固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布
收稿日期: 2021-04-11
网络出版日期: 2021-05-10
基金资助
国家自然科学基金资助项目(21872017)
Exploring the Na+ Locations and Al Distributions in SSZ-39 Zeolite by Solid-State NMR Spectroscopy and DFT Calculations
Received date: 2021-04-11
Online published: 2021-05-10
具有AEI结构的SSZ-39分子筛的骨架外阳离子落位和铝分布对其催化性能影响显著.AEI笼中有三个结晶学不等价位，且铝取代T位具有一定的倾向性.本文结合固体核磁共振（NMR）技术（27Al/23Na MQ MAS NMR），以及密度泛函理论（DFT）计算，研究了不同硅铝比Na-SSZ-39分子筛中的Na+落位和铝分布.在孤立铝分布的情况下，铝原子优先占据于T3位，Na+主要落位于AEI笼中的SIIa0和SIII'a0位点上，其中SIII'a0位点的优先度较高，此外少部分Na+还落位于六棱柱内部的SIa0.当铝对存在时，AlSiSiAl分布的铝对占据六元环的对位（T3-T3），对应的Na+分别落位于SIIa1和SⅢ'a1位点.随着分子筛结构的部分破坏，游离的Na+可能形成明显的SIII'b位点.本文可加深对SSZ-39分子筛构效关系的理解，为更好地调控催化性能奠定基础.
关键词： 固体核磁共振; SSZ-39分子筛; 铝分布; 阳离子落位; 密度泛函理论（DFT）计算
陈翰迪 , 孔海宇 , 赵侦超 , 张维萍 . 固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布[J]. 波谱学杂志, 2021 , 38(4) : 543 -551 . DOI: 10.11938/cjmr20212906
The catalytic performance of zeolite SSZ-39 with AEI structure is significantly affected by the locations of its extra-framework cation and aluminum distributions. The AEI cage contains three crystallographically inequivalent T sites that tend to be substituted by aluminum. In this work, the Na+ locations and Al distributions in Na-SSZ-39 with different Si/Al ratios were studied by 27Al/23Na MQ MAS NMR spectroscopy together with density functional theory (DFT) calculations. For isolated Al substitution, the T3 site was found to be preferentially occupied by Al, and Na+ was mainly located in the 6-MR (SIIa0) or 8-MR (SIII'a0) sites of the AEI cage, although the priority of SIII'a0 site was slightly higher, and minor Na+ was located inside the hexagonal prism (SIa0). For paired Al substitution, stable AlSiSiAl structure was found to be located in 6-MR, and the corresponding Na+ cations were located at SIIa1 and SIII'a1 sites, respectively. In post-modified zeolites with partial destruction of the framework structure, some free Na+ cations were found to form distinct SIII'b sites. This study deepened the understanding on the structure-reactivity correlation of SSZ-39 zeolite and provided insights into how to fine-tune its catalytic performance.
| 1 | 徐如人, 庞文琴, 等. 分子筛与多孔材料化学[M]. 北京: 科学出版社, 2004. |
| 2 | CORMA A . From microporous to mesoporous molecular sieve materials and their use in catalysis[J]. Chem Rev, 1997, 97 (6): 2373- 2420. |
| 3 | MOLINER M , FRANCH C , PALOMARES E , et al. Cu-SSZ-39, an active and hydrothermally stable catalyst for the selective catalytic reduction of Nox[J]. Catal Commun, 2012, 48 (66): 8264- 8266. |
| 4 | WANG Y , LI G G , ZHANG S Q , et al. Promoting effect of Ce and Mn addition on Cu-SSZ-39 zeolites for NH3-SCR reaction: Activity, hydrothermal stability, and mechanism study[J]. Chem Eng J, 2020, 393, 124782. |
| 5 | MEMIOGLU O , IPEK B . A potential catalyst for continuous methane partial oxidation to methanol using N2O: Cu-SSZ-39[J]. Chem Commun, 2021, 57 (11): 1364- 1367. |
| 6 | MARTIN GARCIA N , LI Z B , MARTINEZ TRIGUERO L J , et al. Nanocrystalline SSZ-39 zeolite as an efficient catalyst for the methanol-to-olefin (MTO) process[J]. Catal Commun, 2016, 52 (36): 6072- 6075. |
| 7 | DUSSELIER M , DEIMUND M A , SCHMIDT J E , et al. Methanol-to-olefins catalysis with hydrothermally treated zeolite SSZ-39[J]. ACS Catal, 2015, 5 (10): 6078- 6085. |
| 8 | DěDECEK J , CAPEK L , KAUCKY D , et al. Siting and distribution of the Co ions in Beta zeolite: A UV-Vis-NIR and FTIR study[J]. J Catal, 2002, 211 (1): 198- 207. |
| 9 | VJUNOV A , FULTON J L , HUTHWELKER T , et al. Quantitatively probing the Al distribution in zeolites[J]. J Am Chem Soc, 2014, 136 (23): 8296- 8306. |
| 10 | GREY C P , POSHNI F I , GUALTIERI A F . Combined MAS NMR and X-ray powder diffraction structural characterization of hydrofluorocarbon-134 adsorbed on zeolite NaY: Observation of cation migration and strong sorbatecation interactions[J]. J Am Chem Soc, 1997, 119 (8): 1981- 1989. |
| 11 | PENG L M , GUO X F , DING W P . 17O Solid-state NMR studies of zeolites: A review[J]. Chinese J Magn Reson, 2009, 26 (2): 173- 187. |
| 11 | 彭路明, 郭学锋, 丁维平. 沸石17O固体核磁共振研究进展[J]. 波谱学杂志, 2009, 26 (2): 173- 187. |
| 12 | YU Z W , ZHENG A M , WANG Q , et al. Acidity characterization of solid acid catalysts by solid-state NMR spectroscopy: A review on recent progresses[J]. Chinese J Magn Reson, 2010, 27 (4): 485- 515. |
| 12 | 喻志武, 郑安民, 王强, 等. 固体核磁共振研究固体酸催化剂酸性进展[J]. 波谱学杂志, 2010, 27 (4): 485- 515. |
| 13 | GAO X Z , ZHANG Y , WANG X M , et al. Structure and acidity changes in ultra-stable Y zeolites during hydrothermal aging: A solid-state NMR spectroscopy study[J]. Chinese J Magn Reson, 2020, 37 (1): 95- 103. |
| 13 | 高秀枝, 张翊, 王秀梅, 等. NMR研究超稳Y分子筛水热老化过程中结构与酸性的变化[J]. 波谱学杂志, 2020, 37 (1): 95- 103. |
| 14 | MASSIOT D , TOUZO B , TRUMEAU D , et al. Two-dimensional magic-angle spinning isotropic reconstruction sequences for quadrupolar nuclei[J]. Solid State Nucl Mag, 1996, 6 (1): 73- 83. |
| 15 | LI S K , ZHAO Z C , ZHAO R R , et al. Aluminum location and acid strength in an aluminum-rich Beta zeolite catalyst: A combined density functional theory and solid-state NMR study[J]. ChemCatChem, 2017, 9 (8): 1494- 1502. |
| 16 | ZHAO R R , Zhao Z C , LI S K , et al. Insights into the correlation of aluminum distribution and Bronsted acidity in H-Beta zeolites from solid-state NMR spectroscopy and DFT calculations[J]. J Phys Chem Lett, 2017, 8 (10): 2323- 2327. |
| 17 | LI S H , LI S K , XING Y D , et al. Aluminum distribution and Br?nsted acidity of Al-Rich SSZ-13 zeolite: A combined DFT calculation and solid-state NMR study[J]. Acta Phys Chim Sin, 2020, 36 (4): 1903021. |
| 17 | 李诗涵, 李世坤, 邢友东, 等. DFT计算结合固体NMR研究富铝SSZ-13的铝分布和Br?nsted酸性[J]. 物理化学学报, 2020, 36 (4): 1903021. |
| 18 | KLEIN P , PASHKOVA V , THOMAS H M , et al. Local structure of cationic sites in dehydrated zeolites inferred from 27Al MAS NMR and DFT calculations. A study on Li-, Na-, and K-chabazite[J]. J Phys Chem C, 2016, 120 (26): 14216- 14225. |
| 19 | SKLENAK S , DěDECEK J , LI C B , et al. Aluminum siting in silicon-rich zeolite frameworks: A combined high-resolution 27Al NMR spectroscopy and quantum mechanics/molecular mechanics study of ZSM-5[J]. Angew Chem Int Ed, 2007, 46 (38): 7286- 7289. |
| 20 | OMEGNA A , VASIC M , VAN BOKHOVEN R A , et al. Dealumination and realumination of microcrystalline zeolite beta: An XRD, FTIR and quantitative multinuclear (MQ) MAS NMR study[J]. Phys Chem Chem Phys, 2003, 6 (2): 88- 99. |
| 21 | HUNGER M , SARV P , SAMOSON A . Two-dimensional triple-quantum 23Na MAS NMR spectroscopy of sodium cations in dehydrated zeolites[J]. Solid State Nucl Mag, 1997, 9 (2-4): 115- 120. |
| 22 | ZHAO Z C , XING Y D , LI S H , et al. Mapping Al distributions in SSZ-13 zeolites from 23Na solid-state NMR spectroscopy and DFT calculations[J]. J Phys Chem C, 2018, 122 (18): 9973- 9979. |
| 23 | MOINI A, MCGUIRE R, MULLER U. A Process for preparing a zeolitic material comprising a metal M and having framework type AEI: WO2018210815-A1[P]. 2018-11-22. |
| 24 | XIE P , ZHANG Y Z , LI S L , et al. Isomorphous substitution of faujusite with (NH4)2 SiF6 Ⅱ. dealumination of (Nh4Na)Y with different na contents and nay[J]. Chinese Journal of Catalysis, 1993, 12 (1): 32- 38. |
| 24 | 谢鹏, 张盈珍, 李淑莲, 等. 八面沸石用(NH4)2 SiF6脱铝补硅的研究[J]. 催化学报, 1993, 12 (1): 32- 38. |
| 25 | ZHU X X , LIU S L , SONG Y Q , et al. Post-treatment with ammonium hexafluorosilicate: An effective way to synthesize high silica MCM-22 zeolite[J]. Catal Commun, 2005, 6 (11): 742- 746. |
| 26 | SOMMER L , MORES D , SVELLE S , et al. Mesopore formation in zeolite H-SSZ-13 by desilication with NaOH[J]. Micropor Mesopor Mat, 2013, 132 (3): 384- 394. |
| 27 | AMOUREUX J P , FERNANDEZ C , STEUERNAGEL S . Z filtering in MQ MAS NMR[J]. J Magn Reson, 1996, 123 (1): 116- 118. |
| 28 | MASSIOT D , FAYON F , CAPRON M , et al. Modelling one- and two-dimensional solid-state NMR spectra[J]. Magn Reson Chem, 2002, 40 (1): 70- 76. |
| 29 | ZHENG A M , ZHANG H , LEI C , et al. Relationship between 1H chemical shifts of deuterated pyridinium ions and Br?nsted acid strength of solid acids[J]. J Phys Chem B, 2007, 111 (12): 3085- 3089. |
| 30 | FRISCH M J, TRUCKS G W, SCHLEGE H B et al. Gaussian 09, Revision D. 01; Gaussian Inc: Wallingford, CT, 2013 |
| 31 | LI Y H , DENG J L , SONG W Y , et al. Nature of Cu species in Cu-SAPO-18 catalyst for NH3-SCR: combination of experiments and DFT calculations[J]. J Phys Chem C, 2016, 120 (27): 14669- 14680. |
| 32 | SMITH L J , ECKERT H , CHEETHAM A K . Potassium cation effects on site preferences in the mixed cation zeolite Li, Na-chabazite[J]. Chem Mater, 2012, 13 (2): 385- 391. |
| 33 | PAOLUCCI C , PAREKH A A , KHURANA I , et al. Catalysis in a cage: Condition-dependent speciation and dynamics of exchanged Cu cations in SSZ-13 zeolites[J]. J Am Chem Soc, 2016, 138 (18): 6028- 6048. |
/
| 〈 |
|
〉 |