A new cluster-based chalcogenide zeolite analogue with a large inter-cluster bridging angle

Zhou Wua, Xiao-Li Wanga, Dandan Hua, Sijie Wua, Chengdong Liua, Xiang Wanga, Rui Zhoua, Dong-Sheng Lib and Tao Wu*a
aCollege of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu 215123, China. E-mail: wutao@suda.edu.cn
bCollege of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002, China

Received 19th August 2019 , Accepted 10th September 2019

First published on 11th September 2019


Chalcogenide-based semiconductor zeolite analogues with unique structures have been intensively applied in the fields of gas adsorption, ion exchange and catalysis. However, there are still great limitations in expanding the topological structures of such materials, compared to typical oxide-based zeolites. In this work, a new chalcogenide-based semiconductor zeolite analogue (denoted as SOF-20) with a supertetrahedral T2-InSnS cluster as a secondary building unit (SBU) is reported. Notably, T2 clusters were found to assemble into a zeolitic-like open framework with a gsi topology via an unusually large inter-cluster bridging angle, which is for the first time observed in the family of chalcogenide-based zeolite analogues. Besides, a T2 cluster-based twisted dia framework (denoted as SOF-21) was also created. Both zeolite analogues exhibit good activity in electrocatalytic oxygen reduction reactions (ORRs) due to active Sn components in these semiconducting frameworks.


Introduction

Crystalline porous materials with well-defined structures and highly ordered porosity have attracted great attention during the past half century.1–4 Among them, zeolite-type materials are enthusiastically desired and extensively studied5–9 since their remarkable thermal and chemical stability makes them involved in many applications, such as gas adsorption/separation,10 ion exchange11 and shape-selective catalysis.12 Natural zeolites, built from metal–oxygen tetrahedra (TO4, T = Si4+ and Al3+) with a flexible T–O–T bridging angle in the range of 140°–150°,13 have been widely created and researched.14–16 However, the extended applications of oxide-based zeolites in the areas of electrocatalysis and photocatalysis were usually restricted due to the insulating nature of their feature elements. One approach for developing and improving the catalytic-related performance is to confine classical catalysts into the channels of zeolites.17–19 The other intelligent strategy is to replace the tetrahedrally-coordinated framework cations (Si4+ or Al3+) with main-group or transition metal ions (Ga3+, In3+, Ge4+, Sn4+, Zn2+, Cu+, Mn2+, etc.) and bi-coordinated O2− with chalcogenides (S2− and Se2−).20–27

Since the pioneering work done by Bedard et al. initiated the family of open-framework chalcogenides,28 great efforts have been devoted to creating microporous chalcogenides with zeolite-like topologies.29–31 It should be noted that compared to natural zeolites, chalcogenide zeolite analogues are more interesting due to their intrinsic properties arising from the feature compositions. The substitution of the TO4 primary unit by chalcogenide clusters provides more possibilities for expanding the applications of zeolite-like frameworks into the fields of photocatalysis and electrocatalysis. For instance, the chalcogenide zeolite analogue of CSZ-5-InSe showed tunable electro-/photoelectrochemical properties.32 Besides, some zeolite-like chalcogenides exhibit promising photoreduction ability toward water and carbon dioxide.33–35 In theory, it is plausible and feasible to create porous chalcogenides with diverse zeolite-like topologies through the assembly of chalcogenide clusters. However, very limited cases have been documented until now.36–38 It is meaningful but still challenging to expand the family members of semiconductor chalcogenides with zeolitic topologies.

Generally, metal-chalcogenide open frameworks with zeolite-like topologies can be regarded as the self-assembly of tetrahedrally-shaped nanoclusters. Among these zeolite-like nets, each supertetrahedral cluster usually serves as a four-connected node and further assembles into multifarious frameworks due to the different orientations and unequal bridging angles between adjacent supertetrahedral clusters. For instance, as for the common T2-cluster-based chalcogenide zeolite analogues, the bond angle of T2–S–T2 lies at 107.3°–108.8° in UCR-20 with a SOD net,39 108.1°–109.5° in UCR-21 with a dia net, 104.7°–105.9° in UCR-23 with the CrB4 topology, and so on. It has been well accepted that such chalcogenide open frameworks with new topological structures can be realized by tuning the inter-cluster bridging angles.

Herein, through the superbase-oriented solvothermal method, two chalcogenide zeolite analogues based on the supertetrahedral T2 cluster were prepared, which are denoted as SOF-20 [(In2Sn2S8)·1.3(H+-DBN)·0.4(H+-AEP)·0.3(H+-AEAE)] (DBN = 1,5-diazabicyclo[4.3.0]-5-nonene, AEP = N-aminoethylpiperazine, AEAE = N-(2-aminoethyl)ethanolamine) and SOF-21 [(In2.6Sn1.4S8)·0.2(H+-DBU)·1.9(H+-PR)·0.5(H+-AEAE)] (DBU = 1,8-diazabicyclo[5.4.0]-7-undecene, PR = piperidine), respectively. Both SOF-20 and SOF-21 are constructed by T2-InSnS clusters. Notably, the framework of SOF-20 displays the gsi topology via a large inter-cluster bridging angle, and SOF-21 represents a twisted structure with a non-interpenetrated dia net.

Experimental section

Materials

Indium powder (In, 99.99%, powder), hydrated indium nitrate (In(NO3)3·xH2O, 99%), tin (Sn, 99%, powder), stannous chloride (SnCl2, 99%, powder), sublimed sulfur (S, 99.9%, powder), thiourea (CH4N2S, 99.9%, powder), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU, 97%, liquid), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN, 97%, liquid), 3,5-dimethylpiperidine (3,5-DMP, 99%, liquid), piperidine (PR, 99%, liquid), N-aminoethylpiperazine (AEP, 99%, liquid), and N-(2-aminoethyl)ethanolamine (AEAE, 99%, liquid) were used in this work. All solid and liquid reagents in this research were purchased without additional purification.

Synthesis of SOF-20 [(In2Sn2S8)·1.3(H+-DBN)·0.4(H+-AEP)·0.3(H+-AEAE)]

In a 23 mL Teflon-lined stainless autoclave, 115 mg of In powder, 120 mg of Sn powder and 96 mg of sublimed sulfur powder were added in the mixed organic solvents of DBN (1 mL), AEP (2 mL) and AEAE (2 mL). After being stirred for half an hour, the autoclave was sealed and placed in a 190° oven for 8 days. Then the mixture was cooled to room temperature. Pale yellow crystals were obtained with a yield of 15% based on indium powder. Remarkably, when AEP was substituted by 3,5-DMP, SOF-20 can also be synthesized.

Synthesis of SOF-21 [(In2.6Sn1.4S8)·0.2(H+-DBU)·1.9(H+-PR)·0.5(H+-AEAE)]

In a 23 mL Teflon-lined stainless autoclave, 191 mg of In(NO3)3·xH2O powder, 48 mg of SnCl2 powder and 200 mg of thiourea powder were added in the mixed organic solvents of DBU (1 mL), PR (2 mL) and AEAE (2 mL). After being stirred for half an hour, the autoclave was sealed and placed in a 190° oven for 7 days. Then the mixture was cooled to room temperature. Pale yellow crystals were obtained with a yield of 40% based on In(NO3)3·xH2O powder.

Ion exchange

To remove the protonated organic amine for pore opening, an ion exchange experiment was performed. SOF-20 (5 mg) was immersed in 5 mL CsCl aqueous solution (1 M) in a glass bottle and then placed at 85 °C. After 24 h, the crystals were taken out from the glass bottle and washed with deionized water to remove the Cs+ species adsorbed on the surface of crystals. The samples were placed at room temperature for about 24 h for further drying. The ion-exchange experiment for SOF-21 was also explored according to the above method.

Single-crystal structure characterization

All single-crystal X-ray diffraction (SC-XRD) measurements were obtained on a Bruker Photon II CPAD diffractometer equipped with graphite-monchromated Mo-Kα (λ = 0.71073 Å) radiation at 120 K under a N2 flow. Direct methods in SHELXS-2014 were adopted to solve the crystal structures; besides, the refinement against all reflections of the two compounds was also treated using SHELXL-2014. The SQUEEZE program in PLATON was used to solve the highly disordered solvent molecules and protonated organic amines.

Material characterization

Powder X-ray diffraction (PXRD) was performed on a D2 PHASER desktop diffractometer, which was operating at 30 kV and 10 mA using Cu-Kα (λ = 1.54056 Å) radiation. The microstructures and element ratios of both compounds were investigated using a scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS), which was operated at 25 kV and 20 s accumulation time was applied. A VARIDEL III elemental analyzer was used to collect the element content of C, H, and N derived from the organic solvents. Thermogravimetric (TG) curves were obtained by using a Shimadzu TGA-50 thermal analyzer, the operating temperature of which ranges from 25 °C to 800 °C with a heating rate of 10 °C min−1 under a nitrogen flow. A SHIMADZU UV-3600 UV-vis-NIR spectrophotometer by using BaSO4 as the reflectance reference coupled with an integrating sphere was used to collect the solid-state UV-vis diffusion reflectance spectra of SOF-20 and SOF-21 materials. The reflectance spectra of SOF-20 and SOF-21 by using the Kubelka–Munk function: F(R) = α/S = (1 − R)2/2R, where R, α, and S are the reflection, absorption and the scattering coefficients, were used to estimate the absorption spectra. A Thermo Nicolet Avatar 6700 Fourier transform-Infrared (FT-IR) spectrometer was used to collect the FT-IR spectra of SOF-20 and SOF-21 from the range of 600 cm−1 to 4000 cm−1.

Electrochemical measurements

A three-electrode system, including a GC disk (4 mm in diameter) as a working electrode, the Ag/AgCl electrode as a reference electrode and the Pt plate as a working electrode, was used to explore the catalytic performance of crystalline SOF-20 and SOF-21. The electrocatalytic activity of both compounds was researched by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) techniques. In order to study the ORR performance, we prepared the SOF-20 decorated electrode through the following steps: firstly, 3 mg crystalline SOF-20 samples and 3 mg carbon black (CB) were mixed and fully ground three times, then, 4 mg of the mixture were added in the mixed solvents of 400 μL water, 100 μL anhydrous ethanol and 20 μL 5% Nafion (5 wt% in propanol, Alfa Aesar), which was denoted as SOF-20/CB, and then sonicated for one hour to make a homogeneous ink; lastly, 7 μL of SOF-20/CB was coated onto the pre-treated GC disk and dried in an evaporator for 24 hours for the following characterization steps. Before the measurement of CV curves (with a scanning rate of 50 mV s−1), highly pure O2 and N2 gases were purged into 0.1 M KOH for 30 min, respectively. LSVs in the O2-saturated 0.1 M KOH aqueous solution were collected at different rotation rates from 625 to 2500 rpm. Before each measurement of LSV at different rotation speeds, highly pure O2 was purged for a fresh electrolyte for about 2 min. The catalytic performance of SOF-21 was also investigated through the above procedures, except that the samples of crystalline SOF-20 were replaced by SOF-21. All the potentials measured reported here were against the Ag/AgCl electrode and relative to the reversible hydrogen electrode (RHE).

Results and discussion

In the presence of the superbase template (herein DBU, DBN and PR), SOF-20 and SOF-21 were successfully synthesized via the solvothermal method. Like other zeolite-type chalcogenides, SOF-20 and SOF-21 were typical anionic inorganic skeletons, which were determined by SC-XRD analysis. The SC-XRD results suggest that both SOF-20 and SOF-21 consist of the same SBUs of T2-InSnS clusters and crystallized in the same space group of Pbca (no. 61) with a comparable cell volume around 11[thin space (1/6-em)]217 Å3 and 12[thin space (1/6-em)]055 Å3, respectively. The crystal data and refinement results of SOF-20 and SOF-21 are listed in Table S1. Since In3+ and Sn4+ ions have similar scattering factors, they can't be accurately distinguished by the X-ray diffraction method. The precise ratios of In/Sn were measured as 1.02 for SOF-20 and 1.86 for SOF-21 by energy dispersive X-ray spectroscopy (EDS) (Fig. S1 and S2). Even though the templated molecules can't be accurately determined due to the high disorder, they are essential to balance the negatively-charged framework and were further ascertained through elemental analysis (EA) (Table S4), Fourier transform-infrared (FT-IR) spectra (Fig. S3 and S4) and thermogravimetric (TG) (Fig. S5 and S6) measurements. The final molecular formulas of SOF-20 and SOF-21 were determined to be [(In2Sn2S8)·1.3(H+-DBN)·0.4(H+-AEP)·0.3(H+-AEAE)] and [(In2.6Sn1.4S8)·0.2(H+-DBU)·1.9(H+-PR)·0.5(H+-AEAE)], respectively.

Secondary building unit and connection mode

The secondary building unit in SOF-20 and SOF-21 is the supertetrahedral T2-InSnS cluster (Fig. 1a), which is exactly the fragment of a cubic zinc blende-type lattice. Each T2 cluster consists of four tetrahedrally-coordinated metal cations (In3+ and Sn4+) and ten bi-coordinated sulfide atoms. The bond lengths of M–S (M = In, Sn) in the T2 cluster are in the range from 2.374(5) Å to 2.448(3) Å, which are reasonable and consistent with the reported values.41–44 In the framework of SOF-20, each T2 cluster is bonded to four adjacent T2 clusters through corner sharing mode with the inter-cluster bridging angles of 107.065°, 108.073°, 108.392° and 128.131° (Fig. 1b). It should be noted that the bridging angles for T2-cluster-based zeolite analogues usually lie in the range of 104° to 110° in the previously reported cases, as displayed in Table 1. The bridging angle in SOF-20 is the maximum inter-cluster bridging angle observed in 3D chalcogenide frameworks. This case also provides new insight into the geometric configuration between T2 clusters. As for SOF-21, each T2 cluster is also connected to four adjacent T2 clusters through sharing a bi-coordinated S2−. However, the inter-cluster bridging angles in this case are in the range from 106.124° to 113.342° (Fig. 1c and d). Therefore, different orientations of SBUs can lead to a new structure.
image file: c9qi01051c-f1.tif
Fig. 1 (a) Ball-and-stick model and the polyhedral diagram of SBU in SOF-20 and SOF-21; (b) each T2 cluster connects to four adjacent T2 clusters observed in SOF-20; (c and d) two kinds of the polyhedral diagram of the T2 cluster connects to four adjacent T2 clusters observed in SOF-21.
Table 1 Structure topology of T2-cluster-based chalcogenide zeolites and zeolite analogues
Compounds M–S–M angle Topology Ref.
Intra-cluster Inter-cluster (T2 as a node)
UCR-20 103°–104° 107°–109° SOD 39
UCR-21 102°–105° 108°–110° dia 39
UCR-22 102°–106° 103°–105° dia 39
UCR-23 103°–104° 104°–106° CrB4 39
CSZ-5 100°–106° 105° bor 32
SCU-36 103°–108° 104° etc 40
SOF-20 102°–105° 107°–128° gsi This work
SOF-21 102°–106° 106°–113° dia This work


Windows and cages

Both compounds reported here are T2-cluster-based 3D frameworks. The assembly of T2 clusters results in three kinds of 24-MR windows observed in SOF-20 (MR = member rings, while metal and sulfur ions are considered) with different aperture sizes: window A (Fig. 2a) is constructed by six T2 clusters with the largest aperture size of 14.05 Å × 9.17 Å (Fig. S7a); window B (Fig. 2b) is also composed of six T2 clusters (aperture: 11.78 Å × 7.62 Å) (Fig. S7b); besides, six T2 clusters are co-assembled into window C (Fig. 2c) with the medium size of 12.88 Å × 10.00 Å (Fig. S7c). Cage α (Fig. 2d and 2e) consists of two window A, two window B and two window C, and the connectivity between cage α leads to the formation of a uniform 3D framework (Fig. 2f). Superbase template molecules are located in these void spaces, and its potential porosity is 58.4% (6551 Å3) of the crystal unit cell volume (11[thin space (1/6-em)]217 Å3), as calculated by the PLATON program.45 Ion exchange was ever confirmed to be an effective method for opening the highly hollow pores of metal-chalcogenide open frameworks.46–48 Unfortunately, N2 adsorption cannot be measured since the original structure of crystalline samples of SOF-20 was observed to collapse after ion exchange with small-sized alkali metal cations (Cs+ used here) (Fig. S8).
image file: c9qi01051c-f2.tif
Fig. 2 (a–c) Three kinds of windows in the structure of SOF-20: window A, window B and window C; (d and e) cage α with two window A and two window B and two window C; (f) 3D framework.

For SOF-21, co-assembly of supertetrahedral T2 clusters leads to the formation of window D (Fig. 3a) (aperture: 12.23 Å × 10.63 Å) (Fig. S9a) and window E (Fig. 3b) (aperture: 14.75 Å × 8.16 Å) (Fig. S9b). Three window D and one window E are further assembled into irregular adamantane cage β with a size around 4.4 Å (represented by a yellow sphere) (Fig. 3c). Cage γ, with the same-sized nanocage as cage β, is constructed by one window D and three window E (Fig. 3d). The interconnection between cage β and cage γ contributes to the twisted T2-based 3D open framework of SOF-21 (Fig. 3e), which is different from the previously reported UCR-21 due to the different orientations and inter-cluster bridging angles. The structure of SOF-21 remains unchanged after the treatment with 1 M CsCl for 24 h (Fig. S10a). Unfortunately, the Cs+@SOF-21 sample experienced structural collapse during the degassing process (Fig. S10b). Therefore, no gas adsorption experiment was performed.


image file: c9qi01051c-f3.tif
Fig. 3 (a and b) Two kinds of windows in the structure of SOF-21: window D and window E; (c) cage β with three window D and one window E; (d) cage γ with one window D and three window E; (e) 3D framework.

Structure topology

During the past two decades, many open-framework chalcogenides with variable structure topologies have been obtained.49–51 However, novel structure topologies based on supertetrahedral chalcogenide clusters are quite limited. We herein enriched the topological family members of chalcogenide frameworks by a rare 3D gsi net. When tetrahedral-shaped T2 clusters are treated as nodes, SOF-20 can be simplified into a non-interpenetrated gsi net (Fig. 4a and Fig. S11) with the vertex symbol of {6·62·6·62·6·62}. To the best of our knowledge, such a topological type (gsi) is reported in chalcogenide-based zeolite analogues for the first time. In comparison with the reported Si- or Ge-based structure (there are only two cases of the gsi net based on inorganic components so far),52,53 the void space of the crystal unit cell volume dramatically increases from 0% to 58.4% (Fig. S12) by replacing Si or Ge atoms with supertetrahedral T2 clusters. This analysis further emphasizes the significant role of Tn clusters for enlarging the guest-accessible spaces of frameworks and providing more opportunities for their porosity-related research studies.
image file: c9qi01051c-f4.tif
Fig. 4 (a) 3D gsi net of SOF-20 when T2 clusters are treated as nodes; (b) 3D twisted dia net of SOF-21 when T2 clusters are treated as nodes.

In the framework of SOF-21, while each supertetrahedral T2 cluster is treated as a node, the framework of SOF-21 can be simplified into a twisted dia net (Fig. 4b and Fig. S13). The extra-framework space of SOF-21 is calculated to be 60.2%, which is a little larger than that of previously documented UCR-2139 and CPM-12134 (both UCR-21 and CPM-121 are T2-cluster-based single dia frameworks). The successful preparation of such twisted structures provides more possibilities for constructing diverse tetrahedral chalcogenide cluster-based frameworks and expanding their potential applications.

PXRD and optical absorption

The correctness of the as-solved structures and phase purity were further confirmed by PXRD measurement. As illustrated in Fig. S14 and S15, the PXRD patterns of SOF-20 and SOF-21 matched well with the simulated ones from the analyses of single-crystal structures, and no additional diffraction peaks were found. In addition, the synthesized samples could keep their structures unchanged after the treatment with common solvents, such as H2O and ethanol (Fig. S16 and S17), and even after exposure to air for three months (Fig. S18 and S19).

The semiconducting properties of the as-synthesized SOF-20 and SOF-21 were characterized by solid-state UV-vis diffuse reflectance spectra. As shown in Fig. 5, the optical band gaps of SOF-20 and SOF-21 were measured as 3.25 eV and 3.07 eV, respectively, as calculated from the extrapolation of the linear part of the [F(R)]2 plot. Although SOF-20 and SOF-21 possess the same components and SBUs, different band gaps can be observed. This was probably caused by the different metal ratios of In/Sn in them.


image file: c9qi01051c-f5.tif
Fig. 5 Tauc plots of SOF-20 and SOF-21 derived from the UV-vis diffuse-reflectance spectra.

Electrocatalytic properties

The electrocatalytic oxygen reduction reaction (ORR), considered as a promising renewable energy technology, was investigated for catalysts of SOF-20 and SOF-21. Due to the successful introduction of Sn4+ ions into zeolite-like frameworks, both SOF-20 and SOF-21 show ORR activities.54 The ORR activities of SOF-20/CB- and SOF-21/CB-decorated glassy carbon electrodes were calculated using cyclic voltammetry (CV) in 0.1 M KOH solution. As shown in Fig. 6a and b, the featureless current could be observed in N2-saturated KOH solution. However, both SOF-20/CB- and SOF-21/CB-decorated electrodes immersed in O2-saturated solution exhibited a distinct reduction peak at the same potential of around 0.73 V (vs. RHE) but with different current densities of 0.82 mA cm−2 and 0.77 mA cm−2, respectively. It means SOF-20 and SOF-21 could act as potential catalysts for the electrocatalytic ORR.
image file: c9qi01051c-f6.tif
Fig. 6 (a) CV curves of SOF-20/CB-decorated electrodes in N2- and O2-saturated 0.1 M KOH solution; (b) CV curves of SOF-21/CB-decorated electrodes in N2- and O2-saturated 0.1 M KOH solution; (c) LSVs at different rotation speeds of SOF-20/CB-decorated electrodes; (d) LSVs at different rotation speeds of SOF-21/CB-decorated electrodes.

The kinetics of the electrochemical catalytic ORR for SOF-20/CB and SOF-21/CB was further studied from the linear sweep voltammograms (LSVs) recorded at different rotation rates of the electrode. As illustrated in Fig. 6c and d, the current densities of SOF-20/CB- and SOF-21/CB-decorated RDE were gradually increased by adjusting the rotation rate from 625 rpm to 2500 rpm. Besides, the corresponding Koutecky–Levich (K–L) plots21 were further calculated over the potential range from 0.2 V to 0.5 V, and the K–L plots of both compounds showed good linearity (Fig. S20 and S21). The electron-transfer number of SOF-20/CB was calculated to be 2.83 from the K–L equation, which was between 2 and 4, indicating that the ORR occurring in this electrocatalyst adopted a mixed 2-electron/4-electron pathway. Identically, the catalyst of SOF-21 also adopted a mixed pathway in the ORR process with the electron-transfer number determined to be 2.58.

Conclusions

In conclusion, we successfully prepared two metal-chalcogenide open frameworks, namely SOF-20 and SOF-21. Both compounds consist of the same supertetrahedral T2-InSnS clusters as SBUs, which further assemble into 3D frameworks with gsi and twisted dia nets, respectively. Notably, the largest bridging angle between supertetrahedral T2 clusters was observed in SOF-20 for the first time, and this case fills the blank of the gsi net in the family of metal-chalcogenide open frameworks. Furthermore, it is also believed to be the first highly-open gsi framework based on inorganic components. SOF-21 represents a twisted dia net. This work clearly demonstrates that tuning the inter-cluster bridging angle is one of the key points to extend the structure topologies of cluster-based chalcogenide zeolite analogues.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

We acknowledge the National Natural Science Foundation of China (21671142 and 21875150), the Jiangsu Province Natural Science Fund for Distinguished Young Scholars (BK20160006), the Project of Scientific and Technologic Infrastructure of Suzhou (SZS201905) and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

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Footnote

Electronic supplementary information (ESI) available: PXRD patterns, EDS, IR, TGA and other structure figures. CCDC 1936918 and 1936907. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9qi01051c

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