Aluminosilicate zeolites as one of the most important catalytic materials are widely applied in industrial reactions,and understanding of their synthetic mechanism is one of key factors in this field.27Al and 29Si NMR...Aluminosilicate zeolites as one of the most important catalytic materials are widely applied in industrial reactions,and understanding of their synthetic mechanism is one of key factors in this field.27Al and 29Si NMR techniques are one of powerful tools for characterization of zeolite synthesis,but unfortunately the study on 27Al NMR spectra of aluminosilicate solutions is still argumentative,and the assignment of aluminosi-licate species in the solutions are challengeable.In this work,we have carefully compared 27Al NMR spectra of various aluminosilicate solutions,harmonizing the assignments reported previously.Furthermore,we assigned 29Si NMR spectra related to Al species.The peaks at δ:-75.1 and-82.5 in 29Si NMR spectrum are related to Q2 Al species,the peaks at δ:-84.5 and-90.8 are related to Q3 and Q4 Al species in aluminosilicate solutions,respectively.展开更多
Paste and mortar specimens were prepared with sulfoaluminate cement(SAC),P⋅O 42.5 ordinary Portland cement(OPC),and standard sand,and mixed and cured with pure water and artificial seawater,respectively.The mechanical...Paste and mortar specimens were prepared with sulfoaluminate cement(SAC),P⋅O 42.5 ordinary Portland cement(OPC),and standard sand,and mixed and cured with pure water and artificial seawater,respectively.The mechanical properties of mortar specimens were tested.Hydration and microstructure of paste specimens were also investigated using X-ray diffraction(XRD),scanning electron microscope(SEM),and 27Al nuclear magnetic resonance(NMR),respectively.The results indicate that SAC mortar samples mixed and cured by seawater have faster strength growth before 28 d and higher compressive strength than OPC mortar samples.Compared to curing in deionized water,the hydration products of SAC are somewhat coarser when cured in simulated seawater.The evolution of aluminum phase hydration products during the hydration process of SAC mixed and cured in simulated seawater is quite different from that of OPC.From 3 to 28 d,the content of each aluminum phase hydration product in SAC paste cured in simulated seawater changed little,while that in OPC paste changed significantly;for example,from 7 to 28 d,the content of ettringite(AFt)in OPC paste increased significantly.This type of AFt formed loosely,harming the mortar's microstructure.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
Aluminum is the primary structural material in nuclear engineering,and its cross section induced by 14-MeV neutrons is of great significance.To address the issue of insufficient accuracy for the^(27)Al(n,2n)^(26)Al re...Aluminum is the primary structural material in nuclear engineering,and its cross section induced by 14-MeV neutrons is of great significance.To address the issue of insufficient accuracy for the^(27)Al(n,2n)^(26)Al reaction cross section,the activation method and accelerator mass spectrometry(AMS)technique were used to determine the^(27)Al(n,2n)^(26)Al cross section,which could be used as a D-T plasma ion temperature monitor in fusion reactors.At the China Academy of Engineering Physics,neutron activation was performed using a K-400 neutron generator produced by the T(d,n)4He reaction.The^(26)Al∕^(27)Al isotope ratios were measured using the newly installed GYIG 1 MV AMS at the Institute of Geochemistry,Chinese Academy of Sciences.The neutron flux was monitored by measuring the activity of 92mNb produced by the 93Nb(n,2n)92mNb reaction.The measured results were compared with available data in the experimental nuclear reaction database,and the measured values showed a reasonable degree of consistency with partially available literature data.The newly acquired cross-sectional data at 12 neutron energy points through systematic measurements clarified the divergence,which has two different growth trends from the existing experimental values.The obtained results are also compared with the corresponding evaluated database,and the newly calculated excitation functions with TALYS−1.95 and EMPIRE−3.2 codes,the agreement with CENDL−3.2,TENDL-2021 and EMPIRE−3.2 results are generally acceptable.A substantial improvement in the knowledge of the^(27)Al(n,2n)^(26)Al reaction excitation function was obtained in the present work,which will lay the foundation for the diagnosis of the fusion ion temperature,testing of the nuclear physics model,evaluation of nuclear data,etc.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
文摘Aluminosilicate zeolites as one of the most important catalytic materials are widely applied in industrial reactions,and understanding of their synthetic mechanism is one of key factors in this field.27Al and 29Si NMR techniques are one of powerful tools for characterization of zeolite synthesis,but unfortunately the study on 27Al NMR spectra of aluminosilicate solutions is still argumentative,and the assignment of aluminosi-licate species in the solutions are challengeable.In this work,we have carefully compared 27Al NMR spectra of various aluminosilicate solutions,harmonizing the assignments reported previously.Furthermore,we assigned 29Si NMR spectra related to Al species.The peaks at δ:-75.1 and-82.5 in 29Si NMR spectrum are related to Q2 Al species,the peaks at δ:-84.5 and-90.8 are related to Q3 and Q4 Al species in aluminosilicate solutions,respectively.
基金Funded by Science and Technology Development Project of China Railway Design Corporation(Nos.2023A0226407,2023B03040003)。
文摘Paste and mortar specimens were prepared with sulfoaluminate cement(SAC),P⋅O 42.5 ordinary Portland cement(OPC),and standard sand,and mixed and cured with pure water and artificial seawater,respectively.The mechanical properties of mortar specimens were tested.Hydration and microstructure of paste specimens were also investigated using X-ray diffraction(XRD),scanning electron microscope(SEM),and 27Al nuclear magnetic resonance(NMR),respectively.The results indicate that SAC mortar samples mixed and cured by seawater have faster strength growth before 28 d and higher compressive strength than OPC mortar samples.Compared to curing in deionized water,the hydration products of SAC are somewhat coarser when cured in simulated seawater.The evolution of aluminum phase hydration products during the hydration process of SAC mixed and cured in simulated seawater is quite different from that of OPC.From 3 to 28 d,the content of each aluminum phase hydration product in SAC paste cured in simulated seawater changed little,while that in OPC paste changed significantly;for example,from 7 to 28 d,the content of ettringite(AFt)in OPC paste increased significantly.This type of AFt formed loosely,harming the mortar's microstructure.
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the Open Project of Guangxi Key Laboratory of Nuclear Physics and Nuclear Technology(NLK 2022-04)the Central Government Guidance Funds for Local Scientific and Technological Development,China(No.Guike,ZY22096024)+1 种基金the National Natural Science Foundation of China(12065003)Guangxi Key R&D Project(2023AB07029).
文摘Aluminum is the primary structural material in nuclear engineering,and its cross section induced by 14-MeV neutrons is of great significance.To address the issue of insufficient accuracy for the^(27)Al(n,2n)^(26)Al reaction cross section,the activation method and accelerator mass spectrometry(AMS)technique were used to determine the^(27)Al(n,2n)^(26)Al cross section,which could be used as a D-T plasma ion temperature monitor in fusion reactors.At the China Academy of Engineering Physics,neutron activation was performed using a K-400 neutron generator produced by the T(d,n)4He reaction.The^(26)Al∕^(27)Al isotope ratios were measured using the newly installed GYIG 1 MV AMS at the Institute of Geochemistry,Chinese Academy of Sciences.The neutron flux was monitored by measuring the activity of 92mNb produced by the 93Nb(n,2n)92mNb reaction.The measured results were compared with available data in the experimental nuclear reaction database,and the measured values showed a reasonable degree of consistency with partially available literature data.The newly acquired cross-sectional data at 12 neutron energy points through systematic measurements clarified the divergence,which has two different growth trends from the existing experimental values.The obtained results are also compared with the corresponding evaluated database,and the newly calculated excitation functions with TALYS−1.95 and EMPIRE−3.2 codes,the agreement with CENDL−3.2,TENDL-2021 and EMPIRE−3.2 results are generally acceptable.A substantial improvement in the knowledge of the^(27)Al(n,2n)^(26)Al reaction excitation function was obtained in the present work,which will lay the foundation for the diagnosis of the fusion ion temperature,testing of the nuclear physics model,evaluation of nuclear data,etc.
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.
