Fourier transformed infrared spectrometry (FTIR) and 27Al Magic Angle spinning (MAS) nuclear magnetic resonance spectroscopy were employed to characterize arsenate adsorption on amorphous Al gels with Keggin structure...Fourier transformed infrared spectrometry (FTIR) and 27Al Magic Angle spinning (MAS) nuclear magnetic resonance spectroscopy were employed to characterize arsenate adsorption on amorphous Al gels with Keggin structure at pH =4–10. These studies have proven that: the surface complex species of arsenate show significant differences under acidic and alkaline conditions, which was deduced based on the As-O stretching vibration bands located respectively at 774 and 870 cm-1; poorly crystalline Al13 (or Al)-arsenate precipitation could be easily formed under acid medium condition and high loading level, which was supported by comparing the As-O vibration (at ≈732 cm-1) of precipitation to adsorbed Al gels; arsenate (AsO43-) adsorption has no effect on the Keggin structure of Al gels with basicity (R) =2.6 and 3.0, even at high loading level, as evidenced by the signal at ≈63×10-6 of magic angle spinning (MAS)-27Al NMR. The adsorption envelope was determined by conventional batch experiments.展开更多
随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO...随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO反应中表现出较好的丙烯选择性和反应寿命,引起了广泛关注.研究表明,分子筛的酸中心分布与MTO反应性能密切相关,因此,研究ITQ-13沸石中铝分布与MTO反应性能的关系,对进一步提升其MTO催化性能具有重要意义.本文分别以与ITH具有共同基本结构单元(双四元环,D4Rs)的LTA沸石(LTA-ITH)和薄水铝石(C-ITH)为铝源,合成了两类铝硅酸盐ITH沸石.X射线衍射、扫描电子显微镜以及氮气吸脱附表征结果表明,这两类分子筛具有相似的片状形貌和微孔性质.氨气程序升温脱附结果表明,具有相近硅铝比的两类ITH沸石具有相近的酸量.进一步采用27Al魔角旋转核磁共振(MAS NMR)、密度泛函理论计算和1-己烯裂解反应对两类ITH分子筛的铝分布进行研究.结果表明,两类分子筛具有不同的铝分布,LTA-ITH中有更多的铝进入ITH的正弦孔道与直孔道,而C-ITH中有更多的铝分布在交叉孔道.当前,研究者普遍认为MTO反应过程遵循双循环烃池机理,ITH交叉孔道由于具有较大的空间,相比于正弦孔道和直孔道,更有利于芳烃循环中间体的产生,从而有利于形成芳烃循环产物(乙烯),而正弦孔道和直孔道却更有利于烯烃循环过程,导致产生更多的丙烯.对两类ITH进行了MTO催化性能测试,结果表明,LTA-ITH比C-ITH表现出更高的丙烯选择性,并且表现出更高的丙烯与乙烯的比率,表明其烯烃循环过程得到加强,这与^(27)Al MAS NMR以及1-己烯裂解反应得到的结论一致,进一步证明ITH分子筛的铝分布得到有效调控.综上,本文阐明了ITH沸石中铝分布与其反应性能的关系,为调整沸石骨架中的Al位点提供一种新策略,为未来制备高效的MTO沸石基催化剂提供参考.展开更多
The coordination structure of aluminum in magnesium aluminum hydroxide was studied by 27Al NMR. The result showed that tetrahedral aluminum (AlIV) existed in magnesium aluminum hydroxide, and the contents of AlIV inc...The coordination structure of aluminum in magnesium aluminum hydroxide was studied by 27Al NMR. The result showed that tetrahedral aluminum (AlIV) existed in magnesium aluminum hydroxide, and the contents of AlIV increased with the increase of the ratio of Al/Mg and with the peptizing temperature. AlIV originated from the so-called Al13 polymer with the structure of one Al tetrahedron surrounded by twelve Al octahedrons.展开更多
Poly(aluminum chloride)(PAC) solutions of different basicity were prepared from pure aluminum foil and hydrochloric acid. Aluminum species were investigated by 27Al NMR spectroscopy and the tridecameric polycation Al ...Poly(aluminum chloride)(PAC) solutions of different basicity were prepared from pure aluminum foil and hydrochloric acid. Aluminum species were investigated by 27Al NMR spectroscopy and the tridecameric polycation Al 13 was detected. With the increase of PAC′s basicity, the molar ratio of Al 13 to Al m in PAC increases. The jar tests with kaolin water and water from Huangpu River at the same PACs dosage showed that the more basicity and content of Al 13, the more effective the coagulation effect on water with middle-high turbidity, while only less effect of the basicity was observed on water with low turbidity.展开更多
探讨了运用Al-Ferron逐时络合比色分光光度法进行Al30分析的适用性.与传统ferron比色法属于操作性的定义不同,该方法对Al-Ferron逐时络合比色的时间扫描数据进行非线性拟合,并假定3种动力学可测形态:一种是瞬时完成的0级反应的铝单体;...探讨了运用Al-Ferron逐时络合比色分光光度法进行Al30分析的适用性.与传统ferron比色法属于操作性的定义不同,该方法对Al-Ferron逐时络合比色的时间扫描数据进行非线性拟合,并假定3种动力学可测形态:一种是瞬时完成的0级反应的铝单体;另两种是一级反应的待定形态.以拟合得到的特征k值和吸光度,作为定性和定量的依据.结果表明:通过优化拟合改进的ferron比色法,可以获得Al30的特征k值,其值在15 mL ferron比色体系中为7×10-5数量级;Al30用ferron比色法的定量分析结果与27Al NMR鉴定结果基本一致,可用以定量分析Al30.该方法既可替代昂贵的27Al NMR鉴定,又能弥补传统ferron比色法定性模糊的不足.展开更多
基金supported by the specialized research funds for the doctoral program of Higher Education of China (Grant No. 2006029009)the Program for New Century Excellent Talents in Universities and Colleges (Grant No. NCET-07-0801)
文摘Fourier transformed infrared spectrometry (FTIR) and 27Al Magic Angle spinning (MAS) nuclear magnetic resonance spectroscopy were employed to characterize arsenate adsorption on amorphous Al gels with Keggin structure at pH =4–10. These studies have proven that: the surface complex species of arsenate show significant differences under acidic and alkaline conditions, which was deduced based on the As-O stretching vibration bands located respectively at 774 and 870 cm-1; poorly crystalline Al13 (or Al)-arsenate precipitation could be easily formed under acid medium condition and high loading level, which was supported by comparing the As-O vibration (at ≈732 cm-1) of precipitation to adsorbed Al gels; arsenate (AsO43-) adsorption has no effect on the Keggin structure of Al gels with basicity (R) =2.6 and 3.0, even at high loading level, as evidenced by the signal at ≈63×10-6 of magic angle spinning (MAS)-27Al NMR. The adsorption envelope was determined by conventional batch experiments.
文摘随着低碳烯烃需求量的增加,甲醇制烯烃(MTO)成为由非石油资源制取低碳烯烃的关键技术,其中沸石由于具有可调节的酸度、有序的微孔结构和较好的择型性能而被广泛用作MTO反应催化剂.ITQ-13沸石(ITH拓扑结构)由于其独特的九元环结构在MTO反应中表现出较好的丙烯选择性和反应寿命,引起了广泛关注.研究表明,分子筛的酸中心分布与MTO反应性能密切相关,因此,研究ITQ-13沸石中铝分布与MTO反应性能的关系,对进一步提升其MTO催化性能具有重要意义.本文分别以与ITH具有共同基本结构单元(双四元环,D4Rs)的LTA沸石(LTA-ITH)和薄水铝石(C-ITH)为铝源,合成了两类铝硅酸盐ITH沸石.X射线衍射、扫描电子显微镜以及氮气吸脱附表征结果表明,这两类分子筛具有相似的片状形貌和微孔性质.氨气程序升温脱附结果表明,具有相近硅铝比的两类ITH沸石具有相近的酸量.进一步采用27Al魔角旋转核磁共振(MAS NMR)、密度泛函理论计算和1-己烯裂解反应对两类ITH分子筛的铝分布进行研究.结果表明,两类分子筛具有不同的铝分布,LTA-ITH中有更多的铝进入ITH的正弦孔道与直孔道,而C-ITH中有更多的铝分布在交叉孔道.当前,研究者普遍认为MTO反应过程遵循双循环烃池机理,ITH交叉孔道由于具有较大的空间,相比于正弦孔道和直孔道,更有利于芳烃循环中间体的产生,从而有利于形成芳烃循环产物(乙烯),而正弦孔道和直孔道却更有利于烯烃循环过程,导致产生更多的丙烯.对两类ITH进行了MTO催化性能测试,结果表明,LTA-ITH比C-ITH表现出更高的丙烯选择性,并且表现出更高的丙烯与乙烯的比率,表明其烯烃循环过程得到加强,这与^(27)Al MAS NMR以及1-己烯裂解反应得到的结论一致,进一步证明ITH分子筛的铝分布得到有效调控.综上,本文阐明了ITH沸石中铝分布与其反应性能的关系,为调整沸石骨架中的Al位点提供一种新策略,为未来制备高效的MTO沸石基催化剂提供参考.
基金This research is supported by NNSFC No:20273041.
文摘The coordination structure of aluminum in magnesium aluminum hydroxide was studied by 27Al NMR. The result showed that tetrahedral aluminum (AlIV) existed in magnesium aluminum hydroxide, and the contents of AlIV increased with the increase of the ratio of Al/Mg and with the peptizing temperature. AlIV originated from the so-called Al13 polymer with the structure of one Al tetrahedron surrounded by twelve Al octahedrons.
文摘Poly(aluminum chloride)(PAC) solutions of different basicity were prepared from pure aluminum foil and hydrochloric acid. Aluminum species were investigated by 27Al NMR spectroscopy and the tridecameric polycation Al 13 was detected. With the increase of PAC′s basicity, the molar ratio of Al 13 to Al m in PAC increases. The jar tests with kaolin water and water from Huangpu River at the same PACs dosage showed that the more basicity and content of Al 13, the more effective the coagulation effect on water with middle-high turbidity, while only less effect of the basicity was observed on water with low turbidity.
文摘探讨了运用Al-Ferron逐时络合比色分光光度法进行Al30分析的适用性.与传统ferron比色法属于操作性的定义不同,该方法对Al-Ferron逐时络合比色的时间扫描数据进行非线性拟合,并假定3种动力学可测形态:一种是瞬时完成的0级反应的铝单体;另两种是一级反应的待定形态.以拟合得到的特征k值和吸光度,作为定性和定量的依据.结果表明:通过优化拟合改进的ferron比色法,可以获得Al30的特征k值,其值在15 mL ferron比色体系中为7×10-5数量级;Al30用ferron比色法的定量分析结果与27Al NMR鉴定结果基本一致,可用以定量分析Al30.该方法既可替代昂贵的27Al NMR鉴定,又能弥补传统ferron比色法定性模糊的不足.
