Jie
Liang
ab,
Wei
Xia
c,
Junliang
Sun
*ab,
Jie
Su
b,
Maofeng
Dou
d,
Ruqiang
Zou
c,
Fuhui
Liao
a,
Yingxia
Wang
*a and
Jianhua
Lin
a
aCollege of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China. E-mail: yxwang@pku.edu.cn; junliang.sun@pku.edu.cn
bBerzelii Center EXSELENT on Porous Materials and Inorganic and Structural Chemistry, Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, 10691, Sweden
cCollege of Engineering, Peking University, Beijing, 100871, China
dDepartment of Materials Science and Engineering, Royal Institute of Technology, Stockholm, 10044, Sweden
First published on 25th January 2016
A novel quasi-zeolite PKU-15, with a rare 3-dimensional structure containing interconnected large (12-ring), medium (10-ring) and small (7-ring) multi-pore channels, was hydrothermally synthesised and characterised. A unique tri-bridging O2− anion is found to be encapsulated in the cage-like (Ge,Si)12O31 building unit and energetically stabilises the PKU-15 framework. The removal of this oxygen atom would convert PKU-15 into a hypothetical zeolite PKU-15H. Thus, PKU-15 can be considered as a unique ‘quasi-zeolite’, which bridges porous germanates and zeolites. Owing to the absence of terminal Ge–OH groups in its structure, PKU-15 shows a remarkably high thermal stability of up to 600 °C. PKU-15 is also the first microporous germanate that exhibits permanent porosity, with a BET area of 428 m2 g−1 and a good adsorption affinity toward CO2.
The hydrothermal conditions for the synthesis of zeolites usually involve alkaline or nearly neutral fluoride medium. OH− or F−, acting as mineralizers, may be involved in the small building units, e.g. [46], [415262], [415462], [4354], and [435261] cages, during the process.18–24 Generally, these anions can be removed together with organic templates during calcination. But in some cases, the interactions between OH−/F− and the T atoms are so strong that these anions can become part of the framework as terminal groups and/or bridging species, for instance in the gallophosphate Mu-28,25 the AFR-type aluminophosphate (AlPO4-40),26 the SFO-type aluminophosphate (SSZ-51)27 and the ZON-type gallophosphate (DAB-2).28 The effect of extra-framework anions encapsulated inside the small cages of the zeolite framework is substantial. On the one hand, these anions make their adjacent T atoms 5- or 6-coordinated, resulting in the porous compounds becoming ‘quasi-zeolites’. On the other hand, theoretical calculations reveal that the inclusion of OH− and F− in the small building units may provide additional stabilisation energy for the formation of as-made zeolites.29–31 Although the occlusion of OH− or F− anions in zeolite cages is common, little is known regarding the effect of O2− anions encapsulated inside similar cages on the structures of zeolites. Herein we report the first example of a quasi-zeolite |(CH3)3N(C3H7)|2[Ge10.75Si1.25O19O12/2][Ge3O3O6/2] (denoted as PKU-15) with a unique tri-bridging O2− anion encapsulated within the cage-like (Si,Ge)12O31 building unit. The interaction between the trapped O2− anion and the PKU-15 framework was also investigated by theoretical calculations. PKU-15 represents a unique fully interconnected multi-pore system with large (12-ring), medium (10-ring), and small (7-ring) channels. Its thermal stability and gas adsorption properties were also investigated.
PKU-15 crystallizes in the orthorhombic space group Pnma (no. 62) with the lattice constants a = 16.8108(5) Å, b = 19.7138(7) Å and c = 23.9394(9) Å. The framework is built from a novel (Ge,Si)12O31 cluster and Ge3O9 3-ring units. The 3-ring unit is rare in silicates, but is relatively common in germanates due to the favourable bond parameters of [GeO4] units.32 The (Ge,Si)12O31 cluster, consisting of three GeO5 trigonal bipyramids and nine (Ge,Si)O4 tetrahedra, is a novel building unit (BU) which has never been reported before (Fig. 1a). In each (Ge,Si)12O31 cluster, an oxygen anion is encapsulated within the BU and linked to three Ge atoms (Ge1, Ge2 and Ge3), making them 5- rather than 4-coordinated, with a trigonal bipyramidal geometry. This produces a Ge3O7 trimer in the centre of the cluster (Fig. 1b). Nine (Ge,Si)O4 tetrahedra are then connected to the trimer through corner-sharing oxygen atoms, giving rise to the non-centrosymmetric (Ge,Si)12O31 cluster [simplified as (Ge,Si)12 hereafter].
The PKU-15 framework can be described as (Ge,Si)12O25 layers interconnected by Ge3O9 3-rings (Fig. 2). The (Ge,Si)12O25 layer is formed solely by (Ge,Si)12 clusters, where one (Ge,Si)12 cluster connects to two neighbouring clusters by sharing a pair of oxygen vertices along the a-axis, and to another two clusters by sharing one corner of the tetrahedron along the b-axis. Such a connection gives rise to the (Ge,Si)12O25 layer with elliptical 10-ring holes in the ab-plane (Fig. 2a). Neighbouring (Ge,Si)12O25 layers, related by an a-glide normal to the c-axis, are then linked via Ge3O9 3-rings, forming the 3D framework of PKU-15 (Fig. 2b and c). The PKU-15 framework can be sketched as a 4,8-heterocoordinated sqc21 net (Fig. 2d), in which the (Ge,Si)12 cluster shares all its 12 corners and acts as an 8-linkage node, and the Ge3O9 3-ring acts as a 4-linkage knot. This also results in a 3D interconnected channel system in PKU-15. A 12-ring sinusoidal channel with an opening of 3.7 Å × 8.7 Å runs along the a-axis, a 7-ring (2.3 Å × 4.0 Å) channel runs along the b-axis, and a 10-ring channel (4.0 Å × 6.1 Å) runs along the c-axis, assuming that the van der Waals radius is 1.35 Å for oxygen (Fig. S3 and S4†). Note that, unlike the circular 12-ring pores in other zeolite frameworks, the 12-ring pore window in PKU-15 is rather squashed. This, combined with the unique 3D 12 × 10 × 7-ring multi-pore channel system, makes PKU-15 a potential catalyst candidate in the petrochemical industry.
The most interesting structural feature of PKU-15 is the presence of the tri-coordinated oxygen atom (O26) within the cage-like (Ge,Si)12 cluster. The removal of O26 could transform PKU-15 into a hypothetical zeolite framework (denoted as PKU-15H), and the (Ge,Si)12 cluster could be described by a hypothetical zeolitic -4-4-4- BU, which is transformed from the known 4-4- BU by inserting a third 4-ring in the middle (Fig. 3a and b). The structure of PKU-15H can be illustrated with the aid of the ZON framework, which is solely built from the 4-4- BU.28,33–36 Similar to the connection mode of the 4-4- BU in ZON, neighbouring -4-4-4- BUs in the PKU-15H framework are joined in a ‘head to tail’ fashion to form chains running parallel to the a-axis (Fig. 3c and e). The adjacent chains, related by inversion symmetry, are linked directly in the ZON framework (Fig. 3c), whereas they are crosslinked via Ge3O9 3-rings in PKU-15H (Fig. 3e). The involvement of the Ge3O9 3-rings endows PKU-15H with a larger sinusoidal 12-ring channel along the a-axis (Fig. 3f), as compared with the sinusoidal 8-ring channel in the ZON framework (Fig. 3d). It is worth noting that in the aluminophosphate analogue of ZON (UiO-7), a similar di-bridging fluoride anion is observed within the cage-like 4-4- BU.35 However, in the zinco-aluminophosphate analogue of ZON (ZAPO-M1), no similar bridging position is found.33 This hints that, by introducing negative charges in the framework, such as substituting Ge4+ with Al3+, the tri-bridging oxygen anion may be removed from the framework and realize the transformation from PKU-15 into PKU-15H. Related work is being studied.
As mentioned above, the tri-coordinated oxygen atom makes PKU-15 a quasi-zeolite. To further understand its role in the formation of the PKU-15 framework, we performed total energy calculations for PKU-15 and PKU-15H based on first-principles.36,37 The two systems were set in the same unit cell, and the only difference is the absence of the tri-coordinated O26 atom in PKU-15H (see Experimental section). To investigate the role that other anions, such as F−, played in the framework formation, similar calculations were also performed for UiO-7 and UiO-7 without the di-bridging F atom (denoted as UiO-7H).35 As expected, the calculated energies for PKU-15 and UiO-7 are about 3.77 eV and 2.2 eV lower than those for PKU-15H and UiO-7H, respectively, suggesting that the extra-framework anions (O2− and F−) do provide additional stabilisation for the frameworks. The much larger energy difference in the PKU-15 system than in the UiO-7 system may suggest that the O2− anion is more crucial for the formation of PKU-15 than the F− anion for the formation of UiO-7. Thus, it may be more difficult to release O2− anions from the cages, as compared with the F− species. As indicated in the literature, the F− anions in UiO-7 can be removed by calcination at approximately 450–550 °C;35 however, in our calculations, the O2− anions can only escape from the -4-4-4- cages in PKU-15 when the heating temperature reaches 1000 °C. Since the PKU-15 framework will collapse at 600 °C due to the breaking of other Ge–O bonds, we cannot obtain the PKU-15 framework without the tri-coordinated O26 atom by direct heating.
Except for the tri-coordinated O26 atom, all the other oxygen atoms in PKU-15 are shared by two neighbouring germanium atoms; thus, there is no terminal group in the PKU-15 framework. As is known, –OH terminal groups are a common feature of porous germanates and can induce a condensation process which may cause the collapse of the framework during heating.38,39 Thus, it is expected that the absence of terminal –OH groups may endow PKU-15 with a high thermal stability. This is proved by TG analysis and in situ variable-temperature powder X-ray diffraction (Fig. 4). In the TG curve, the weight loss of 11.7 wt% (calcd 11.8 wt%) in the range between 200 °C and 700 °C is attributed to the removal of organic templates (Fig. 4a). A main endothermic peak at approximately 450 °C is also observed in the DSC curve, owing to SDA removal (Fig. 4a). As evidenced by the in situ variable-temperature powder X-ray diffraction data, PKU-15 retains its framework integrity up to about 600 °C, even after guest removal (Fig. 4b). The thermal stability of PKU-15 is among the highest reported for porous germanates, and is even higher than some germanate-based zeolites, such as SU-16,40 PKU-9,41 GaGe-JU-64,42 and PKU-14.43
Four half-occupied [(CH3)3N(C3H7)]+ (shortened to Me3PrN+) cations are located in the 12- and 10-ring channels to compensate the −2 charge of the PKU-15 framework (Fig. S5†). Unlike other germanates that usually undergo structure collapse during the removal of organic species, the Me3PrN+ cations in PKU-15 can be totally removed while keeping the framework integrity after heating in ozone for 6 hours (Fig. S6†). Thus, the porosity of the germanate-based PKU-15 quasi-zeolite can be characterised. The N2 sorption isotherms of the ozone-treated sample at 77 K exhibit a typical type-I behavior, indicating the microporous features of PKU-15 (Fig. 5a). The BET area is 428 m2 g−1, compared with about 750 m2 g−1 for a silicate analogue. At 273 K, the ozone-treated PKU-15 sample can adsorb a large amount of CO2 (1.0 mmol g−1, 22.6 cm3 g−1) at 1.0 bar (Fig. 5b). This value is lower than that of the ‘benchmark’ 13X zeolite (7.06 mmol g−1),44 but is higher than that of our recently reported mesoporous germanate PKU-17 (0.7 mmol g−1).45 In light of the unique channel system in PKU-15, we further tested its selective gas adsorption properties. In addition to the CO2 adsorption measurements, CH4, C2H4, C2H6 and N2 adsorption studies were also carried out at 273 K. As expected, PKU-15 can adsorb a moderate amount of CH4 (0.5 mmol g−1, 11.3 cm3 g−1), slightly lower amounts of C2H4 (0.32 mmol g−1, 7.3 cm3 g−1) and N2 (0.28 mmol g−1, 6.3 cm3 g−1), and a limited amount of C2H6 (0.18 mmol g−1, 4.2 cm3 g−1). In view of the kinetic diameters of 3.3 Å for CO2, 3.6 Å for CH4, 3.8 Å for N2, 4.2 Å for C2H4, and 4.4 Å for C2H6, it can be inferred that the pore openings in PKU-15 should be approximately 3.8–4.2 Å in diameter. This is consistent with the crystallographically observed aperture size of 3.7 Å × 8.7 Å for PKU-15. The adsorption selectivity for CO2 over other gases shown by PKU-15 may have applications in the separation of CO2 from flue-gas streams and the separation of CO2 from hydrocarbons.
Fig. 5 Gas sorption isotherms of ozone-treated PKU-15. (a) N2 sorption isotherms at 77 K. (b) CO2, CH4, C2H4, N2 and C2H6 adsorption isotherms at 273 K. P0 represents the standard pressure. |
Footnote |
† Electronic supplementary information (ESI) available: Synthesis, detailed structure description, structure refinement, NMR spectra, and CIFs. CCDC 1059012. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc04916d |
This journal is © The Royal Society of Chemistry 2016 |