A new solid acid catalyst,SO4^2-/TiO2 modified with tin,was prepared using a sol-gel method and its physicochemical properties were revealed by nitrogen adsorption-desorption,X-ray powder diffraction,scanning electron...A new solid acid catalyst,SO4^2-/TiO2 modified with tin,was prepared using a sol-gel method and its physicochemical properties were revealed by nitrogen adsorption-desorption,X-ray powder diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,infrared spectroscopy of adsorbed pyridine,temperature-programmed desorption of ammonia and thermal gravimetric analysis.The structure,acidity and thermal stability of the SO4^2-/TiO2-SnO2 catalyst were studied.Incorporating tin enlarged the specific surface area and decreased crystallite size of the SO4^2-/TiO2 catalyst.The total acid sites of the modified catalyst increased and Bronsted acid strength remarkably increased with increasing tin content.The decomposition temperature of sulfate radical in the modified catalyst was 100 ℃ greater and its mass loss was more than twice that of the SO4^2-/TiO2 catalyst.The SO4^2-/TiO2-SnO2 catalyst was designed to synthesize 1,6-hexanediol diacrylate by esterification of 1,6-hexanediol with crylic acid.The yield of 1,6-hexanediol diacrylate exceeded 87% under the optimal reaction conditions：crylic acid to 1,6-hexanediol molar ratio = 3.5,catalyst loading = 7%,reaction temperature = 130 ℃ and reaction time = 3 h.The modified catalyst exhibited excellent reusability and after 10 cycles the conversion of 1,6-hexanediol was above 81%.展开更多
A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of c...A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.展开更多
Palladium-catalyzed carboxylative Suzuki coupling reactions of benzyl chlorides with allyl pinacol-borate were successfully conducted in the absence of any extra ligand to produce β,γ-unsaturated esters in satisfact...Palladium-catalyzed carboxylative Suzuki coupling reactions of benzyl chlorides with allyl pinacol-borate were successfully conducted in the absence of any extra ligand to produce β,γ-unsaturated esters in satisfactory to good yields. The carboxylative Suzuki coupling reaction proceeded smooth-ly under mild conditions in the presence of palladium nanoparticles generated in situ through the formation of a π-benzylpalladium chloride intermediate.展开更多
To obtain porous alumina ceramic with high strength,a novel gelcasting system based on 2-hydroxyethyl methacrylate(HEMA)dissolved in tert-butyl alcohol(TBA)was developed.The polymerization of the HEMA-TBA gelcasting s...To obtain porous alumina ceramic with high strength,a novel gelcasting system based on 2-hydroxyethyl methacrylate(HEMA)dissolved in tert-butyl alcohol(TBA)was developed.The polymerization of the HEMA-TBA gelcasting system,the thermal behavior of obtained green body,and the microstructures and mechanical properties of the sintered bodies were investigated by rheometer,TG-DSC,SEM and bending strength testing,respectively.The results show that,(1)10 mg/mL of the initiator(benzoyl peroxide)is the optimal amount for polymerization of this gelscasting system at 25 ℃;(2)The alumina suspension of the HEMA-TBA gelcasting system showing shear-thinning behavior is sufficiently low for gelcasting process;(3)The bending strength of porous alumina ceramic samples,whose porosities range from 42% to 56%,is from(8±0.5)to(91±4.5)MPa.展开更多
文摘A new solid acid catalyst,SO4^2-/TiO2 modified with tin,was prepared using a sol-gel method and its physicochemical properties were revealed by nitrogen adsorption-desorption,X-ray powder diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,infrared spectroscopy of adsorbed pyridine,temperature-programmed desorption of ammonia and thermal gravimetric analysis.The structure,acidity and thermal stability of the SO4^2-/TiO2-SnO2 catalyst were studied.Incorporating tin enlarged the specific surface area and decreased crystallite size of the SO4^2-/TiO2 catalyst.The total acid sites of the modified catalyst increased and Bronsted acid strength remarkably increased with increasing tin content.The decomposition temperature of sulfate radical in the modified catalyst was 100 ℃ greater and its mass loss was more than twice that of the SO4^2-/TiO2 catalyst.The SO4^2-/TiO2-SnO2 catalyst was designed to synthesize 1,6-hexanediol diacrylate by esterification of 1,6-hexanediol with crylic acid.The yield of 1,6-hexanediol diacrylate exceeded 87% under the optimal reaction conditions：crylic acid to 1,6-hexanediol molar ratio = 3.5,catalyst loading = 7%,reaction temperature = 130 ℃ and reaction time = 3 h.The modified catalyst exhibited excellent reusability and after 10 cycles the conversion of 1,6-hexanediol was above 81%.
基金Supported by the Changcheng Scholars Program of Beijing(CIT&TCD 20150316)
文摘A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.
文摘Palladium-catalyzed carboxylative Suzuki coupling reactions of benzyl chlorides with allyl pinacol-borate were successfully conducted in the absence of any extra ligand to produce β,γ-unsaturated esters in satisfactory to good yields. The carboxylative Suzuki coupling reaction proceeded smooth-ly under mild conditions in the presence of palladium nanoparticles generated in situ through the formation of a π-benzylpalladium chloride intermediate.
基金Project(51202296) supported by the National Natural Science Foundation of China
文摘To obtain porous alumina ceramic with high strength,a novel gelcasting system based on 2-hydroxyethyl methacrylate(HEMA)dissolved in tert-butyl alcohol(TBA)was developed.The polymerization of the HEMA-TBA gelcasting system,the thermal behavior of obtained green body,and the microstructures and mechanical properties of the sintered bodies were investigated by rheometer,TG-DSC,SEM and bending strength testing,respectively.The results show that,(1)10 mg/mL of the initiator(benzoyl peroxide)is the optimal amount for polymerization of this gelscasting system at 25 ℃;(2)The alumina suspension of the HEMA-TBA gelcasting system showing shear-thinning behavior is sufficiently low for gelcasting process;(3)The bending strength of porous alumina ceramic samples,whose porosities range from 42% to 56%,is from(8±0.5)to(91±4.5)MPa.
