The development of polyoxometalates for olefin oxidation is critical to achieving the green chemical process of the C5 fraction further processing.Di-lacunary silicotungstic anions were easily obtained by continuously...The development of polyoxometalates for olefin oxidation is critical to achieving the green chemical process of the C5 fraction further processing.Di-lacunary silicotungstic anions were easily obtained by continuously adjusting the p H instead of the traditional step-by-step method,which exhibited excellent performance in the catalytic oxidation of cyclopentene(CPE)to aldehydes or alcohols.The 93.69%CPE conversion and 97.15%total product selectivity(41.38%for glutaraldehyde(GA)and 55.77%for 1,2-cyclopentanediol(1,2-diol)were achieved by using H_(2)O_(2)as the oxidant and acetonitrile as the solvent.Through complementary characterization,it was found that the optimized di-lacunary silicotungstic polyoxometalate retained a complete Keggin structure,and exhibited better catalytic activity and stability than the mono-lacunary or saturated silicodecatungstate because it exposed more catalytic active centers.Furthermore,in situ FT-IR spectra was utilized to monitor the reaction process,revealing the formation of the active species W(O_(2))on the di-lacunary silicotungstic polyoxometalate and the intermediate epoxycyclopentane during the catalytic oxidation of cyclopentene.展开更多
Alkali salts of tungsten based heteropoly acids with different central atom such as P, Si and Co were prepared and evaluated for transes- terification of both edible and non-edible oils to their corresponding fatty ac...Alkali salts of tungsten based heteropoly acids with different central atom such as P, Si and Co were prepared and evaluated for transes- terification of both edible and non-edible oils to their corresponding fatty acid methyl esters. The catalyst of sodium salt of tungstic acid with Co as central atom （Na5CoW12O40） showed optimum activity towards transesterification compared with other heteropoly tungstates. The catalysts activities were correlated with the observed physico-chemical characteristics derived from FT-infrared （FT-IR）, X-ray diffraction （XRD）, temperature-programmed desorption of ammonia （NH3-TPD） and carbon dioxide （CO2-TPD）. The Na5CoW12O40 catalyst exhibiting high activity even at 65 ℃ is due to the presence of strong acidic as well as basic sites. The disclosed catalyst is tolerable towards water and free fatty acids present in the oils. The influence of catalyst loading, reaction time and reaction temperature is studied to optimize the reaction parameters.展开更多
The all-lithium salts of heteropoly acid Li_xXM_ 12O_ 40(HPA-Li)(X=P, Si; M=Mo, W) were obtained via ion exchange and characterized by means of IR and UV spectroscopies, TG and elemental analyses. The conductivity o...The all-lithium salts of heteropoly acid Li_xXM_ 12O_ 40(HPA-Li)(X=P, Si; M=Mo, W) were obtained via ion exchange and characterized by means of IR and UV spectroscopies, TG and elemental analyses. The conductivity of the electrolytic solution consisting of Li_3PW_ 12O_ 40 and PC/DME mixing solvent(1/2.5, volume ratio) is up to 7.2×10 -2 S/cm, being higher than that of LiClO_4 as the electrolyte. The all-lithium salts were used as electrolytes in secondary lithium-ion batteries. The discharge capacity of the PAS/Li batteries with Li_3PW_ 12O_ 40 electrolyte solutions reaches to 148 (mA·h)/g and the cyclic life is up to 380 times, much better than those of commercialized products with LiClO_4 and LiAsF_6 as electrolytes.展开更多
Direct hydroxylation of benzene catalyzed by vanadium-con- taining heteropoly compounds with Keggin or Dawson structure has been investigated.The effects of several factors upon the hydroxylation reaction have also be...Direct hydroxylation of benzene catalyzed by vanadium-con- taining heteropoly compounds with Keggin or Dawson structure has been investigated.The effects of several factors upon the hydroxylation reaction have also been examined.It is indicated that the highest yield of phenol reached 76%(based on H_2O_(?))with 99.4～100% selectivity.展开更多
基金the Science and Technology Project of Maoming(China)(200203094555139)for financial support。
文摘The development of polyoxometalates for olefin oxidation is critical to achieving the green chemical process of the C5 fraction further processing.Di-lacunary silicotungstic anions were easily obtained by continuously adjusting the p H instead of the traditional step-by-step method,which exhibited excellent performance in the catalytic oxidation of cyclopentene(CPE)to aldehydes or alcohols.The 93.69%CPE conversion and 97.15%total product selectivity(41.38%for glutaraldehyde(GA)and 55.77%for 1,2-cyclopentanediol(1,2-diol)were achieved by using H_(2)O_(2)as the oxidant and acetonitrile as the solvent.Through complementary characterization,it was found that the optimized di-lacunary silicotungstic polyoxometalate retained a complete Keggin structure,and exhibited better catalytic activity and stability than the mono-lacunary or saturated silicodecatungstate because it exposed more catalytic active centers.Furthermore,in situ FT-IR spectra was utilized to monitor the reaction process,revealing the formation of the active species W(O_(2))on the di-lacunary silicotungstic polyoxometalate and the intermediate epoxycyclopentane during the catalytic oxidation of cyclopentene.
文摘Alkali salts of tungsten based heteropoly acids with different central atom such as P, Si and Co were prepared and evaluated for transes- terification of both edible and non-edible oils to their corresponding fatty acid methyl esters. The catalyst of sodium salt of tungstic acid with Co as central atom （Na5CoW12O40） showed optimum activity towards transesterification compared with other heteropoly tungstates. The catalysts activities were correlated with the observed physico-chemical characteristics derived from FT-infrared （FT-IR）, X-ray diffraction （XRD）, temperature-programmed desorption of ammonia （NH3-TPD） and carbon dioxide （CO2-TPD）. The Na5CoW12O40 catalyst exhibiting high activity even at 65 ℃ is due to the presence of strong acidic as well as basic sites. The disclosed catalyst is tolerable towards water and free fatty acids present in the oils. The influence of catalyst loading, reaction time and reaction temperature is studied to optimize the reaction parameters.
文摘The all-lithium salts of heteropoly acid Li_xXM_ 12O_ 40(HPA-Li)(X=P, Si; M=Mo, W) were obtained via ion exchange and characterized by means of IR and UV spectroscopies, TG and elemental analyses. The conductivity of the electrolytic solution consisting of Li_3PW_ 12O_ 40 and PC/DME mixing solvent(1/2.5, volume ratio) is up to 7.2×10 -2 S/cm, being higher than that of LiClO_4 as the electrolyte. The all-lithium salts were used as electrolytes in secondary lithium-ion batteries. The discharge capacity of the PAS/Li batteries with Li_3PW_ 12O_ 40 electrolyte solutions reaches to 148 (mA·h)/g and the cyclic life is up to 380 times, much better than those of commercialized products with LiClO_4 and LiAsF_6 as electrolytes.
文摘Direct hydroxylation of benzene catalyzed by vanadium-con- taining heteropoly compounds with Keggin or Dawson structure has been investigated.The effects of several factors upon the hydroxylation reaction have also been examined.It is indicated that the highest yield of phenol reached 76%(based on H_2O_(?))with 99.4～100% selectivity.
