ZSM-5分子筛铝分布的研究方法
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摘要
按凝胶中硅铝比分别为40和80,合成了板状和球形两种形貌的ZSM-5分子筛。通过将~(27)Al MAS NMR、Co(Ⅱ)离子交换能力及UV-Vis-DRS技术相结合表征了孤立铝和铝对的含量及骨架铝原子的落位信息;采用~(29)Si MAS NMR技术表征了骨架中Si(nSi,(4-n)Al)(n=0~4)序列群体;采用XPS结合XRF表征了ZSM-5分子筛体相、表面和内部的铝分布,并对上述表征骨架铝分布的方法进行了对比。结合多种表征技术,确定了合成的ZSM-5分子筛的铝分布和落位,确定了ZSM-5分子筛骨架中Al的化学环境,为构建ZSM-5分子筛的铝分布和落位与反应性能的关系提供了数据支持。
The ZSM-5 zeolites of plate and spherical were synthesized from the gel with the silicaalumina ratio from 40 to 80. The single Al-Al pairs and the location of the Al atoms of the framework were characterized by UV-Vis-DRS of Co( Ⅱ) ions and ~(27)Al MAS NMR. ~(29)Si MAS NMR was used for determination of the population of Si(nSi,(4-n)Al)(n 0-4)sequences in the framework. The surface and bulk aluminum distribution was characterized by XPS combined with XRF. The above methods of characterizing for the framework of aluminum distribution were compared and summarized. A method for the aluminum distribution and location of ZSM-5 zeolite was provided,which gives data support for the relationship between the aluminum distribution and the reaction performance.
The ZSM-5 zeolites of plate and spherical were synthesized from the gel with the silicaalumina ratio from 40 to 80. The single Al-Al pairs and the location of the Al atoms of the framework were characterized by UV-Vis-DRS of Co( Ⅱ) ions and ~(27)Al MAS NMR. ~(29)Si MAS NMR was used for determination of the population of Si(nSi,(4-n)Al)(n 0-4)sequences in the framework. The surface and bulk aluminum distribution was characterized by XPS combined with XRF. The above methods of characterizing for the framework of aluminum distribution were compared and summarized. A method for the aluminum distribution and location of ZSM-5 zeolite was provided,which gives data support for the relationship between the aluminum distribution and the reaction performance.
引文
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[20]Sazama P,Dědecek J,GábováV,et al.Effect of aluminium distribution in the framework of ZSM-5 on hydrocarbon transformation.Cracking of 1-butene[J].J Catal,2008,254(2):180-189.
[2]Susanne M O,Tianli Z.Influence of the Si/Al ratio and Al distribution on the H-ZSM-5 lattice and Br?nsted acid site characteristics[J].Microporous Mesoporous Mater,2016,222:256-270.
[3]Dědecek J,Dalibor K,Blanka W,et al.Co2+ions as probes of Al distribution in the framework of zeolites.ZSM-5 study[J].Phys Chem Chem Phys,2002,4(21):5406-5413.
[4]赵国良,李学兵,滕加伟.合成条件对ZSM-5分子筛骨架铝分布的影响[J].石油化工,2014,43(增刊):137-139.
[5]Yokoi T,Mochizuki H,Namba S,et al.Control of the Al distribution in the framework of ZSM-5 zeolite and its evaluation by solid-state NMR technique and catalytic properties[J].J Phys Chem C,2015,119(27):15303-15315.
[6]Ling Tingyu,Chen Jialing,Qin Zhangfeng,et al.Conversion of methanol to olefins over H-ZSM-5 zeolite:Reaction pathway is related to the framework aluminum siting[J].ACS Catal,2016,6(11):7311-7325.
[7]Ruiz-Salvador A R,Grau-Crespo R,Gray A E,et al.Journal of solid state chemistry aluminium distribution in ZSM-5 revisited:The role of Al—Al interactions[J].J Solid State Chem,2013,198(2):330-336.
[8]Děde?ek J,KauckyD,WichterlováB.Al distribution in ZSM-5 zeolites:An experimental study[J].Chem Commun,2001,11(11):970-971.
[9]Hughes A E,Wilshie K G,Sexton B A,et al.Aluminum distribution in ZSM-5 as determined by X-ray photoelectron spectroscopy[J].J Catal,1983,80(1):221-227.
[10]Pinar A B,Márquez-álvarez C,Grande-Casas M,et al.Template-controlled acidity and catalytic activity of ferrierite crystals[J].J Catal,2009,263(2):258-265.
[11]Dědecek J,WichterlováB.Co2+ion siting in Pentasil-containing Zeolites.Ⅰ.Co2+ion sites and their occupation in mordenite.A Vis-NIR diffuse reflectance spectroscopy study[J].J Phys Chem B,1999,103(1):1462-1476.
[12]Děde?ek J,KauckyD,WichterlováB.Co2+ion siting in Pentasil-containing zeolites,part 3.Co2+ion sites and their occupation in ZSM-5:A Vis diffuse reflectance spectroscopy study[J].Microporous Mesoporous Mater,2000,35/36(1):483-494.
[13]Li Hansheng,He Shichao,Ma Ke,et al.Micro-mesoporous composite molecular sieves H-ZSM-5/MCM-41 for methanol dehydration to dimethyl ether:Effect of SiO2/Al2O3 ratio in HZSM-5[J].Appl Catal,A,2013,450(15):152-159.
[14]吉向飞,赵娇娇,安转转,等.不同形貌ZSM-5分子筛的制备及其催化甲醇转化制烯烃性能[J].燃料化学学报,2015,43(6):747-753.
[15]Han O H,Kim C S,Hong S B.Direct evidence for the nonrandom nature of Al substitution in zeolite ZSM-5:An investigation by 27Al MAS and MQ MAS NMR[J].Angew Chem,In Ed,2002,41(3):469-472.
[16]Dědecek J,BalgováV,Pashkova V,et al.Synthesis of ZSM-5 zeolites with defined distribution of Al atoms in the framework and multinuclear MAS NMR analysis of the control of Al distribution[J].Chem Mater,2012,24(16):3231-3239.
[17]Stepan S,Dědecek J,Cheng B L,et al.Aluminium siting in the ZSM-5 framework by combination of high resolution27Al NMR and DFT/MM calculations[J].Phys Chem Chem Phys,2009,11(8):1237-1247.
[18]Miroslaw D,Priit S,Xian Y S,et al.Reversibility of the modification of HZSM-5 with phosphate anions[J].J Phys Chem C,2014,118(12):6122-6131.
[19]Sarv P,Fernandez C,Amoureux J,et al.Distribution of tetrahedral aluminium sites in ZSM-5 type Zeolites:An 27Al(Multiquantum)magic angle spinning NMR study[J].J Phys Chem,1996,100(50):19223-19226.
[20]Sazama P,Dědecek J,GábováV,et al.Effect of aluminium distribution in the framework of ZSM-5 on hydrocarbon transformation.Cracking of 1-butene[J].J Catal,2008,254(2):180-189.