No abstract

The reaction of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) with RhCl 3 ‚3H 2 O has been studied under different experimental conditions. This reaction in ethanol resulted in the formation of [Rh(tptz)Cl 3 ]‚2H 2 O (1), whereas the bis-chelate complex [Rh(tptz) 2 ][ClO 4 ] 3 ‚2H 2 O (2) was obtained in a two-step reaction in acetone; the chlorides from RhCl 3 were removed in the first step using AgClO 4 , and the ligand tptz was added in the second step. Complexes 1 and 2, when refluxed in ethanol-water (1:1), resulted in metal-promoted hydrolysis of tptz to bis-(2-pyridylcarbonyl)amide anion (bpca) and 2-picolinamide (pa), yielding the complexes [Rh(bpca)(pa)Cl][PF 6 ]‚ H 2 O (3) and [Rh(bpca) 2 ][ClO 4 ] (6), respectively. A mixed-ligand complex, [Rh(bpca)(tpy)][PF 6 ] 2 ‚CH 3 CN (4), was obtained by the reaction of either 1 with tpy or [Rh(tpy)Cl 3 ] (5) with tptz in ethanol-water medium. The crystal structures of complexes 1 and 4 have been determined. Crystal data: complex 1, monoclinic, P2 1 /c, a ) 11.642(2) Å, b ) 7.302(2) Å, c ) 24.332(3) Å, β ) 96.420(10)°, Z ) 4, R ) 0.040, and wR2 ) 0.117; complex 4, triclinic, P1 h, a ) 9.581(1) Å, b ) 12.933(2) Å, c ) 14.493(2) Å, R ) 82.480(10)°, β ) 71.810(10)°, γ ) 75.100(10)°, Z ) 2, R ) 0.030, and wR2 ) 0.082. The two water molecules of complex 1 make short contacts with the carbon atoms adjacent to the metal-bound nitrogen atom of the triazine ring; this observation provides some insight about the "intermediate" of the hydrolysis. X-ray and NMR data suggest that the electron-withdrawing effect of the metal ion is the major responsible factor for the hydrolysis of tptz. The cyclic voltammograms of the complexes exhibit a metal-based 2e reduction (Rh(III) f Rh(I)) at the potential range -0.42 to -0.98 V vs SCE, followed by ligand-based redox couple(s). These novel complexes show effective catalytic properties for the electrocatalytic reduction of carbon dioxide in the potential range -1.26 to -1.44 V.

Nanocrystalline zirconia samples having predominantly tetragonal crystalline phase were synthesized using sol-gel and conventional precipitation techniques from zirconium hydroxide obtained by the hydrolysis of both zirconium propoxide and zirconium oxychloride precursors. Thermal drying of zirconium hydroxide gel in an oven (110 °C, 12 h) results in lower crystallite size (11-13 nm) as compared to drying under vacuum (50 mbar, 70 °C), which shows higher crystallite size (20-21 nm) during both sol-gel and conventional precipitation synthesis. The progressive transformation of tetragonal to monoclinic phase of zirconia with increasing calcination temperature was observed to be related to the critical crystallite size and lattice strain. Sol-gel synthesis was found to be advantageous because of the stabilization of tetragonal phase at higher temperature, whereas complete phase transformation was observed in the samples prepared by precipitation method at 600-700 °C temperature. Sol-gel synthesis resulted in spherical-shaped particles whereas cubic-/ rectangular-shaped particles of varying sizes were predominantly formed by conventional precipitation synthesis.

Sorption of N 2 , O 2 , Ar, and CH 4 in zeolites X, Y, and mordenite in powder as well as pellets was studied using gas chromatography. Heats of sorption in pellets formed using clay as a binder increased by 34-78% for N 2 and 7-18% for CH 4 relative to the respective zeolite powder. Surface acidity of zeolites upon pelletization as measured by ammonia temperature-programmed desorption showed that high-strength acid sites completely disappear for both zeolite Y and mordenite when bound with bentonite and attapulgite. Decreases in weaker acid sites upon pelletization for mordenite and HY are 47-52% and 34%, respectively. Fourier transform infrared spectroscopy also showed a decrease in acidity upon pelletization of zeolite powders as observed from the reduction in the intensity of the peaks corresponding to acidic hydroxyl groups. Influence of the decrease in surface acidity upon pelletization was also observed from conversion values for alkylation of toluene with methanol in zeolite pellets. For example, reduction in total xylene formed was by 50%, 87%, and 100% for HY520, HY510, and HM510, respectively. These observations have been interpreted in terms of solid-state migration of cations present in clay interlayer space to zeolite extraframework sites during pelletization. Reexchange of cations in zeolites HY and HM with an aqueous solution of Na + /Ca 2+ salts shows sorption isotherms closer to the respective pelletized samples. X-ray diffraction studies of zeolites in powders as well as pellets confirm migration of clay cations to zeolite extraframework sites.

A series of Mg−Al−CO3 layered double hydroxide (LDH) samples have been synthesized by conventional precipitation and coprecipitation methods. The effect of various synthetic parameters, such as cation molar ratio, mode of addition of magnesium and aluminum precursors, addition temperature, agitation, and drying conditions, on the structural, textural, and thermal behavior of the samples has been studied. These properties were correlated with the CO2 adsorption capacity of the samples. The Mg−Al−CO3 LDH sample prepared with optimized synthetic parameters has shown the higher CO2 adsorption capacity (22 cm3/g).