterized by elemental analysis, IR, XPS, XRD, TGA and single-crystal X-ray diffraction analysis. The result of structure determination shows that isomorphic compounds 1, 2 and 3 feature a one-dimensional chain built from the reduced tetra-capped pseudo-Keggin polyoxoanion, which is further interconnected by [M(en)₂]²⁺ (M = Cu, Co and Ni) groups via the terminal oxygen atoms of polyoxoanions. The crystal data for these compounds are the following: 1, monoclinic, space group C2/c, a = 26.702(3) Å, b = 13.4539(14) Å, c = 19.5987(19) Å, β = 108.650(2)°, V = 6671.0(12) Å³, Z = 4; 2, monoclinic, space group C2/c, a = 26.244(3) Å, b = 13.5070(17) Å, c = 19.581(3) Å, β = 106.881(2)°, V = 6641.8(15) Å³, Z = 4; 3, monoclinic, space group C2/c, a = 26.2789(15) Å, b = 13.5408(6) Å, c = 19.6312(9) Å, β = 106.2590(10)°, V = 6706.1(6) Å³, Z = 4. Variable-temperature magnetic susceptibility measurements of compounds 1 and 3 reveal the feature of antiferromagnetic exchange in these compounds.     

Reactions of β-diketiminatoaluminum hydrides with tert-butyl hydrogenperoxide – Facile formation of dialuminoxanes containing Al–O–Al groups

Treatment of diphenyl-β-diketiminatoaluminum dihydride, LAlH₂ [1, L = {H₅C₆–NC(Me)}₂CH] with neopentyl- or trimethylsilylmethyllithium afforded the corresponding alkylderivatives LAlH(R) [R = CH₂–SiMe₃ (2), CH₂–CMe₃ (3)] by the precipitation of lithium hydride. Deprotonation of a methyl group instead of salt elimination occurred by the similar reaction of the more basic alkyllithium compound LiC(SiMe₃)₃. The reactions of the hydrides 1–3 with tert-butyl hydrogenperoxide did not yield the expected peroxo derivatives, instead the dialuminoxanes LAl(R)–O–Al(R)L [R = OCMe₃ (5), CH₂SiMe₃ (6), CH₂CMe₃ (7)] were isolated in high yields. Their Al–O–Al bridges deviated from linearity and had Al–O–Al bond angles of about 155° on average.     

N-heterocyclic carbene–palladium catalysts for the bisdiene cyclization-trapping reaction with sulfonamides under thermal and microwave conditions

Simple palladium-N-heterocyclic carbene catalysts readily effect the palladium-catalyzed cyclization-trapping of bisdienes with sulfonamides. The reaction is quite efficient for a variety of sulfonamides and several bisdienes. For example, using 0.1% of the in situ generated or preformed (IMes)Pd(η³-C₃H₅)Cl complex, the cyclization-trapping of a simple bisdiene with TsN(H)CH₂Ph proceeds in good yield under thermal conditions (74–75%, 75 °C, 9 h). The same reaction run under microwave irradiation proceeds somewhat faster and in even higher yield (86%, 75 °C, 2.5 h).     

Catalytic conversion of CO2–CH4 mixture into synthetic gas—Effect of electron-beam radiation

The radiolysis of methane (0.7 MeV electron beam) was studied as a function of its concentration at two doses: 5 and 20 kGy. In both cases the G (–CH₄) value raised with the increase of the substrate concentration. Thereby the yields observed at 20 kGy are much lower, because of recombination processes. Results are also reported on the conversion of the gas mixture CH₄:CO₂:He=1:1:1 into synthetic gas (H₂/CO) at 500 °C, using two catalysts : (N5) and (N20), containing 5 wt% Ni and 20 wt% Ni, respectively, supported on γ-Al₂O₃. In an experimental series the catalysts (N5) and (N20) were treated by irradiation (4 MGy dose) before use. The highest conversion yields (above 35%) were observed by implementation of N5 and N20 catalyst at 500 °C under the influence of electron beam radiation.     

A new method of one-pot synthesis of dicarboxylic acid derivatives and diketones containing quaternary carbon atom and remote functional groups from linear acyl halides

The one-pot, regioselective synthesis of branched diacid derivatives – diesters, dithioesters, diamides [YC(O)O(CH₂)_mC(Me)₂OC(O)Y] and diketones of aromatic and heteroaromatic series, [ArCO(CH₂)_mC(Me)₂C(O)Ar,) from available linear acyl halides, C_nH_2 n+1COCl (n = 7–9), CO (1 at) and various nucleophiles (YH = EtOH, CF₃CH₂OH, H(CF₂)₂CH₂OH, thiophene, anisole, Et₂NH, aniline, and morpholine) in the presence of the superelectrophilic complex, CBr₄·2AlBr₃ has been performed for the first time. This method provides access to new and promising groups of dicarboxylic acid derivatives and diketones containing quaternary carbon atom and remote functional groups.     

Separation performance of polyimide composite membrane prepared by dip coating process

The effects of the preparation conditions in a dip coating process on polyimide composite membranes have been investigated. Polyimide precursor obtained from pyromellitic dianhidride (PMDA) and 4,4′-oxydianiline (ODA) was mixed with triethylamine and poly(amic acid)tri-ethylamine salt (PAA salt) was made. An asymmetric polyimide membrane (PI-2080) as a supporting membrane was dipped in a PAA salt (concentration 0–5 wt.%) methanol solution. The coating layers of PAA salt were converted to these of polyimide by annealing at 200°C for 3 h in an ordinary vacuum oven.The performance of the polyimide composite membrane was evaluated by gas permeation (N₂, O₂, CO₂, at 1 kg/cm²) and pervaporation (feed: a 95 vol.% ethanol aqueous solution at 30–60°C). The composite membranes prepared using a coating solution of 5 wt.% PAA salt showed the CO₂/N₂ selectivity of over 25 on gas permeation, and separation factor α (H₂O/EtOH) of over 800 with a total flux of 0.21 kg/m² h on pervaporation.