A Stacking Faults-Containing Silicogermanate with 24-Ring Channels

Article pubs.acs.org/crystal

A Stacking Faults-Containing Silicogermanate with 24-Ring Channels and Unbranched Zweier Silica Double Chains Liqiu Tang,†,§ Xiaoyan Ren,‡,§ A. Ken Inge,† Tom Willhammar,† Daniel Grüner,† Jihong Yu,*,‡ and Xiaodong Zou*,† †

Inorganic and Structural Chemistry and Berzelii Center EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden ‡ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, People's Republic of China S Supporting Information *

ABSTRACT: A novel open-framework silicogermanate SU-JU-14 (Stockholm University-Jilin University-Number 14), |NH3CH2CH2NH3|3[Ge6.40Si0.60O15(OH)]2[Ge0.73Si3.27O8], was synthesized by using ethylenediamine as the structure-directing agent under solvothermal conditions. Singlecrystal structure analysis reveals that the crystal structure of SU-JU-14 consists of extended 24-ring channels built from [(Ge,Si)7O12O6/2(OH)]3− [(Ge,Si)7] clusters and unbranched zweier silica double chains [Ge0.73Si3.27O4O8/2]. Charge neutrality is achieved by diprotonated ethylenediamine guest molecules. The structure consists of stacking faults of layered arrays in two different configurations along the a-axis. SU-JU14 was characterized by X-ray diffraction, X-ray energy dispersive spectroscopy, scanning electron microscopy, nuclear magnetic resonance, inductively coupled plasma, and thermogravimetric analyses. Crystallographic data: monoclinic, space group C2/c, and unit cell parameters: a = 35.625 (7) Å, b = 28.580 (6) Å, c = 10.403 (2) Å, and β = 98.30 (3)°.

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INTRODUCTION The field of crystalline microporous materials has expanded dramatically during the past decades, due to rich structural diversity and potential industrial applications in adsorption, gas separation, and catalysis.1 An important challenge in this field is to design and synthesize inorganic open-framework materials with extra-large pores, which may show some advantages in the catalysis and separation of large molecules.2 So far, a number of inorganic open-framework materials with extra-large pore structures have been found in silicates,3 phosphates,4 phosphites,5 and germanates.6 A summary of inorganic openframework structures with at least 24-ring channels together with chemical compositions and pore sizes is presented in Table 1. Among them, germanates SU-M7 and JU-84 (also known as JLG-128) as well as germanosilicate zeolite ITQ-37 (zeotype-ITV)9 have the largest 30-ring channels. Reasons for using germanium as a framework element are not limited by its similar properties to silicon but also for its ability to form different coordination polyhedra with oxygen/ fluorine atoms including tetrahedra, trigonal-bipyramids, and octahedra. The linkage of various Ge-centered polyhedra can result in the formation of some large and complex secondary building units (SBUs), such as Ge7X19 (Ge7),10,11 Ge9X26‑m (Ge9),12 and Ge10X27 (Ge10)13 clusters (X = O, OH, F; m = 0− 1), which can be used to construct open-framework structures with large pore sizes and low framework densities as predicted by Férey based on the concept of “Scale Chemistry”.14 In an © 2012 American Chemical Society

attempt to modify the pore size, reduce the cost of materials, and improve the thermal stability of germanates, silicon substitution has been investigated. Partial replacement of germanium atoms in tetrahedral positions by silicon atoms can also enrich the structural novelty of germanates. Silicogermanates with interesting structural features have been reported including SU-1215 with 24-ring channels and SU-6116 with 26-ring channels. One feasible method for the preparation of inorganic openframework structures is to utilize organic structure-directing agents (SDAs) with various sizes, shapes, and charges to direct the pore formation in the frameworks. We are currently searching for possibilities to synthesize novel silicogermanates with extra-large pores using commercially available amines as templates. Here, we report an open-framework silicogermanate, |NH 3 CH 2 CH 2 NH 3 | 3 [Ge 6.40 Si 0.60 O 15 (OH)] 2 [Ge 0.73 Si 3.27 O 8 ] (named as SU-JU-14, Stockholm University-Jilin UniversityNumber 14), with 24-ring channels templated by a simple SDA ethylenediamine.

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EXPERIMENTAL SECTION

Synthesis. SU-JU-14 was prepared by a solvothermal reaction of a mixture of GeO2, H2O, tetraethylorthosilicate (TEOS), ethylenediReceived: April 16, 2012 Revised: June 4, 2012 Published: June 22, 2012 3714

dx.doi.org/10.1021/cg300519t | Cryst. Growth Des. 2012, 12, 3714−3719

Crystal Growth & Design

Article

Table 1. Summary of Inorganic Open-Framework Materials with at Least 24-Ring Channelsa material ND-1 NTHU-1 VSB-1 VSB-5 JU-32b NTHU-5 ASU-16 SU-12 FDU-4 FJ-1a FJ-1b SU-61 ITQ-43 SU-M SU-MB JU-84c ITQ-37

formula

max pore size

ref

[H2DACH][Zn3(PO4)2(PO3OH)]·2H2O [(C4N3H16)(C4N3H15)][Fe5F4(H2PO4)(HPO4)3(PO4)3]·H2O [Ga2(DETA)(PO4)2]2·H2O [Ni18(HPO4)4(OH)3F9][(H3O,NH4)4]·12H2O [Ni20(OH)12(H2O)6][(HPO4)8(PO4)4]·12H2O (C4H12N)2[Zn3(HPO3)4] (C4H9NH3)2[AlFZn2(HPO3)4] (H2DAB)3(DAB)0.5[Ge14O29F4]·16H2O [(CH3CH2CH2NH3)3(H2O)2.5][(Ge6.44Si0.56)O14.5F2] [Ge9O17(OH)4][N(CH2CH2NH3)3]2/3·[HCON(CH3)2]1/6·(H2O)11/3 [Ni(en)3]2[Ni@Ge14O24(OH)3] [Ni(enMe)3]2[Ni@Ge14O24(OH)3] |C6H16N2H2|2[Ge8.7Si1.3O16O11/2OH][Ge0.71Si0.29O4/2][Ge0.22Si0.78O3/2OH]2 [Ge0.31Si0.69O2]10 |(H2MPMD)2(H2O)x|[Ge10O20.5(OH)3] |(H2MPMD)5.5(H2O)x|{[Ge10O21(OH)2]2[Ge7O14F3]} |C6N2H18|30[Ge9O18X4]6[Ge7O14X3]4[Ge7O14.42X2.58]8[GeX2]1.73(X = OH, F) |(C22N2H40)10.5(H2O)x|[Ge80Si112O400H32F20]

24 24 24 24 24 24 26 24 24 24 24 24 26 28 30 30 30 30

4a 4b 4c 4d 4e 5a 5b 10b 15 12a 25 25 16 26 7 7 8 9

a

DACH, 1,2-diaminocyclohexane; DETA, diethylenetriamine; DAB, diaminobutane; en, ethylenediamine; enMe, 1,2-diaminopropane; and MPMD, 2-methylpenta-methylenediamine. bJU-32 is also known as ZnHPO-CJ1. cJU-84 is also known as JLG-12.

amine, and HF in a molar ratio of 1:60:0.8:74.8:2.7. Typically, 0.104 g of GeO2 was dispersed in a mixture of 1.0 mL of H2O and 5 mL of ethylenediamine while stirring. 0.20 mL of TEOS and 0.12 mL of HF solution (40 wt %) were then added to this solution. A homogeneous gel was formed after stirring for about 2 h and was then transferred to a 15 mL Teflon-lined stainless steel autoclave and heated at 180 °C for 7 days under static conditions. The colorless single crystals were separated by filtration, washed by distilled water, and then dried in the air. Structure Determination. A suitable single crystal of SU-JU-14 with dimensions of 0.12 mm × 0.02 mm × 0.02 mm was selected for single-crystal X-ray diffraction (XRD) analysis. Data were collected on a Bruker AXS SMART APEX II diffractometer with graphitemonochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. Data processing was performed with the SAINT processing program.17 The structure was solved by direct methods and refined on F2 by full matrix least-squares technique with the SHELXTL-97 crystallographic software package.18 All framework atoms could be located from the electron density maps. It was found that many framework atom positions were too close to each other, indicating disorder of some atoms in the crystal. Unwarped images from single-crystal XRD data also indicated stacking faults in crystals of SU-JU-14. All diffraction spots with odd l indices gave streaks along the a*-axis instead of sharp spots (Supporting Information, Figures S1−S3). Thus, the intensities extracted from the reflections with odd l indices containing streaks were less accurate (Rint = 0.1823) as compared to the sharp reflections with even l indices (Rint = 0.0696), even though the structure could still be solved using all hkl reflections. Structure determination and refinement were performed using all hkl reflections. When only sharp hkl reflections with even l values and I > 2σ(I) were used, the R1 and wR2 values were much lower, 0.0616 and 0.1808, respectively. Structure determination showed that part of the SU-JU-14 structure built from (Ge, Si)7 clusters is disordered, with two different configurations denoted as A and B, where B is shifted with respect to A by 1/2c. For the refinement, all of the atomic positions in B were restricted to the corresponding atomic positions in A shifted by (0 0 1/2). The ratio of the two configurations was refined. The ordered part of the structure contains only tetrahedrally coordinated T-atoms. They are refined as mixed occupancies of Si and Ge atoms. Atomic positions were refined anisotropically. Squeeze was applied to manage solvent-accessible voids.19 The crystallographic data and the results of structure refinement for SU-JU-14 are listed in Table 2. Single-crystal and

powder XRD simulations that account for stacking faults were made using the software DIFFaX.20

Table 2. Crystallographic Information of SU-JU-14a identification code empirical formula formula weight temperature (K) wavelength crystal system, space group unit cell dimensions

volume Z, calculated density absorption coefficient F(000) crystal size θ range for data collection limiting indices reflections collected/unique completeness to θ = 25.35 absorption correction refinement method data/restraints/parameters goodness-of-fit on F2 final R indices [I > 2σ(I)] R indices (all data) largest diff. peak and hole

SU-JU-14 C1.46H7.32Ge13.54N1.46O40Si4.46 1793.98 293(2) 0.71073 Å monoclinic, C2/c a = 35.625(7) Å α = 90° b = 28.580(6) Å β = 98.30(3)° c = 10.403(2) Å γ = 90° 10481(4) Å3 8, 2.271 g/cm3 7.836 mm−1 6736 0.120 mm × 0.020 mm × 0.020 mm 4.08−25.35° −42 ≤ h ≤ 42, −34 ≤ k ≤ 33, −12 ≤ l ≤ 11 30123/9554 [R(int) = 0.0914] 99.5% SADABS full-matrix least-squares on F2 9554/71/610 0.989 R1 = 0.0885, wR2 = 0.2511 R1 = 0.1255, wR2 = 0.2785 2.284 and −2.876 e. Å−3

a R1 = Σ[ΔF/Σ(Fo)], wR2 = (Σ[w(Fo2 − Fc2)])/Σ[w(Fo2)2]1/2, w = 1/ [σ2(Fo2) + (0.1755P)2 + 0.0000P], where P = (Fo2 + 2Fc2)/3.

Characterization. Powder XRD data were collected on a Siemens D5005 diffractometer with Cu Kα radiation (λ = 1.5418 Å). The 2θ step size was 0.02°, and the exposure time was 4 s/step. Scanning electron microscopy (SEM) was performed on a JSM-6700F electron microscope operating at 5.0 kV. Chemical analysis of silicon and germanium was carried out by X-ray energy dispersive spectroscopy (EDS, LINK AN1000) on a JEOL JSM820 scanning electron 3715



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microscope. The TG analysis was performed on a NETZSCH STA 449C TG/DTA analyzer in air, with a heating rate of 10 °C/min. Inductively coupled plasma (ICP) analysis was performed on a PerkinElmer Optima 3300Dv spectrometer. Elemental analysis was conducted on a Perkin-Elmer 2400 elemental analyzer. Fluoride analysis was conducted on a Mettler-Toledo LE302 Reference Electrode. The 13C NMR spectrum was recorded on a Varian Infinity Plus 400 spectrometer at a magnetic field strength of 9.4 T.

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RESULTS AND DISCUSSION On the basis of the structure refinement and chemical analysis, the chemical formula of SU-JU-14 can be assigned as: |NH 3 CH 2 CH 2 NH3 |3 [Ge 6.40 Si 0.60 O 15 (OH)] 2[Ge 0.73Si 3.27 O 8 ]. Figure 1 shows the SEM image of as-synthesized SU-JU-14

Figure 2. (a) (Ge,Si)7 composite building unit in SU-JU-14 [color code: GeO5(OH), red; GeO5, yellow; and (Ge,Si)O4, green]. (b) Unbranched zweier double chain in SU-JU-14 with the composition [Ge0.73Si3.27O8] [color code: (Ge,Si)O4, purple].

(Ge,Si)7 cluster in SU-JU-14 possesses the T4P2 connection mode,10c which means that each (Ge,Si)7 cluster connects with other building units via its four tetrahedra and two trigonal bipyramids. The 4-ring unit is built from four corner-shared [(Ge,Si)O4/2] tetrahedra. Condensation of such square 4-ring units by edge-sharing along one direction results in an infinite zigzag− zigzag chain parallel to the c-axis,21 as shown in Figure 2b. According to the classification of Liebau, this type of chain is also called an “unbranched zweier double chain” and can be described by the following structural formula: {uB,21∞}[2(Ge,Si)4O10]4−.22 Similar ribbons have been described in Li4[SiGe3O10]23 and ZnGe2O5(NH2CH2CH2NH2).24 The (Ge,Si)7 clusters are connected through corner-shared tetrahedra to form 24-ring channels extended along the [001] direction. The 24-ring channels are C-centered and connect with the unbranched zweier double chains through their trigonal bipyramids, resulting in a three-dimensional (3D) framework with parallel 12- and 24-ring channels along the [001] direction. Figure 3 shows the polyhedral representation of SU-JU-14 viewed along the c-axis. The 24-ring channels are elongated along the b-axis forming a turtle-like shape. All

Figure 1. SEM image of SU-JU-14.

single crystals with rodlike morphology. It is clear that the product is pure and highly crystalline. EDS analysis was carried out on different points, both on the same crystal and from different crystals. The average Ge/Si molar ratio found by EDS was 2.90. ICP analysis gave the contents of Ge and Si as 50.05 and 6.35 wt %, respectively (calcd: Ge, 50.77; Si, 6.47 wt %) with a Ge/Si molar ratio of 3.04, which was consistent with the EDS result. Elemental analysis gave the contents of C, H, and N as 4.11, 1.77, and 4.51 wt %, respectively (calcd: C, 3.72; H, 1.67; N, 4.34 wt %). The experimental XRD pattern of SU-JU-14 shows discrepancies with the pattern calculated from the ideal framework structure model of SU-JU-14 without any stacking faults. The XRD pattern simulated by taking into account the stacking disorders using the software DIFFaX20 shows good agreement with the experimental data (Supporting Information, Figure S4), indicating that the model is correct. The TGA curve of the SU-JU-14 sample pretreated at 100 °C overnight (Supporting Information, Figure S5) shows a total weight loss of 11.94 wt % occurring between 60 and 800 °C, which corresponds to the decomposition of the occluded ethylenediamine molecules and the release of terminal groups as H2O molecules (calcd: 11.40 wt %) in the sample. SU-JU-14 is built up from two different building units: a composite building unit of (Ge,Si)7O12O6/2(OH) [(Ge,Si)7] and a SBU of 4-rings [(Ge,Si)4O4O8/2]. The (Ge,Si)7 cluster consists of one [GeO 4/2 O 1/3 (OH)] octahedron, two [GeO4/2O1/3] trigonal bipyramids, and four [(Ge,Si)O4/2] tetrahedra (Figure 2a). An oxygen atom is located at the core of the cluster and tricoordinated with three germanium atoms from the octahedron and two trigonal bipyramids. There is only one terminal group on the octahedron per (Ge,Si)7 cluster, which is a hydroxyl group because no fluorine was found from the result of fluoride ion selective electrode analysis. The

Figure 3. Polyhedral representation of SU-JU-14 viewed along the caxis. Nonframework cations are not shown for clarity. Color code: GeO5(OH), red; GeO5, yellow; (Ge,Si)O4 in clusters, green; and (Ge,Si)O4 in unbranched zweier double chains, purple. 3716



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terminal −OH groups of the GeO5(OH) octahedra protrude into the 24-ring channels. There are 9- and 10-ring windows intersecting the 12- and 24-ring channels, respectively (Figure 4). The 9-ring windows

Figure 5. Polyhedral presentation of single 24-ring tube viewed in parallel to the 24-ring of (a) SU-12 and (b) SU-JU-14. Color code: GeO5(OH), red; GeO5, yellow; and (Ge,Si)O4 in clusters, green.

Figure 4. Polyhedral representations of the (a) 9-ring and (b) 10-ring windows connected to the 12- and 24-ring channels, respectively, in SU-JU-14. Color code: GeO5(OH), red; GeO5, yellow; (Ge,Si)O4 in clusters, green; and (Ge,Si)O4 in unbranched zweier double chains, purple.

JU-14, the number of terminal atoms is different. In SU-12, there are two terminal atoms per (Ge,Si)7 cluster, one from the octahedron and one from a trigonal bipyramid, while in SU-JU14, there is only one terminal atom per (Ge,Si)7 cluster, which is from the octahedron. Because of the presence of additional tetrahedra in the form of zweier double chains in SU-JU-14, the framework charge density of SU-JU-14 becomes lower (0.33 e− per Ge or Si atom) than that of SU-12 (0.43 e− per Ge or Si atom). The framework density of SU-JU-14 is 13.7 T atoms per 1000 Å3, much higher than that of SU-12 (8.6 T atoms per 1000 Å3). Crystals of SU-JU-14 always contain stacking faults, with a constant ratio of the two different configurations that is independent of different synthesis conditions. The structure consists of ordered zweier double chains that propagate along the c-axis. The (Ge,Si)7 clusters form a layered domain in the bc-plane (Figure 6a) and attach to the zweier double chains in one of two possible locations (Figure 6b). 12- and 24-ring channels are parallel to the layer. The thick layers are stacked along the a-axis to form a 3D framework. The stacking faults occur as an intergrowth of two different domains. The neighboring domains are shifted from each other by 1/2c. Similar disorder has also been observed in the structure of the open-framework germanate ASU-21, where the cylindrical channels are shifted by 1/2c, giving rise to twinning.27 The domains are connected by sharing the 4-ring units, which generates stacking faults. The ratio of the two configurations according to the structure refinement is 74:26. The stacking faults give rise to streaking of reflection rows with odd l indices along the a*-axis. The intensity distribution of the diffraction streaks is determined by the sequence by how the layers containing either A or B type domains are stacked along the a*axis. There are two ordered types of sequences, the first one is built from either consecutive A or B type layers, AAA or BBB, and the second is made from alternating A and B type layers, for example, ABA. In SU-JU-14, the sequence does not follow any of these ordered sequences but is an intergrowth of the two. We performed simulation of the XRD pattern of the disordered SU-JU-14, with the same probability for a consecutive domain type stacking and alternating domain type stacking. The simulated h1l reflections show diffuse streaks

are formed by seven tetrahedra and two trigonal bipyramids. Three of the seven tetrahedra are from the 4-ring units, and the remaining tetrahedra and trigonal bipyramids are from the (Ge,Si)7 clusters. The 10-ring windows are formed by eight tetrahedra and two trigonal bipyramids, all from (Ge,Si)7 clusters. The free diameters of the 24-ring channel are 19.5 Å × 3.8 Å, and the free diameters of the 12-ring channel are 8.0 Å × 4.2 Å (assuming the van der Waals radius of oxygen atoms to be 1.35 Å). The refinement shows that the silicon contents are much higher in the 4-ring units (Si:Ge = 82:18) as compared with those in the tetrahedra of (Ge,Si)7 clusters (Si:Ge = 15:85). Because of the quality of the present data and the disorder of the structure in the crystal, only one unique NH3CH2CH2NH3 cation was located in the asymmetric unit near the wall of the 24-ring channels, resulting in eight NH3CH2CH2NH3 cations in one unit cell. The 13C NMR spectrum (Supporting Information, Figure S6) indicates that NH3CH2CH2NH3 cations keep intact in the structure of SU-JU-14, and there should be 24 NH3CH2CH2NH3 cations in the unit cell, according to the elemental and TG analyses. The (Ge,Si)7 clusters have been found in many 3D openframework germanates including ASU-12,10a ASU-16,10b Ge10O21(OH)·N4C6H21,11f STAG-1,11g SU-8,11h SU-44,11h SU-MB,7 JLG-12,8 and PKU-10,11i as well as in silicogermanate SU-1215 with 24-ring channels. Although the structures of SUJU-14 and SU-12 are both built from (Ge,Si)7 clusters and contain 1D 24-ring channels, the connections between clusters are different. Firstly, as aforementioned, the (Ge,Si)7 clusters in SU-JU-14 adopt the T4P2 linkage mode, while SU-12 possesses the T4P linkage mode, where the clusters connect through four corner-shared GeO4 tetrahedra and one GeO5 trigonal bipyramid. Secondly, the relative orientations of the (Ge,Si)7 clusters around the 24-rings are different, as shown in Figure 5. In SU-12, the eight (Ge,Si)7 clusters circumscribing the 24-ring are situated on a plane, while in SU-JU-14, the (Ge,Si)7 clusters alternate up and down around the 24-ring forming a sawtoothlike structure. Thirdly, because of the different connection modes of the (Ge,Si)7 clusters in SU-12 and SU3717



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CONCLUSION In conclusion, a novel silicogermanate SU-JU-14 has been solvothermally synthesized, which is built from both (Ge,Si)7 clusters and unbranched zweier double chains. The (Ge,Si)7 clusters are connected to each other to form 24-ring channels along the c-axis and further connected by the unbranched zweier double chains to form a 3D framework structure containing intersecting 9-, 10-, 12-, and 24-ring channels. The crystal structure of SU-JU-14 is somewhat disordered, resulting from the intergrowth of stacking faults of the layered arrays with two different configurations along the a-axis. The successful structure determination exemplifies the use of single-crystal XRD to solve disordered structures that exhibit diffuse scattering. Silicogermanates SU-JU-14 and SU-12 both have 24-ring channels and were synthesized using simple organic amines, ethylenediamine and 1-aminopropane, respectively, under the similar solvothermal conditions. The successful synthesis of such materials suggests further opportunities for making novel silicogermanates with extra-large pores by choosing simple amines as templates, which can be of great interest.

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ASSOCIATED CONTENT

* Supporting Information S

Figures of unwarped single-crystal XRD images, XRD patterns, TG curves, 13C NMR spectrum, and infrared spectrum (PDF), and an X-ray crystallographic file (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

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Figure 6. (a) Stacking domains of SU-JU-14 indicated in blue and black viewed along the [001] direction. Layers in the bc-plane form stacking faults along the c-axis. (b) The two stacking domains related by a shift of 1/2 c.

AUTHOR INFORMATION

Corresponding Author

*Tel: +86-431-85168608. Fax: +86-431-85168608. E-mail: [email protected] (J.Y.). Tel: +468162389. Fax: +468152187. E-mail: [email protected] (X.Z.).

along the a*-axis for all reflections with an odd l index, well in correspondence with the experimental data (Figure 7). All hk2 reflections in the simulated XRD pattern appear as sharp spots where as all hk3 reflections show streaks along a*. The intensity distribution along the streaks also shows good agreement with the observed intensities.7

Author Contributions §

These authors contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This project is supported by the Swedish Research Council (VR), the Swedish Governmental Agency for Innovation Systems (VINNOVA) through the Berzelii Center EXSELENT, the Göran-Gustafsson Foundation for nature sciences and medical research, the State Basic Research Project of China (Grant No. 2011CB808703), and the National Natural Science Foundation of China. We thank Dr. Junliang Sun for advice on the structure refinement.

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REFERENCES

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Figure 7. Selected 2D slices of the reciprocal lattice planes of SU-JU14 (a−c) reconstructed from the single-crystal XRD data and (d−f) simulated from the structure model containing stacking faults using DIFFaX.20 3718



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