The role of C2 intermediates in Fischer-Tropsch synthesis over ruthenium

The C₂ products formed over Ru during Fischer-Tropsch synthesis often lie well below the Anderson-Schulz-Flory line describing the C₄₊ products. This has led to speculation that either the surface precursor to C₂ hydrocarbons is exceptionally long lived, or that the ethylene formed by CO hydrogenation readsorbs and thereby reenters the chain growth process. In this study, the role of ethylene readsorption on the dynamics of chain initiation and growth is investigated using¹³CO/H₂ and¹²C₂H₄ to differentiate between the carbon sources. Ethylene addition is found to suppress the rate of methanation and increase the rates of formation of C₃₊ hydrocarbons. Ethylene serves as an effective chain initiator, as well as a source of C₁ monomer species which participate in chain propagation. No evidence is seen, though, for the participation of C₂ species in chain propagation.     

Lithium ion-exchanged zeolite faujasite as support of iron catalyst for Fischer-Tropsch synthesis

Among various microporous and mesoporous materials investigated, the Li⁺-exchanged zeolite faujasite has been found to be the most efficient support of iron catalyst for producing C₅⁺ hydrocarbon fuels via Fischer-Tropsch synthesis. The location of iron species in the catalyst is a key issue in obtaining high selectivities to C₅⁺ hydrocarbons. It is proposed that the Li⁺ cation and the supercage structure of zeolite faujasite both play important roles in improving the selectivities to C₅⁺ hydrocarbons over the Fe catalyst.     

Performance of a slurry bubble column reactor for Fischer-Tropsch synthesis: Determination of optimum condition

The CO conversion and selectivity to C₁+ and C₁₁+ wax products over Co/Al₂O₃ as well as Ru/Co/Al₂O₃ Fischer-Tropsch (F-T)catalysts were investigated by varying reaction temperature (210-250 °C), system pressure (1.0-3.0 MPa), GHSV (1000-6000 L/kg/h), superficial gas velocity (1.7-13.6 cm/s) and slurry concentration (9.09-26.67 wt.%) in a slurry bubble column reactor (0.05 m diameter × 1.5 m height) to determine the optimum operating conditions. Squalane or paraffin wax was used as initial liquid media. The overall CO conversion increased with increasing reaction temperature, system pressure and catalyst concentration. However, the local maximum CO conversion was exhibited at GHSV of 1500-2000 L/kg/h and superficial gas velocity of 3.4-5.0 cm/s. The CO conversion in the case of Ru/Co/Al₂O₃ was much higher and stable than that in the case of Co/Al₂O₃. The selectivity to C₁₁+ wax products increased slightly with increasing GHSV; on the other hand, it decreased with increasing reaction temperature, system pressure, and solid concentration in a slurry bubble column reactor. It could be concluded that the optimum operating conditions based on the yield of hydrocarbons and wax products were; U_G = 6.8-10 cm/s, Cs = 15 wt.%, T = 220-230 °C, P = 2.0 MPa in a slurry bubble column reactor for F-T synthesis.     

Fischer-Tropsch synthesis. Evidence for two chain growth mechanisms

The results show that n-pentanol serves to initiate Fischer-Tropsch synthesis reactions. Product accumulation in the CSTR is not adequate to explain the deviation from a constant¹⁴C activity/mole with increasing carbon number for alkane products. A second Fischer-Tropsch synthesis mechanism that produces only alkanes is needed to explain the deviation of the C activity/mole with increasing carbon number for n-alkanes. Furthermore, the two chain growth pathways must be completely independent without the possibility of a carbon number species that is common to both mechanisms. It is suggested that the pathway that incorporates added¹⁴C labeled alcohol has an oxygen containing surface intermediate while the other reaction pathway involves an oxygen-free reaction intermediate.     

Mass transfer limitations on fixed-bed reactor for Fischer-Tropsch synthesis

Mass transfer limitations on fixed-bed for Fischer-Tropsch synthesis were investigated by changing synthesis gas superficial velocity, catalyst pellet size, and catalyst amount. To study external mass transfer limitation, synthesis gas superficial velocity was changed from 8.47 × 10^− 4 m s^− 1 to 3.39 × 10^− 3 m s^− 1. As a result, the synthesis gas superficial velocity of 3.39 × 10^− 3 m s^− 1 was most suitable for hydrocarbon chain growth resulting to liquid hydrocarbon formation. In case of internal mass transfer limitations, the effects of catalyst pellet size and catalyst amount (W_cat/F) were discussed. The large catalyst pellet showed higher C₅₊ selectivity and a lower α value compared to the small pellet because of more severe internal mass transfer limitations of α-olefin and long-chained hydrocarbons in the large pellet, respectively. Catalyst amount (W_cat/F) was inversely proportional to the internal mass transfer limitation because increased catalyst amount gave more time for liquid hydrocarbon products to diffuse from the catalyst pellet and, therefore, the catalyst amount of 4.5 g (W_cat/F = 45 g_cat min L^− 1) was most appropriate for liquid hydrocarbon formation.     

Cyclic voltammetry studies of TiO2 nanotube arrays electrode: Conductivity and reactivity in the presence of H and aqueous redox systems

In this paper, we use cyclic voltammetry to investigate the effect of protons on the conductivity and reactivity of TiO₂ nanotube array (NTA) electrodes in an aqueous redox system. The H⁺ ion can change the TiO₂ nanotube (anatase phase) surface states for electrons transfer. It can also act as an intermediate state for electron transfer to the acceptor species in the electrolyte surrounding the TiO₂. The higher the concentration of H⁺ ions in the aqueous electrolyte, the easier it is for the electrons transfer from the TiO₂ to the electrolyte oxidized species. The reduction is facile, with a similar reduction potential for various acceptor species, but re-oxidation is not possible. It is apparently an electrochemical reduction involving a single-proton transfer and single-electron transfer. Based on this conclusion, an electrode (PB/Au/TiO₂ NTAs) was fabricated by means of electrodeposition. The electrode used to detect hydrogen peroxide. The sensitivity of the detector is high, and its the detection limit can be as low as 100 nM.     

Structural characterization of maleic anhydride grafted polyethylene by C NMR spectroscopy

Maleic anhydride grafted polyethylene, [2,3-¹³C₂] MA-g-PE, which was synthesized with ¹³C labeled maleic anhydride [2,3-¹³C₂] MA in solution, was characterized by ¹³C NMR spectroscopy in order to make clear the structure of graft groups. The results reveal that [2,3-¹³C₂] MA-g-PE has succinic anhydride oligomeric grafts with a terminal unsaturated MA ring in addition to well-known saturated succinic anhydride oligomeric grafts and that the former grafts are longer but fewer than the latter.     

The contribution of class-F fly ash to the strength of cementitious mixtures

The contribution of fly ash to the physical properties of cementitious mixtures has received considerable attention since its inclusion as an essential ingredient of High Performance Concrete (HPC). However, the chemical contribution to the overall structure development has not been fully understood because of the masking of its hydration products by those of cement. In a mixture of class-F fly ash and lime (Ca/Si=2), portlandite diminishes and C₄AH₁₃ forms due to addition of Al to solution. The latter converts to hydrogarnet and C₃ASH₄. CSH is detected at 3 days and continues to increase in intensity. The ²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR) showed that the Al/Si ratio is 0.24 and the average chain length is 10 units. The presence of Al as approximately one-fifth of the Si in a chain length of 10 units suggests that Al tetrahedra may be present in bridging positions.     

Synthesis of ternary zinc spinel oxides and their application in the photodegradation of organic pollutant

Ternary zinc spinel oxides such as Zn₂SnO₄, ZnAl₂O₄ and ZnFe₂O₄ were synthesized and characterized, and their activities in the photodegradation of phenol molecules were investigated. Zn₂SnO₄, ZnAl₂O₄ and ZnFe₂O₄ powders were synthesized by hydrothermal, metal–chitosan complexation and solvothermal routes, respectively. The face-centered cubic spinel structure of each material was confirmed by powder X-ray diffractometry (XRD) and its porous structure by N₂ adsorption–desorption isotherms. The characterization of spinels was complemented with Fourier transform infrared spectroscopy (FTIR) and X-rays fluorescence (XRF), revealing the formation of spinel structures with high purity. The photocatalytic activity in the degradation of phenol was observed only with Zn₂SnO₄ oxide. Mineralization degree of phenol molecules by Zn₂SnO₄ photocatalyst determined by total organic carbon analysis (TOC) reached 80% at 360 min under sunlight.     

The role of alkali promoters in Fischer-Tropsch synthesis on Ru/SiO2 surfaces

Cs-promoted Ru-Na/SiO₂ catalysts were characterized via¹H NMR spectroscopy. Contrary to the results of studies using single crystals, we did not find any evidence of a ruthenium-mediated electronic interaction between the alkali promoter and adsorbed hydrogen. The site blocking effects of the Cs promoter diminished after exposure to hydrogen for extended periods of times. This effect was partly reversible after thermal evacuation of the hydrogen. In the presence of Cs, the surface of the support was also modified; the intensity of the diamagnetic resonance in the spectrum (predominantly Si-OH) decreased, and an additional resonance appeared in the spectra. There is evidence that hydrogen spillover and hydrogen mobility were also restricted in the Na-Cs-promoted system.     

Synthesis and characterization of manganese oxide-doped dicalcium silicates obtained from rice hull ash

This work describes the synthesis and hydration behavior of dicalcium silicates doped with manganese. The syntheses were performed using silica obtained from rice hull ash. The solids (SiO₂, CaO and MnO) were weighed in stoichiometric proportions to prepare silicates having a ratio (Ca + Mn)/Si = 2. Insertion of manganese varied from 1 to 10% (mol). Solids were grounded and water was added rendering aqueous suspensions. The suspensions were sonicated for 60 min in an ultrasonic bath. After drying, the resulting solids were grounded and burned at 800 °C. The preparation of calcium silicates containing up to 10% of manganese oxide was observed.Hydration degree of a dicalcium silicate and calcium silicate containing 5% of manganese was determined by thermal analysis. Both materials present similar behavior. Hydration degree reaches approximately 70% after 60 days.     

Effect of WSi2 addition on densification and properties of ZrB2

Abstract

Effect of WSi₂ addition on densification and properties of ZrB₂ has been investigated. Samples of the following composition with controlled addition of WSi₂ were prepared by hot pressing (1) ZrB₂, (2) ZrB₂+2·5%WSi₂, (3) ZrB₂+5%WSi₂ and (4) ZrB₂+10%WSi₂. Hot pressing of monolithic ZrB₂ at 1750°C resulted in achieving a density of only 80·1% ρ_th. Addition of WSi₂ enhanced the densification and resulted in near theoretical density. Microstructural investigations revealed the presence of reaction product containing Si and Zr. An increase in WSi₂ content led to an increase in hardness of the product. A slight increase in fracture toughness was observed with WSi₂ addition. Crack deflection was observed in the microstructure. Oxidation study of the composite samples revealed that the oxidised layer is not adherent and resulted in spallation at the end of the test.     

Synthesis and photophysical properties of a charm-bracelet type C60-grafted PPV derivative

Synthesis and photophysical properties of a new soluble C₆₀-grafted PPV polymer have been described. Fluorescence quenching of the PPV moiety in C₆₀-grafted PPV polymer was observed, suggesting the energy- and/or electron transfer within the polymer. The fluorescence decay profiles at around 500 nm of this polymer both in chloroform and benzonitrile display a single exponential decay giving the fluorescence lifetimes of 1.10-1.27 ns, which are slightly shorter than that of PPV (about 1.50 ns). The nanosecond transient absorption band of C₆₀-grafted PPV polymer was observed at 740 nm corresponded to the excited triplet state of C₆₀, which decreased in benzonitrile, indicating the existence of the extra decay path of the singlet excited state of the C₆₀ other than intersystem crossing. Upon heating this polymer exhibits typical semilunar liquid crystalline texture, being closely associated with its polymeric structure with long solubilizing alkoxy side chains.     

Synthesis and characterization of B13C2 boron carbide ceramic by pulsed electric current sintering

Approximately 400 nm grain sized boron-carbon ceramic was synthesized by the pulsed electric current sintering (PECS) method using boron and carbon powders. Relative density of up to 95% was achieved at sintering temperature of 1900 °C. This ceramic was composed with B₁₃C₂ as major phase and few B₄C and C, which were characterized by X-ray diffraction (XRD) and Rietveld refinement quantitative analysis and chemical analysis (CA) and electron probe microanalysis (EPMA). The microstructure was also observed via transmission electron microscope (TEM).     

Synthesis gas production using steam hydrogasification and steam reforming

Experimental work has been carried out on the mixed reforming reaction, i.e., simultaneous steam and CO₂ reforming of methane under a wide range of feed compositions and four different reaction temperatures from 700 °C to 850 °C using a commercial steam reforming catalyst. The experiments were conducted for a CO₂/CH₄ ratio from 0 to 2 and a steam to methane ratio from 3 to 5. The effect of CO₂/CH₄ ratio on the exit H₂/CO ratio and the conversions of the reactants indicate that the dry reforming reaction is dominant under increased carbon dioxide in the feed. Steam reforming of typical steam hydrogasification product gas consisting of CO, H₂ and CO₂ in addition to steam and methane has also been investigated. The H₂/CO ratio of the product synthesis gas varies from 4.3 to 3.7 and from 4.8 to 4.1 depending on the feed composition and reaction temperature. The CO/CO₂ ratios of the synthesis gas varied from 1.9 to 2.9 and 2.0 to 3.3. The results are compared with simulation results obtained through the Aspen Plus process simulation tool. The results demonstrate that a coupled steam hydrogasification and reforming process can generate a synthesis gas with a flexible H₂/CO ratio from carbon-containing feedstocks.     

Trapping of CH3O formed from CO + H2

Methoxy formed on Al₂O₃ from¹³CO and H₂ coadsorption on Ni/Al₂O₃ was trapped by C₂H₅OH adsorption and temperature-programmed reaction (TPR). The presence of excess C₂H₅OH significantly increases the rate of¹³CH₃OH and (¹³CH₃)₂O formation. The¹³CH₃OH forms by the reaction of C₂H₅OH with¹³CH₃O on Al₂O₃. In the absence of C₂H₅OH,TPR following¹³CO and H₂ coadsorption did not produce significant amounts of¹³CH₃OHor(¹³CH₃)₂O.     

Synthesis and preliminary gas permeation studies of a tubular NaA zeolite membrane (NZM)

Different from traditional seeded method, NaA zeolite membranes (NZMs) were prepared by in situ synthesis onto the inner side of porous α-alumina tubular supports in a hydrothermal synthesis reactor. The influences of pretreatment of porous tubular support, temperature, time, and synthetic cycle for the synthesis of the zeolite membranes were investigated. The operating conditions were optimized. Characterization of the membranes by scanning electron microscopy and X-ray diffraction showed that the crystalline materials on the inner surface of the porous α-alumina tubes were NaA-type zeolite. Single- and binary-gas permeation tests were conducted. Single-component permeabilities of hydrogen and nitrogen through the NZM changed slightly when the transmembrane pressure difference varied from 80 to 420?kPa. Its selectivity for H₂ relative to N₂ was about 5.3, which was greater than that of the Knudsen diffusion. The separation factors of binary gases H₂/N₂ and H₂/CO₂ at 473?K were 3.9 and 5.7, respectively, again exceeding the Knudsen diffusion level. The separation of binary gases suggests that the NaA-type zeolite membranes on α-alumina substrate were defect free and able to provide molecular sieving. The results demonstrate that the unseeded synthetic method presented in this work is successful and reliable.     

Hydrogen Peroxide Generation as an Underlying Response to High Extracellular Inorganic Phosphate (Pi) in Breast Cancer Cells

According to the growth rate hypothesis (GRH), tumour cells have high inorganic phosphate (Pi) demands due to accelerated proliferation. Compared to healthy individuals, cancer patients present with a nearly 2.5-fold higher Pi serum concentration. In this work, we show that an increasing concentration of Pi had the opposite effect on Pi-transporters only in MDA-MB-231 when compared to other breast cell lines: MCF-7 or MCF10-A (non-tumoural breast cell line). Here, we show for the first time that high extracellular Pi concentration mediates ROS production in TNBC (MDA-MB-231). After a short-time exposure (1 h), Pi hyperpolarizes the mitochondrial membrane, increases mitochondrial ROS generation, impairs oxygen (O₂) consumption and increases PKC activity. However, after 24 h Pi-exposure, the source of H₂O₂ seems to shift from mitochondria to an NADPH oxidase enzyme (NOX), through activation of PKC by H₂O₂. Exogenous-added H₂O₂ modulated Pi-transporters the same way as extracellular high Pi, which could be reversed by the addition of the antioxidant N-acetylcysteine (NAC). NAC was also able to abolish Pi-induced Epithelial-mesenchymal transition (EMT), migration and adhesion of MDA-MB-231. We believe that Pi transporters support part of the energy required for the metastatic processes stimulated by Pi and trigger Pi-induced H₂O₂ production as a signalling response to promote cell migration and adhesion.     

Fluorescence improvement of Ba1.3Ca0.7SiO4:Eu,Mn phosphors via Dy addition and their color-tunable properties

A series of novel single-phase white phosphors Ba_1.3Ca_0.69−x−ySiO₄:0.01Eu²⁺,xMn²⁺, yDy³⁺ were synthesized by the solid-state method. The excitation spectra of these phosphors exhibit a broad band in the range of 260–410 nm, which can meet the application requirements for near-UV LED chips (excited at 350–410 nm). The emission spectra consist of two broad bands positioned around 455 nm and 596 nm, which are assigned to 5d→4f transition of Eu²⁺, and ⁴T₁→⁶A₁ transition of Mn²⁺, respectively. The luminescence intensity of phosphors enhances obviously by doping Dy³⁺ ions, and the intensity of two bands reaches an optimum when Dy³⁺ amounts to 2 mol%. In addition, thermoluminescence investigation of phosphor was conducted, getting two shallow trap defects with activation energy of 0.43 eV and 0.45 eV, which demonstrates the energy transfer mechanism of Dy–Eu through the process of hole and electron traps. By precisely tuning the Mn²⁺ content, an optimized white light with color rendering index (CRI) of R_a=84.3%, correlated color temperature (CCT) of T_c=8416 K and CIE chromaticity coordinates of (0.2941, 0.2937) is generated. The phosphor could be a potential white phosphors for near-UV light emitting diodes.