首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化...首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化剂催化合成环氧化大豆油的催化性能。结果表明:以叔丁基过氧化氢(TBHP)为氧化剂,固体催化剂对大豆油的环氧反应具有良好的催化性能,相比于催化剂1(磺酸化低聚苯乙烯基膦酸-磷酸氢锆),在相同的条件下,催化剂2(磺酸化聚(苯乙烯-苯乙烯膦酸)-磷酸氢锆)表现出更高的催化活性(产率:58.6% vs 53.3%),这主要归因于催化剂2拥有更大的比表面积、孔容以及孔径,为底物和催化剂的接触提供足够的催化场所。催化剂2重复使用7次后,催化活性未见明显降低。第8次反应结束后,将其置于2 mol·L^-1稀盐酸中静置过夜后,在进行第9和10次循环时,催化活性又得以恢复。展开更多
The layered zirconium [N-(phosphonomethyl)iminodiacetic acid-phosphate] Zr(HPO4)1.34[O3PCH2N- (CH2CO2H)2]0.66·H2O can only be prepared in the series of the zirconium phosphonate-phosphates Zr(HPO4)2-x [O3PCH2N(CH...The layered zirconium [N-(phosphonomethyl)iminodiacetic acid-phosphate] Zr(HPO4)1.34[O3PCH2N- (CH2CO2H)2]0.66·H2O can only be prepared in the series of the zirconium phosphonate-phosphates Zr(HPO4)2-x [O3PCH2N(CH2CO2H)2]x·H2O (ZPPMIDA) by the reaction of zirconium oxychloride with phosphonic acid and H2O3PCH2N(CH2CO2H)2 in the designed x range of 0 < x < 2, which had been monitored by using the phosphorus integration value ratio of HPO42- and [O3PCH2N(CH2CO2H)2]2- group in the 31P MAS NMR spectra. After intercala- tion of n-butyl amine, the 31P chemical shift of HPO42- group at - 8.0￣- 10.0 ppm moved to 6.0 ppm with a change of 14.0￣16.0 ppm and that of [O3PCH2N(CH2CO2H)2]2- group at - 29.1 ppm changed only 0.5 ppm. Due to the pil- lared effect of [O3PCH2N(CH2CO2H)2]2- groups on the interlayer spacing, intercalated amines such as n-butylamine, n-hexyl amine and n-octyl amine easily reacted with HPO42- group in ZPPMIDA (x=0.66) rather than that in α- ZrP, and carboxylic group (-CO2H) in ZPPMIDA (x=0.66).展开更多
Chloromethyl-zirconium oligo-polystyrenyl-phosphonatephosphate was used as the support of salen Mn(Ⅲ) which was synthesized by statistical method.The chloromethyl group of the support reacted with the free hydroxy of...Chloromethyl-zirconium oligo-polystyrenyl-phosphonatephosphate was used as the support of salen Mn(Ⅲ) which was synthesized by statistical method.The chloromethyl group of the support reacted with the free hydroxy of salen,and then with Mn(OAc)2·4H2O,so a new type of salen Mn(Ⅲ) catalyst supported on zirconium oligo-polystyrenyl-phosphonate-phosphate was synthesized.The catalyst was characterized by IR,SEM,element analysis and BET surface area.展开更多
Gas phase reduction of carbon monoxide to formaldehyde and ethylene was found in electrochemical cell with an inorganic ion exchanger α-Zr(HPO4)2·H2O used as solid proton-conducting electrolyte at room temperatu...Gas phase reduction of carbon monoxide to formaldehyde and ethylene was found in electrochemical cell with an inorganic ion exchanger α-Zr(HPO4)2·H2O used as solid proton-conducting electrolyte at room temperature and atmospheric pressure.The type and amount of the electroreduction of CO depend on the different metal electrodes and current densities,which gives a lank between heterogeneous catalysis and electrochemistry.展开更多
文摘首先制备了2种磺酸功能化的有机聚苯乙烯/无机磷酸氢锆非均相催化剂,运用傅里叶红外光谱(FT-IR)、N2吸附-脱附测试、X射线衍射(XRD)、扫描电子显微镜(SEM)等测试技术对催化剂进行了表征,提出了催化剂可能的模型。其次,考察了非均相催化剂催化合成环氧化大豆油的催化性能。结果表明:以叔丁基过氧化氢(TBHP)为氧化剂,固体催化剂对大豆油的环氧反应具有良好的催化性能,相比于催化剂1(磺酸化低聚苯乙烯基膦酸-磷酸氢锆),在相同的条件下,催化剂2(磺酸化聚(苯乙烯-苯乙烯膦酸)-磷酸氢锆)表现出更高的催化活性(产率:58.6% vs 53.3%),这主要归因于催化剂2拥有更大的比表面积、孔容以及孔径,为底物和催化剂的接触提供足够的催化场所。催化剂2重复使用7次后,催化活性未见明显降低。第8次反应结束后,将其置于2 mol·L^-1稀盐酸中静置过夜后,在进行第9和10次循环时,催化活性又得以恢复。
文摘The layered zirconium [N-(phosphonomethyl)iminodiacetic acid-phosphate] Zr(HPO4)1.34[O3PCH2N- (CH2CO2H)2]0.66·H2O can only be prepared in the series of the zirconium phosphonate-phosphates Zr(HPO4)2-x [O3PCH2N(CH2CO2H)2]x·H2O (ZPPMIDA) by the reaction of zirconium oxychloride with phosphonic acid and H2O3PCH2N(CH2CO2H)2 in the designed x range of 0 < x < 2, which had been monitored by using the phosphorus integration value ratio of HPO42- and [O3PCH2N(CH2CO2H)2]2- group in the 31P MAS NMR spectra. After intercala- tion of n-butyl amine, the 31P chemical shift of HPO42- group at - 8.0￣- 10.0 ppm moved to 6.0 ppm with a change of 14.0￣16.0 ppm and that of [O3PCH2N(CH2CO2H)2]2- group at - 29.1 ppm changed only 0.5 ppm. Due to the pil- lared effect of [O3PCH2N(CH2CO2H)2]2- groups on the interlayer spacing, intercalated amines such as n-butylamine, n-hexyl amine and n-octyl amine easily reacted with HPO42- group in ZPPMIDA (x=0.66) rather than that in α- ZrP, and carboxylic group (-CO2H) in ZPPMIDA (x=0.66).
文摘Chloromethyl-zirconium oligo-polystyrenyl-phosphonatephosphate was used as the support of salen Mn(Ⅲ) which was synthesized by statistical method.The chloromethyl group of the support reacted with the free hydroxy of salen,and then with Mn(OAc)2·4H2O,so a new type of salen Mn(Ⅲ) catalyst supported on zirconium oligo-polystyrenyl-phosphonate-phosphate was synthesized.The catalyst was characterized by IR,SEM,element analysis and BET surface area.
文摘Gas phase reduction of carbon monoxide to formaldehyde and ethylene was found in electrochemical cell with an inorganic ion exchanger α-Zr(HPO4)2·H2O used as solid proton-conducting electrolyte at room temperature and atmospheric pressure.The type and amount of the electroreduction of CO depend on the different metal electrodes and current densities,which gives a lank between heterogeneous catalysis and electrochemistry.
