Phase stability and thermophysical properties of neodymium cerium composite oxide

Nd2CexO3+2x (x = 2.25, 2.5, 2.75, 3.0) were synthesized by solid-state reaction, and their phase stabilities and thermophysical properties were investigated. The X-ray diffraction (XRD) results indicated that Nd2CexO3+2x with fluorite structure were stable after long-term annealing at 1673 K. They have higher thermal expansion coefficients (TECs) than yttria-stabilized zirconia (YSZ) which is the typical thermal barrier coating (TBC) material, especially the thermal expansion as a function of temperature is parallel to that of the nickel-based superalloy.

The copolymerization of carbon dioxide and propylene oxide with Y(CCl3COO)(3)-diphenylzinc-glycerol catalyst

Various organometallic compounds (diphenylzinc, dibenzylzinc, dicyclohexylzinc, bis( pentafluorophenyl) zinc, diethylzinc, di(n-butyl) zinc, triethylaluminum) were used to form Y(CCl3COO)(3)-organometallic compound-glycerol catalyst for the copolymerization of carbon dioxide and propylene oxide. It was found that Y(CCl3COO)(3)-diphenylzinc-glycerol catalyst showed the highest catalytic activity, at optimum conditions the yield could be as high as 478.8 ( g polymer/mol Zn h).

Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by aluminum porphyrin-quaternary ammonium salt in the presence of bulky lewis acid

Chloro( 5,10,15,20-tetraphenyl-porphyrinato)-aluminum/tetraethylammonium bromide ( Et4NBr) in combination with bulky Lewis acid was used for the copolymerization of CO2 and cyclohexene oxide ( CHO). Bulky Lewis acid having substituents at the ortho positions of the phenolate ligands, like methylaluminum bis(2,6-di-tert-butyl-4-methylphenolate), significantly shortened the induction period and raised the catalytic activity, the corresponding turnover frequency reached 44.9 h(-1) in 9 h, which was 23.8% higher than that from ( TPP)AlCl/Et4NBr binary catalyst. The resulting polycarbonate has carbonate linkage over 93% with number average molecular weight of ( 4.5-6.5) x 10(3) and polydispersity index below 1.10.

Selective hydrogenation of unsaturated aldehydes in a poly(ethylene glycol)/compressed carbon dioxide biphasic system

Hydrogenation of alpha,beta-unsaturated aldehydes (citral, 3-methyl-2-butenal, cinnamaldehyde) has been studied with tetrakis(triphenylphosphine) ruthenium dihydride (H2Ru(TPP)(4)) catalyst in a poly(ethylene glycol) (PEG)/ compressed carbon dioxide biphasic system. The hydrogenation reaction was slow under PEG/ H-2 biphasic conditions at H-2 4 MPa in the absence of CO2. When the reaction mixture was pressurized by a non-reactant of CO2, however, the reaction was significantly accelerated.

Influence of compressed carbon dioxide on hydrogenation reactions in cyclohexane with a Pd/C catalyst

The potential of CO2-expanded liquid media for chemical reactions has been examined in this work, using cyclohexane as a solvent and Pd/C as a heterogeneous catalyst for hydrogenation of styrene, citral, and nitrobenzene with H-2. The rate of hydrogenation reactions is increased, and the product selectivity is altered in the CO2-expanded cyclohexane phase. In the hydrogenation of citral, the selectivity to citronellal decreases with CO2 pressure, which changes from similar to 80% in the neat cyclohexane to similar to 65% at 16 MPa.

Hydrogenation of o-chloronitrobenzene to o-chloroaniline over Pd/C in supercritical carbon dioxide

Hydrogenation of o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN) with Pd/C has been investigated in supercritical carbon dioxide (scCO(2)) at 308 K. The influences of several parameters such as CO2, H-2 pressures, Fd metal particle size and reaction time have been discussed. CO2 pressure presented markedly effects on the reaction rate and product selectivity under the reaction conditions used, the selectivity to o-CAN at CO2 pressure from 8 to 13 MPa (supercritical region) was larger than that at CO2 pressure below 6 MPa (subcritical region).

Hydrogenation of cinnamaldehyde over Pt/RHCs in supercritical carbon dioxide - Influence of support pretreatment and phase behavior

The selective hydrogenation of cinnamaldehyde (CAL) was investigated using rice husk-based porous carbon (RHCs) supported platinum catalysts in supercritical carbon dioxide (SCCO2). The effects of surface chemistry treatment of the support and the reaction phase behavior have been examined. The Pt/H-RHCs (HNO3-pretreated) was more active for CAL hydrogenation compared with Pt/NH3 - RHCs (NH3 center dot H2O-pretreated). The Pt/RHCs catalyst exhibited a higher selectivity to cinnamyl alcohol (COL) compared with commercial catalyst of Pt/C, which is relative to the micro - mesoporosity structure of the RHCs.

Synergistic extraction and recovery of Cerium(IV) and Fluorin from sulfuric solutions with Cyanex 923 and di-2-ethylhexyl phosphoric acid

Synergistic extraction and recovery of Cerium(IV) (Ce(IV)) and Fluorin (F) from sulfuric solutions using mixture of Cyanex 923 and di-2-ethylhexyl phosphoric acid (D2EHPA) in n-heptane have been carried out. in order to investigate the synergistic extraction of Cyanex 923 + D2EHPA, extraction Ce(IV), F, Ce(III) and Ce-F mixture solution using D2EHPA or Cyanex 923 as extractant alone were studied firstly, and then Synergistic extraction of Ce(IV), F and Ce(IV)-F mixture solution with D2EHPA + Cyanex 923 were carried out. The largest synergistic coefficient of Ce(IV) is obtained at the mole fraction X-Cyanex (923) = 0.8. The synergistic enhancement coefficients (R-max) obtained for Ce(IV) are 23.12 in Ce(IV) solution, and in Ce-F mixed solution R-max for Ce(IV) and F are 2.24 and 3.25 respectively.

The separation of Cerium(IV) from nitric acid solutions containing Thorium(IV) and Lanthanides(III) using pure [C(8)mim]PF6 as extracting phase

The extraction behavior of Ce(IV) along with Th(IV) and Ln(III) (Ln = Ce, Gd, Yb) nitrate by pure ionic liquid, [C(8)mim]PF6, was investigated. [C(8)mim]PF6 alone showed good extraction ability for Ce(IV), while it was slight for Th(IV) and negligible for Ln(III). The extraction behavior of Ce(IV) by [C(8)mim]PF6 was particularly studied, and the most probable extraction mechanism proposed was the anion exchange mechanism. Moreover, the stripping of Ce(IV) from IL phase was also investigated. The Ce(IV) in IL phase can be quantitatively recovered by water.

Development of durable carbon black/titanium dioxide supported macrocycle catalysts for oxygen reduction reaction

Carbon black and titanium dioxide supported iron tetraphenylporphyrin (FeTPP/TiO2/C) catalysts for oxygen reduction reaction (ORR) were prepared by sol-gel and precipitation methods followed by a heat-treatment at temperatures of 400-1000 degrees C. The FeTPP/C and TiO2/C were also studied for comparison. The FeTPP/TiO2/C pyrolyzed at 700 degrees C exhibits significantly improved stability while maintaining high activity towards ORR in comparison with the FeTPP/C counterpart. The electrochemical study combined with XRD, XPS, and SEM/EDX analyses revealed that the appropriate dispersion of TiO2 on the surface of FeTPP/TiO2/C catalysts, which depending on heat-treatment temperature, plays a crucial role in determining the activity and stability of catalysts.

Alternating Copolymerization of Carbon Dioxide and Propylene Oxide Catalyzed by Cobalt Schiff Base Complex

Cobalt 2,4-dinitrophenolate (complex 1) based upon a N,N,O,O-tetradentate Schiff base ligand framework was prepared. X-ray diffraction analysis confirmed that complex 1 was triclinic species with a six-coordinated central cobalt octahedron in the solid. Asymmetric alternating copolymerization of carbon dioxide (CO2) with racemic propylene oxide (rac-PO) proceeded effectively by complex 1 in conjunction with (4-dimethylamino)pyridine (DMAP), yielding a perfectly alternating and bimodal molecular weight distribution PO/CO2 poly(propylene carbonate) (PPC) with a small amount of cyclic carbonate byproducts.

Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.

Selective hydrogenation of maleic anhydride to gamma-butyrolactone in supercritical carbon dioxide

The reaction rates of the hydrogenation of maleic anhydride (MAH) and succinic anhydride (SAH) were significantly accelerated and the selectivity to gamma-butyrolactone (GBL) was enhanced largely when the reaction mixture was pressurized by a non-reactant of CO2. Above 99% selectivity to GBL was achieved in 14 MPa CO2, the superior selectivity in scCO(2) was attributed to that MAH and/or SAH could be extracted to CO2 phase and separated from H2O, the hydrolysis were thus minimized and so the selectivity to GBL was improved.

Selective hydrogenation of nitrobenzene to aniline in dense phase carbon dioxide over Ni/gamma-Al2O3: Significance of molecular interactions

The selective hydrogenation of nitrobenzene (NB) over Ni/gamma-Al2O3 Catalysts Was investigated using different media of dense phase CO2, ethanol, and n-hexane. In dense phase CO2, the total rate of NB hydrogenation was larger than that in organic solvents under similar reaction conditions; the selectivity to the desired product, aniline, was almost 100% over the whole conversion range of 0-100%. The phase behavior of the reactant mixture in/under dense phase CO2 was examined at reaction conditions. In situ high-pressure Fourier transform infrared measurements were made to study the molecular interactions Of CO2 with the following reactant and reaction intermediates: NB, nitrosobenzene (NSB), and N-phenylhydroxylamine (PHA). Dense phase CO2 strongly interacts with NB, NSB, and PHA, modifying the reactivity of each species and contributing to positive effects on the reaction rate and the selectivity to aniline. A possible reaction pathway for the hydrogenation of NB in/under dense phase CO2 over Ni/gamma-Al2O3 is also proposed.

Cyclization of citronellal to p-menthane-3,8-diols in water and carbon dioxide

A clean process has been developed for the synthesis of p-menthane-3,8-diols from cyclization of citronellal in CO2-H2O medium without any additives. With the addition of CO2, the reaction rate could be enhanced about 6 times for the cyclization of citronellal in H2O, because CO2 dissolved into water and formed carbonic acid inducing an increase of the acidity. Although, the reaction conversion in CO2-H2O is slightly lower compared to that obtained with sulfuric acid as catalyst, CO2-H2O could replace the sulfuric acid at a relative higher reaction temperature. The reaction kinetics studies showed that the hydration of isopulegols to p-menthane-3,8-diols is a reversible reaction. The equilibrium constant and the maximum equilibrium yield obtained in CO2-H2O at a range of CO2 pressures are similar to that with sulfuric acid catalyst.