The interaction of the structure-directing agent with the zeolite framework determines germanium distribution in SCM-15 germanosilicate

doi:10.1007/s11705-024-2417-1

2024, Vol. 18

Issue (5) : 58 https://doi.org/10.1007/s11705-024-2417-1

The interaction of the structure-directing agent with the zeolite framework determines germanium distribution in SCM-15 germanosilicate

Stoyan P. Gramatikov¹, Petko St. Petkov¹, Zhendong Wang², Weimin Yang², Georgi N. Vayssilov¹(

)

¹. Faculty of Chemistry and Pharmacy, University of Sofia, 1126 Sofia, Bulgaria
². State Key Laboratory of Green Chemical Engineering and Industrial Catalysis; Sinopec Shanghai Research Institute of Petrochemical Technology Co., Ltd., Shanghai 201208, China

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Abstract

We report results from computational modeling of the relative stability of germanosilicate SCM-15 structure due to different distribution of germanium heteroatoms in the double four-member rings (D4Rs) of the framework and the orientation of the structure directing agent (SDA) molecules in the as-synthesized zeolite. The calculated relative energies of the bare zeolite framework suggest that structures with germanium ions clustered in the same D4Rs, e.g., with large number of Ge–O–Ge contacts, are the most stable. The simulations of various orientations of the SDA in the pores of the germanosilicate zeolite show different stability order—the most stable models are the structures with germanium spread among all D4Rs. Thus, for SCM-15 the stabilization due to the presence of the SDA and their orientation, is thermodynamic factor directing both the formation of specific framework type and Ge distribution in the framework during the synthesis. The relative stability of bare structures with different germanium distribution is of minor importance. This differs from SCM-14 germanosilicate, reported earlier, for which the stability order is preserved in presence of SDA. Thus, even for zeolites with the same chemical composition and SDA, the characteristics of their framework lead to different energetic preference for germanium distribution.

Keywords zeolite density functional theory structure-directing agent SCM-15

Corresponding Author(s): Georgi N. Vayssilov

Just Accepted Date: 01 February 2024 Issue Date: 19 March 2024

Cite this article:

Stoyan P. Gramatikov,Petko St. Petkov,Zhendong Wang, et al. The interaction of the structure-directing agent with the zeolite framework determines germanium distribution in SCM-15 germanosilicate[J]. Front. Chem. Sci. Eng., 2024, 18(5): 58.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2417-1
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I5/58

Tab.1 Summary of the relative stability and some structural parameters for SCM-15 germanosilicate with different Ge distribution with respect to the most stable structure (in eV), number of Ge–O–Ge contacts per unit cell, number of D4R(8Ge) per unit cell containing only Ge as T-atoms, number of 4R(4Ge) containing only Ge as T-atoms without those in D4R(8Ge) per unit cell, average Ge–O–Ge angles

Fig.1 Nine of the modeled structures of SCM-15 germanosilicate with different relative distribution of germanium ions (blue spheres) in the D4R; structures are denoted according to the notation, used in Tab.1.

Fig.2 Relative stabilities of the SCM-15 structures with different germanium distribution in the D4Rs versus the number of the Ge–O–Ge contacts in the unit cell.

Tab.2 Average interatomic distances (in ?) and angles (in degrees) of 9 SCM-15 germanosilicate structures with different Ge distribution

Fig.3 Relative stability of 9 of the SCM-15 structures with different germanium distribution in the D4Rs (three structures with 2 D4Rs made up only by Ge—S15a, S15b and S15c, three models containing 1 D4R(8Ge)—S15d, S15e and S15l, and three models without D4R(8Ge) units—S15k, S15m and S15n): (A) versus the average distance Ge–Si in the unit cell and (B) versus the average angle Ge–O–Si in the unit cell.

Fig.4 Model structure of as-synthesized SCM-15 with SDA in its cavities, shown along each axis.

Tab.3 General information about the models with SDA inside the pores of SCM-15^a)

Fig.5 (a) Relative energies of the models with SDA from Series 1 versus the relative energies of the models with the same distribution of Ge without SDA in the zeolite channels. (b) Relative energies of the models with SDA from Series 1 versus the number of Ge–O–Ge contacts.

Fig.6 The relative energy of the models in Series 2 with different orientations of the SDA.

Fig.7 Calculated relative energy of the SCM-15 structures without SDA (blue circles) and the relative stabilization energy (brown circles) versus the number of completely silicon D4R(8Si) in the zeolite framework. Tentative trend lines are also shown.

Tab.4 Calculated atomic charges (in e) for the as-synthesized germanosilicate models S15a_1 and S15j_1 and total charges of the zeolite framework, SDA and water

1	J Čejka , M Opanasenko , M Shamzhy , Y Wang , W Yan , P Nachtigall . Synthesis and post-synthesis transformation of germanosilicate zeolites. Angewandte Chemie International Edition, 2020, 59(44): 19380–19389 https://doi.org/10.1002/anie.202005776
2	J Jiang , J L Jorda , M J Diaz-Cabanas , J Yu , A Corma . The synthesis of an extra-large-pore zeolite with double three-ring building units and a low framework density. Angewandte Chemie International Edition, 2010, 49(29): 4986–4988 https://doi.org/10.1002/anie.201001506
3	Y Li , J Yu . New stories of zeolite structures: their descriptions, determinations, predictions, and evaluations. Chemical Reviews, 2014, 114(14): 7268–7316 https://doi.org/10.1021/cr500010r
4	P St Petkov , H A Aleksandrov , V Valtchev , G N Vayssilov . Framework stability of heteroatom substituted forms of large pore Ge-silicate molecular sieves: the case of ITQ-44. Chemistry of Materials, 2012, 24(13): 2509–2518 https://doi.org/10.1021/cm300861e
5	C Zhang , E Kapaca , J Li , Y Liu , X Yi , A Zheng , X Zou , J Jiang , J Yu . An extra-large pore zeolite with 24 × 8 × 8-ring channels using a structure directing agent derived from traditional Chinese medicine. Angewandte Chemie International Edition, 2018, 57(22): 6486–6490 https://doi.org/10.1002/anie.201801386
6	Z R Gao , J Li , C Lin , A Mayoral , J Sun , M A Camblor . HPM-14: a new germanosilicate zeolite with interconnected extra-large pores plus odd-membered and small pores. Angewandte Chemie International Edition, 2020, 60(7): 3438–3442 https://doi.org/10.1002/anie.202011801
7	K C Kemp , W Choi , D Jo , S H Park , S B Hong . Synthesis and structure of the medium-pore zeolite PST-35 with two interconnected cages of unusual orthorhombic shape. Chemical Science, 2022, 13(35): 10455–10460 https://doi.org/10.1039/D2SC03628B
8	A Corma , M J Díaz-Cabañas , J L Jordá , C Martínez , M Moliner . High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings. Nature, 2006, 443(7113): 842–845 https://doi.org/10.1038/nature05238
9	P Chlubná-Eliášová , Y Tian , A B Pinar , M Kubů , J Čejka , R E Morris . The assembly-disassembly-organization-reassembly mechanism for 3d-2d-3d transformation of germanosilicate IWW Zeolite. Angewandte Chemie International Edition, 2014, 53(27): 7048–7052 https://doi.org/10.1002/anie.201400600
10	H Xu , J Jiang , B Yang , H Wu , P Wu . Effective Baeyer-Villiger oxidation of ketones over germanosilicates. Catalysis Communications, 2014, 55: 83–86 https://doi.org/10.1016/j.catcom.2014.06.019
11	Z Liu , J Yuan , J M van Baten , J Zhou , X Tang , C Zhao , W Chen , X Yi , R Krishna , G Sastre . et al.. Synergistically enhance confined diffusion by continuum intersecting channels in zeolites. Science Advances, 2021, 7(11): eabf0775 https://doi.org/10.1126/sciadv.abf0775
12	Y Ma , S Song , C Liu , L Liu , L Zhang , Y Zhao , X Wang , H Xu , Y Guan , J Jiang . et al.. Germanium-enriched double-four-membered-ring units inducing zeolite-confined subnanometric Pt clusters for efficient propane dehydrogenation. Nature Catalysis, 2023, 6(6): 506–518 https://doi.org/10.1038/s41929-023-00968-7
13	V I Kasneryk , M V Shamzhy , M V Opanasenko , J Cejka . Tuning of textural properties of germanosilicate zeolites ITH and IWW by acidic leaching. Journal of Energy Chemistry, 2016, 25(2): 318–326 https://doi.org/10.1016/j.jechem.2015.12.003
14	J Li , A Corma , J Yu . Synthesis of new zeolite structures. Chemical Society Reviews, 2015, 44(20): 7112–7127 https://doi.org/10.1039/C5CS00023H
15	K Lu , J Huang , M Jiao , Y Zhao , Y Ma , J Jiang , H Xu , Y Ma , P Wu . Topotactic conversion of Ge-rich IWW zeolite into IPC-18 under mild condition. Microporous and Mesoporous Materials, 2021, 310: 110617 https://doi.org/10.1016/j.micromeso.2020.110617
16	C Luo , X Li , W Fu , Z Yuan , W Tao , Z Wang , W Yang . Hydrothermally stable ITH-type zeolite directed by a simple nonquaternary ammonium pyrrolidine derivative: synthesis, characterization and catalytic performance. Microporous and Mesoporous Materials, 2021, 319: 111058 https://doi.org/10.1016/j.micromeso.2021.111058
17	C Isaac , J Paillaud , T J Daou , A Ryzhikov . Synthesis of BEC-type germanosilicates with asymmetric diquaternary ammonium salts. Microporous and Mesoporous Materials, 2021, 312: 110804 https://doi.org/10.1016/j.micromeso.2020.110804
18	S O Odoh , M W Deem , L Gagliardi . Preferential location of germanium in the UTL and IPC-2a zeolites. Journal of Physical Chemistry C, 2014, 118(46): 26939–26946 https://doi.org/10.1021/jp510495w
19	N Kasian , A Tuel , E Verheyen , C E A Kirschhock , F Taulelle , J A Martens . NMR evidence for specific germanium siting in IM-12 zeolite. Chemistry of Materials, 2014, 26(19): 5556–5565 https://doi.org/10.1021/cm502525w
20	P Kamakoti , T A Barckholtz . Role of germanium in the formation of double four rings in zeolites. Journal of Physical Chemistry C, 2007, 111(9): 3575–3583 https://doi.org/10.1021/jp065092e
21	G Sastre , A Corma . Predicting structural feasibility of silica and germania zeolites. Journal of Physical Chemistry C, 2010, 114(3): 1667–1673 https://doi.org/10.1021/jp909348s
22	E Verheyen , L Joos , K Van Havenbergh , E Breynaert , N Kasian , E Gobechiya , K Houthoofd , C Martineau , M Hinterstein , F Taulelle . et al.. Design of zeolite by inverse sigma transformation. Nature Materials, 2012, 11(12): 1059–1064 https://doi.org/10.1038/nmat3455
23	S P Gramatikov , G N Vayssilov . Petkov P. The relative stability of SCM-14 germanosilicate with different distributions of germanium ions in the absence and presence of structure-directing agents. Inorganic Chemistry Frontiers, 2022, 9(15): 3747–3757 https://doi.org/10.1039/D2QI00697A
24	Y Luo , S Smeets , Z Wang , J Sun , W Yang . Synthesis and structure determination of SCM-15: a 3D large pore zeolite with interconnected straight 12 × 12 × 10-ring channels. Chemistry, 2019, 25(9): 2184–2188 https://doi.org/10.1002/chem.201805187
25	J P Perdew , K Burke , M Ernzerhof . Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868 https://doi.org/10.1103/PhysRevLett.77.3865
26	S J Grimme . Semiempirical GGA-type density functional constructed with a long-range dispersion correction. Journal of Computational Chemistry, 2006, 27(15): 1787–1799 https://doi.org/10.1002/jcc.20495
27	G Kresse , J Hafner . Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Physical Review B: Condensed Matter, 1994, 49(20): 14251–14269 https://doi.org/10.1103/PhysRevB.49.14251
28	G Kresse , J Furthmüller . Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 1996, 6(1): 15–50 https://doi.org/10.1016/0927-0256(96)00008-0
29	P E Blöchl . Projector augmented-wave method. Physical Review B: Condensed Matter, 1994, 50(24): 17953–17979 https://doi.org/10.1103/PhysRevB.50.17953
30	G Kresse , J Joubert . From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B: Condensed Matter, 1999, 59(3): 1758–1775 https://doi.org/10.1103/PhysRevB.59.1758
31	T A Manz , N Gabaldon Limas . Introducing DDEC6 atomic population analysis: Part 1. Charge partitioning theory and methodology. RSC Advances, 2016, 6(53): 47771–47801 https://doi.org/10.1039/C6RA04656H
32	N Gabaldon Limas , T A Manz . Introducing DDEC6 atomic population analysis: part 2. Computed results for a wide range of periodic and nonperiodic materials. RSC Advances, 2016, 6(51): 45727–45747 https://doi.org/10.1039/C6RA05507A
33	M Fischer , C Bornes , L Mafra , J Rocha . Elucidating the germanium distribution in itq-13 zeolites by density functional theory. Chemistry, 2022, 28(14): e202104298 https://doi.org/10.1002/chem.202104298
34	R C Deka , V A Nasluzov , Shor E I Ivanova , A M Shor , G N Vayssilov , N Rösch . Comparison of all sites for Ti substitution in zeolite TS-1 by an accurate embedded-cluster method. Journal of Physical Chemistry B, 2005, 109(51): 24304–24310 https://doi.org/10.1021/jp050056l
35	S Sklenak , J Dědeček , C Li , B Wichterlova , V Gabova , M Sierka , J Sauer . Aluminium siting in the ZSM-5 framework by combination of high resolution 27Al NMR and DFT/MM calculations. Physical Chemistry Chemical Physics, 2009, 11(8): 1237–1247 https://doi.org/10.1039/B807755J
36	S Nystrom , A Hoffman , D Hibbitts . Tuning Brønsted acid strength by altering site proximity in CHA framework zeolites. ACS Catalysis, 2018, 8(9): 7842–7860 https://doi.org/10.1021/acscatal.8b02049
37	M V Shamzhy , P Eliasova , D Vitvarova , M V Opanasenko , D S Firth , R E Morris . Post-synthesis stabilization of germanosilicate zeolites ITH, IWW, and UTL by substitution of Ge for Al. Chemistry, 2016, 22(48): 1–11 https://doi.org/10.1002/chem.201603434
38	P Lu , L Gomez-Hortiguela , Z Gaoa , M A Camblor . Synthesis of germanosilicate zeolite HPM-12 using a short imidazolium-based dication: structure-direction by charge-to-charge distance matching. Dalton Transactions, 2019, 48(48): 17752–17762 https://doi.org/10.1039/C9DT04089G

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