In the present research, magnesium aluminate spinel was prepared as catalyst support using a novel, facile, and efficient mechanochemical method. The Co-promoted catalysts with 20 wt.% of Ni were fabricated using an impregnation route and the samples were analyzed by the X-ray diffraction (XRD), N2 adsorption/desorption (BET), temperature-programmed reduction and desorption (H2-TPR and O2-TPD), and field emission scanning electron microscopy (FESEM) tests. The results confirmed that all samples have a mesoporous structure with a high specific surface area and the presence of cobalt caused complete CH4 oxidation at low temperatures, and no side reactions were observed. The results indicated that the 3%Co-20%Ni/MgAl2O4 catalyst was the optimal sample among the prepared catalysts, owing to the improvement of reduction features and oxygen mobility. The 50 and 90% of methane conversion was obtained at 530 and 600 °C, respectively. Also, the influence of calcination temperature, GHSV, and feed ratio was determined on the catalytic activity. The obtained outcomes revealed that the calcination temperature has a significant effect on the textural properties and catalytic efficiency. The sample calcined at 700 °C showed the weakest performance, which was related to the sintering of particles at high temperatures. The catalytic stability showed that the 3%Co-20%Ni/MgAl2O4 has acceptable stability during 600 min time of reaction.
Enthalpies of mixing (mH) aqueous solutions of CoCl2, CuCl2, and MnCl2 with NaCl solutions were measured at constant ionic strengths of 0.5, 1.0, and 3.0 molal at 25°C. The excess enthalpy equations of Pitzer were then fit to the resulting mH data. The resulting parameters are the temperature derivatives of the activity coefficient mixing parameters in the Pitzer system. The heat of mixing data for CoCl2 and CuCl2 were in agreement with earlier isomolal results by other workers. 相似文献
The dependency of adsorption energy (E) and affinity coefficient (beta) of Dubinin equations (Dubinin-Radushkevich (DR) or Dubinin-Astakhov (DA)) on surface chemistry and porosity of activated carbons was investigated by analyzing adsorption of nitrogen, benzene, trichloroethylene (TCE), and water vapor by several surface-modified activated carbons and carbon fibers. For all studied nonpolar adsorbates, carbons with smaller average micropores showed higher adsorption energies independent of their surface chemistry. For water vapor, carbons with higher surface polarities showed higher adsorption energies due to specific adsorbate-adsorbent interactions. Adsorption energies increased with decreasing average micropore widths. betaN2,DR for different carbons were observed to vary in the 0.292-0.539 range. Carbons with higher degrees of mesoporosity had higher betaN2,DR values, while no dependency was observed between betaN2,DR and surface chemistry. A comparison of DR and DA cases indicates that: (1) the average value of betaN2,DA is considerably above the classical value of this parameter; and (2) the range of betaN2,DA values were smaller compared to betaN2,DR, despite a wide range of mesoporosity of carbons examined. Obtained beta(TCE,DR) values varied in the 0.952-1.243 range, with an average value of 1.085+/-0.083, independent of surface chemistry or porosity of activated carbons. A similar result was observed for beta(TCE,DA). betaH2O,DR values of different granular and fibrous activated carbons changed in the range of 0.081-0.271. They depended more on the carbon surface chemistry and less on the porosity. A similar result was obtained when DA equation was considered. 相似文献
In this paper five equations of state are tested for checking their ability to predict the Joule-Thomson inversion curve.These five equations of state are:Mohsennia-Modarres-Mansoori(MMM),Ji-Lemp(JL),modified Soave-Redlich-Kwang(SRK)equation of state by Graboski(MSRK1),modified SRK equation of state by Peneloux and Rauzy(MSRK2),and modified Peng-Robinson (PR)equation of state by Rauzy(PRmr).The investigated equations of state give good prediction of the low-temperature branch of the inversion curve,except for MMM equation of state.The high-temperature branch and the peak of the inversion curve have been observed,in general,to be sensitive to the applied equation of state.The values of the maximum inversion temperature and maximum inversion pressure are calculated for each component used in this work. 相似文献
Bis(peroxo)vanadium(V) complexes are widely investigated as anticancer agents. They exert their antitumor and cyctotoxic effects through inhibition of tyrosine phosphatases and DNA cleavage, respectively. The latter process remains poorly understood. The mechanism of DNA cleavage by NH(4)[(phen)V(O)(eta(2)-O(2))(2)] (phen = 1,10-phenanthroline) was investigated. Kinetic studies on DNA cleavage revealed that the complex is a single-strand nicking agent with no specificity. EPR experiments using 2,2,6,6-tetramethyl-4-piperidone (TMP) and 5,5'-dimethyl-1-pyrroline-N-oxide (DMPO) as spin-traps for singlet oxygen and hydroxyl radical, respectively, implicated hydroxyl radical production upon photodecomposition of bis(peroxo)vanadium(V). This was corroborated by benzoate inhibition of DNA strand scission and stoichiometric oxidation of 2-propanol to acetone upon irradiation of bis(peroxo)vanadium(V) phenanthroline. High-resolution polyacrylamide gel analysis of the vanadium cleavage reaction and [Fe(II)EDTA](2)(-)/H(2)O(2) resulted in comigration of "ladder" pattern bands, which superimposed when both reactions were run on the same lane. These findings identify hydroxyl radical produced from the photooxidation of the peroxo ligand on vanadium as the active species in DNA cleavage. 相似文献
The nitridorhenium(V) complexes ReNCl(2)(PCy3)(2) (1), ReNBr(2)(PCy3)(2) (2), ReNCl(2)(PPh3)(2) (3), and ReNBr(2)(PPh3)(2) (4) produce structured emission spectra upon excitation at low temperature. The origin, E(00), occurs at 15 775, 16 375, 15 875, and 16 300 cm(-1), respectively. The vibronic peaks are regularly spaced with an average energy separation corresponding to the Re triple bond N stretching frequency. The nitridorhenium stretching frequency ranges from 1095 to 1101 cm(-1), as determined by Raman and IR spectroscopy. The excited-state distortions are calculated by fitting the emission spectra. The excited state arises primarily from a d(xy) (ReN nonbonding) to d(yz) (ReN pi antibonding) transition. The rhenium-nitrogen bond length in the excited state is 0.08 A longer than in the ground electronic state, which is consistent with the difference in bond lengths of ReN bonds of bond order 3 and bond order 2.5 as determined from molecular structures. 相似文献