An Unusual Metal Chalcogenide Zeolitic Framework Built from the

Dec 4, 2017 - ABSTRACT: Reported here is a new metal chalcogenide semiconductor with the double-interpenetrated zeolitic nabesite framework, which is ...
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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

An Unusual Metal Chalcogenide Zeolitic Framework Built from the Extended Spiro‑5 Units with Supertetrahedral Clusters as Nodes Wei Wang,†,‡ Xiang Wang,† Dandan Hu,† Huajun Yang,† Chaozhuang Xue,† Zhien Lin,‡ and Tao Wu*,† †

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China College of Chemistry, Sichuan University, Chengdu 610064, China

‡

S Supporting Information *

built from the units of a 3-ring, which even prefer to fuse into large-sized supertetrahedral clusters, such as Tn (n indicates the metal layer of the cluster) via an edge-sharing mode, rather than a vertex-sharing mode like spiro-5.20 However, it is very interesting that the extended 3-ring and extended spiro-5 unit built from supertetrahedral Tn clusters can still be observed in some metal chalcogenide zeolitic frameworks when clusters are treated as nodes.21 This observation naturally inspired us to design and construct metal chalcogenide frameworks with cluster-based 3ring or spiro-5 units because these larger-sized secondary building units are more desirable for targeting larger pores or more void space.12,22 Unfortunately, reported zeolitic topologies, such as ABW,23 SOD,24,25 BCT,24,26 and quartz,27,28 are usually built from 4- and 6-rings when clusters are treated as nodes.29−32 Few topologies with the extended 3-ring or spiro-5 units were observed.21 This is possibly because the commonly used protonated organic amine molecules with relatively large size are hardly used to balance the high density of negative charges concentrating upon the small area of the extended 3-ring.33 To address this issue, a special strategy was provided to use smallsized alkali-metal ions with a high density of positive charge as countercations for balancing the negative charge in the extended 3-ring, as exampled by two pure inorganic chalcogenide frameworks, ICF-24 (InSSe-Na) and ICF-25 (InS-SrCaLi), built by the extended spiro-5 units composed of T2 clusters (Figures S1 and S2).21 Unfortunately, the diversity of such structures is limited by the types of alkali-metal species. To maintain the various organic amines as templates for the construction of zeolitic networks with the extended 3-ring composed of a big-sized Tn cluster, a feasible strategy is to decrease the negative charge of Tn clusters by introducing highvalent metal-like Ge4+ and Sn4+.34−40 In this way, the extended 3ring can be built in organically templated metal chalcogenides by larger-sized Tn clusters, such as T3 and T4. Unfortunately, these extended 3-rings still prefer to fuse together into supersupertetrahedral cluster Tp,q (four Tp supertetrahedral clusters assembled into a self-closed Tq cluster),25,41,42 instead of the extended spiro-5 units. Herein we report a new organically templated metal chalcogenide zeolitic framework built by the extended 3-rings with T3-InSnS supertetrahedral clusters as structural nodes. Interestingly, such a T3-InSnS cluster-based 3-ring subsequently

ABSTRACT: Reported here is a new metal chalcogenide semiconductor with the double-interpenetrated zeolitic nabesite framework, which is constructed by the rare extended spiro-5 units with supertetrahedral clusters serving as building units. Different from the TO4-based simple spiro-5 unit frequently observed in oxide-based zeolites, the extended spiro-5 unit composed of five supertetrahedral T3-InSnS clusters is for the first time observed in the family of open-framework metal chalcogenides. Such secondary building units finally assemble into a rare NAB topological framework with large external space. In addition, the title semiconductor material also displays good properties in photocurrent response and electrocatalytic oxygen reduction reaction.

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luminosilicates, as one family of crystalline microporous zeolite materials, have shown extensive applications in catalysis, gas sorption, and ion exchange.1−5 Topological features in zeolites are generally accepted to play a vital role in directing such established and/or newly emerging applications. Among all reported zeolite structures, one of the extremely desirable topological features is a 3-ring, in which there are three tetrahedral atoms, or T atoms, by ignoring the bridging units.6,7 This is because a 3-ring is inclined to lead to a superior structure with large pores and low framework density. Unfortunately, a 3-ring hardly occurs in the family of aluminosilicates because of the large ring strain caused by a large Si−O−(Si/Al) angle (∼145°). While using large-sized T atoms such as Ge with a small bond angle of Ge−O−Ge (∼130°), the ring strain can be effectively decreased. Therefore, several germinates with a 3-ring were created.8−11 Of particular interest is the formation of the spiro-5 unit by fusing two 3-rings with the common central tetrahedron. As one of the main existing forms of a 3-ring, the spiro-5 unit has contributed to the formation of many zeolites with high 3-ring densities and rarely odd-ring windows, which can be exemplified by BOZ,12 VPI-7,13 PKU-9,10 ASU-15,14 GaGeO-CJ-63,9 JU-64,15 LSJ-10,16 etc. (Table S1). In recent years, there is increasing interest in integrating semiconductor characteristics into porous zeolites.17 This triggers great attention to the synthetic design of zeolite− analogous metal chalcogenide frameworks.17−19 Different from the traditional oxide-based zeolites, in which 3-ring units are rarely observed, metal chalcogenide frameworks are commonly © XXXX American Chemical Society

Received: December 4, 2017

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DOI: 10.1021/acs.inorgchem.7b03057 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry forms the rare extended spiro-5 unit by sharing the terminal S atoms of clusters. The spiro-5 units continuously assemble into a zeolitic framework with double-interpenetrated NAB topology. To the best of our knowledge, this is the first case with a NAB net observed in metal chalcogenide open frameworks. Pale-yellow cubiclike crystals of In8.5Sn1.5S18·4.5H+-DBU were prepared by the solvothermal reaction of indium, stannous chloride, sulfur powder, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), piperidine (PR), and distilled water at 190 °C for 8 days with a yield of 19.1% based on indium (for the detail synthesis method, see the Supporting Information, SI). Some control experiments demonstrated that a superbase organic amine (DBU) plays an important role in the formation of the title compound, so it is named as SOF-27 (SOF = superbase-oriented chalcogenide framework). Although the PR molecules are not observed in the final structure, they are essential for obtaining the resulting crystals. Single-crystal X-ray diffraction (SCXRD) analysis indicated that SOF-27 crystallizes in the tetragonal system with the space group I41/a (No. 88) (Table S2). It was difficult to differentiate the absolute sites of In3+ and Sn4+ in the structure through X-ray diffraction data because of their similar scattering factors. The Sn/In ratio was measured as 0.176 by inductively coupled plasma mass spectrometry results, which is also close to the energy-dispersive spectrometry results (Figure S3). A weight loss of 31.7% is attributed to the carbonization of template molecules between 250 and 450 °C in a thermogravimetric analysis (TGA) experiment under N2 conditions, which is similar to the weight ratio (28.5%) of the template in the formula (Figure S4). SOF-27 was not soluble in water or other organic solvents, and its phase purity was also confirmed by powder X-ray diffraction (PXRD; Figure S5). Generally speaking, metal chalcogenide frameworks based on the T3 cluster built by trivalent metal ions have relatively high negative charge. For example, the T3 cluster of [Ga10S18]6− possesses 0.60− charges per tetrahedron unit.28 In SOF-27, the primary building units (PBUs) are T3-InSnS with a metal composition of In and Sn, which has an average charge of 0.45− charge per tetrahedron unit. It is noted that tetravalent Sn ions in the T3 cluster are useful to lessen the negative charge and facilitate the global charge balance. This also occurred in SOF2.41 In addition, to better understand the charge distribution on the metal site in T3-InSnS cluster, their bond valence sums (BVSs) were determined. As listed in Table S3, the BVSs of 13 metal sites (originally treated as In) in an asymmetric unit range from 3.075 to 3.294. By contrast, the BVSs of the In sites in the T3-InS cluster of UCR-728 range from 3.084 to 3.132 (Table S4). Obviously, the metal sites in T3-InSnS of SOF-27 show higher values of BVSs because some In sites are occupied by tetravalent Sn metals. Although the metal sites of In and Sn cannot be precisely distinguished, we believe that the Sn ions are likely to occupy the vertex of supertetrahedral T3-InSnS clusters. This is because the negative charge at the corner of the cluster is more difficult to balance with protonated DBU molecules than that at the edge or face of the cluster because of the narrow space. More interestingly, the fusion of five T3-InSnS PBUs gives rise to the extended spiro-5 unit with a double 3-ring by sharing the terminal μ2-S2− (Figure 1). As a commonly existing form of the 3ring in an oxide-based zeolite, the spiro-5 unit has been observed in a few germinates. However, so far, there are only two cases reported in cluster-based chalcogenide frameworks that are constructed by the extended spiro-5 units with the T2 cluster as nodes (Table S5). The extended spiro-5 units based on the T3 cluster in SOF-27 connect each other and lead to an open-

Figure 1. Extended spiro-5 unit built by the fusion of double 3-rings in SOF-27.

framework structure with three-dimensional channels (Figure 2a). When T3-InSnS clusters are treated as 4-connected nodes,

Figure 2. (a) 3D framework structure of SOF-27 viewed from the a axis: green, In or Sn atom; pink, S atom. (b) NAB topology of SOF-27 by considering each T3-InSnS cluster as a node. The 9-ring window is highlighted in red. Only one set of superlattices is shown for clarity.

the structure of SOF-27 can be simplified to a 2-foldinterpenetrated NAB net (Figures 2b and S6) with the point symbol of {3.4.82.92}4{32.94}. Along the a or b axis, SOF-27 represents a 9-ring channel (27-ring treating every metal site as a node) with a channel window size of approximately 16.4 Å × 20.6 Å, which is considered to be a rare example of odd-ring zeolite topology (Figure S7). The structure of SOF-27 can also be considered as a pillar-layer-type structure consisting of a 3connected layered net (fes) including 4- and 8-rings and a spiro-5 pillar (Figure S8). In a comparison with a natural zeolite nabesite,43 Na2BeSi4O10·4H2O (the first and only NAB topology framework before this work), the axis length of the unit cell as well as the aperture size in SOF-27 are enlarged about 3 times because the size of the supertetrahedral T3-InSnS cluster is approximately 3 times larger than that of the BeO4 or SiO4 units in nabesite (Figure S9), which shows the advantage of a supertetrahedral Tn cluster for expanding the pore size of the framework. Moreover, the crystal shape of SOF-27 observed under an optical microscope or a scanning electron microscope is similar to that of a naturally grown nabesite because of the same topology structure (Figure S10). Similar to the majority of other open-framework metal chalcogenides, the protonated organic amine molecules in SOF-27 disorderedly locate within the pore of the framework and are not capable of being determined exactly through the SCXRD technique. The large void space in interclusters is calculated to be 64.5% with the program PLATON.44 The solidstate UV−vis diffuse-reflectance spectrum of SOF-27 was also measured. The optical wide band gap was calculated to be 3.2 eV by using the Kubelka−Munt method (Figure 3), demonstrating that SOF-27 is a broad-band semiconductor. To further confirm B

DOI: 10.1021/acs.inorgchem.7b03057 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

ions (Figure S11). As a result, SOF-27 with In and Sn domains had a good ability for transferring peroxide to the final OH− group. In summary, we for the first time introduce the extended spiro5 units into open-framework metal chalcogenides. Such an extended spiro-5 unit is built by supertetrahedral T3-InSnS clusters and finally self-assembled into a double-interpenetrated zeolitic framework with NAB topology. The title metal chalcogenide semiconductor displays a good photocurrent response and ORR electrocatalytic properties. Notably, targeting the extended spiro-5 units is based on the successful strategy of introducing high-valent metal ions into the T3-InS cluster, which may hold promise for the creation of other extended spiro-5 units with a large-sized Tn cluster and other open-framework metal chalcogenides with large void space.

Figure 3. (a) Solid-state UV−vis diffuse-reflectance spectrum of SOF27. Inset: Optical image of the crystals. (b) Photoresponse under pulsed illumination at 0 V potential.

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the semiconductor characteristics of SOF-27, the photocurrent response property was also investigated. The SOF-27-modified indium−tin oxide photoelectrode displays a rapid photocurrent response and good reproducibility and stability at the start and end of the visible-light illumination without biased potential (inset of Figure 3). Electrocatalytic oxygen reduction reaction (ORR) is one of the keys to the realization of renewable applications. Although the ORR properties of transition-metal chalcogenides have been performed,45,46 few examples focused on the ORR property of metal chalcogenides containing In and Sn elements. The ORR properties of a SOF-27/carbon black (CB)-modified glassy carbon electrode were evaluated using cyclic voltammetry (CV) in 1 M KOH. The CV curves in Figure 4a exhibit an obvious

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b03057. Experimental details, SCXRD data, PXRD, elemental analysis, additional structural figures, UV−vis absorption spectra, and TGA (PDF) Accession Codes

CCDC 1581624 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Xiang Wang: 0000-0001-7354-6491 Huajun Yang: 0000-0002-4664-4042 Zhien Lin: 0000-0002-5897-9114 Tao Wu: 0000-0003-4443-1227

Figure 4. (a) CV curves of SOF-27/CB in a N2- and O2-saturated 1.0 M KOH solution. (b) RDE voltammetry at different rotation rates of SOF27/CB. Inset: Corresponding K−L plots at different potentials.

Notes

The authors declare no competing financial interest.

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reduction peak for the sample in an O2-saturated solution, whereas no perceptible voltammetric current was observed in the presence of N2. Rotating-disk-electrode (RDE) voltammetry was further performed to study the kinetics of the electrochemical catalytic ORR for SOF-27/CB. As shown in Figure 4b, the current density was stepwise enhanced by increasing the rotating rate. The corresponding Koutecky−Levich (K−L) plots had good linearity over the potential range from 0.30 to 0.60 V. The electron-transfer number of SOF-27/CB was calculated to be about 2.8 from the K−L equation, and the peroxide species yield was about 60% using a rotating ring disk electrode as the working electrode (Figure S11), indicating that the ORR occurring in the material adopted a mixed 2-electron/4-electron pathway. To understand the role of SOF-27 in SOF-27/CB, the contrast experiment of using only CB as the catalyst was carried out. Unfortunately, the CB catalyst showed an electron-transfer number of 2.2 and a peroxide species yield of 90%. Such 2electron progress as well as a high peroxide species yield demonstrates that CB cannot catalyze peroxide into hydroxide

ACKNOWLEDGMENTS This work was supported by National Natural Science Foundation of China (21671142), Jiangsu Province Natural Science Fund for Distinguished Young Scholars (BK20160006), and Priority Academic Program Development of Jiangsu Higher Education Institutions.

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REFERENCES

(1) Lee, Y.; Vogt, T.; Hriljac, J. A.; Parise, J. B.; Hanson, J. C.; Kim, S. J. Non-Framework Cation Migration and Irreversible Pressure-Induced Hydration in a Zeolite. Nature 2002, 420, 485−489. (2) Davis, M. E. The Quest for Extra-Large Pore, Crystalline Molecular Sieves. Chem. - Eur. J. 1997, 3, 1745−1750. (3) Yang, H.; Luo, M.; Luo, L.; Wang, H.; Hu, D.; Lin, J.; Wang, X.; Wang, Y.; Wang, S.; Bu, X.; Feng, P.; Wu, T. Highly Selective and Rapid Uptake of Radionuclide Cesium Based on Robust Zeolitic Chalcogenide Via Stepwise Ion-Exchange Strategy. Chem. Mater. 2016, 28, 8774− 8780.

C

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Inorganic Chemistry (4) Lin, Q.; Bu, X.; Mao, C.; Zhao, X.; Sasan, K.; Feng, P. Mimicking High-Silica Zeolites: Highly Stable Germanium- and Tin-Rich ZeoliteType Chalcogenides. J. Am. Chem. Soc. 2015, 137, 6184−6187. (5) Wang, W.; Yang, H.; Luo, M.; Zhong, Y.; Xu, D.; Wu, T.; Lin, Z. A 36-Membered Ring Metal Chalcogenide with a Very Low Framework Density. Inorg. Chem. 2017, 56, 14730−14733. (6) Estermann, M.; McCusker, L. B.; Baerlocher, C.; Merrouche, A.; Kessler, H. A Synthetic Gallophosphate Molecular Sieve with a 20Tetrahedral-Atom Pore Opening. Nature 1991, 352, 320−323. (7) Huo, Q.; Xu, R.; Li, S.; Ma, Z.; Thomas, J. M.; Jones, R. H.; Chippindale, A. M. Synthesis and Characterization of a Novel Extra Large Ring of Aluminophosphate JDF-20. J. Chem. Soc., Chem. Commun. 1992, 875−876. (8) Jiang, J.; Yu, J.; Corma, A. Extra-Large-Pore Zeolites: Bridging the Gap between Micro and Mesoporous Structures. Angew. Chem., Int. Ed. 2010, 49, 3120−3145. (9) Han, Y.; Li, Y.; Yu, J.; Xu, R. A Gallogermanate Zeolite Constructed Exclusively by Three-Ring Building Units. Angew. Chem., Int. Ed. 2011, 50, 3003−3005. (10) Su, J.; Wang, Y.; Wang, Z.; Lin, J. PKU-9: An Aluminogermanate with a New Three-Dimensional Zeolite Framework Constructed from CGS Layers and Spiro-5 Units. J. Am. Chem. Soc. 2009, 131, 6080−6081. (11) Chen, F.-J.; Xu, Y.; Du, H.-B. An Extra-Large-Pore Zeolite with Intersecting 18-, 12-, and 10-Membered Ring Channels. Angew. Chem., Int. Ed. 2014, 53, 9592−9596. (12) Littlefield, B. T. R.; Weller, M. T. Lightweight Nanoporous Metal Hydroxide-Rich Zeotypes. Nat. Commun. 2012, 3, 1114. (13) Röhrig, C.; Gies, H.; Marler, B. Rietveld Refinement of the Crystal Structure of the Synthetic Porous Zincosilicate VPI-7. Zeolites 1994, 14, 498−503. (14) Li, H.; Eddaoudi, M.; Plévert, J.; O’Keeffe, M.; Yaghi, O. M. Ge2ZrO6F2·(H2DAB)H2O: A 4-Connected Microporous Material with “Bow Tie” Building Units and an Exceptional Proportion of 3-Rings. J. Am. Chem. Soc. 2000, 122, 12409−12410. (15) Xu, Y.; Li, Y.; Han, Y.; Song, X.; Yu, J. A Gallogermanate Zeolite with Eleven-Membered-Ring Channels. Angew. Chem., Int. Ed. 2013, 52, 5501−5503. (16) Armstrong, J. A.; Weller, M. T. Beryllosilicate Frameworks and Zeolites. J. Am. Chem. Soc. 2010, 132, 15679−15686. (17) Fér ey, G. Supertetrahedra in Sulfides: Matter against Mathematical Series? Angew. Chem., Int. Ed. 2003, 42, 2576−2579. (18) Zheng, N.; Bu, X.; Vu, H.; Feng, P. Open-Framework Chalcogenides as Visible-Light Photocatalysts for Hydrogen Generation from Water. Angew. Chem., Int. Ed. 2005, 44, 5299−5303. (19) Lin, J.; Dong, Y.; Zhang, Q.; Hu, D.; Li, N.; Wang, L.; Liu, Y.; Wu, T. Interrupted Chalcogenide-Based Zeolite-Analogue Semiconductor: Atomically Precise Doping for Tunable Electro-/Photoelectrochemical Properties. Angew. Chem., Int. Ed. 2015, 54, 5103−5107. (20) Bu, X.; Zheng, N.; Feng, P. Tetrahedral Chalcogenide Clusters and Open Frameworks. Chem. - Eur. J. 2004, 10, 3356−3362. (21) Zheng, N.; Bu, X.; Feng, P. Synthetic Design of Crystalline Inorganic Chalcogenides Exhibiting Fast-Ion Conductivity. Nature 2003, 426, 428−432. (22) Yu, J.; Xu, R. Rational Approaches toward the Design and Synthesis of Zeolitic Inorganic Open-Framework Materials. Acc. Chem. Res. 2010, 43, 1195−1204. (23) Cahill, C. L.; Parise, J. B. Synthesis and Structure of MnGe4S10· (C6H14N2)·3H2O: A Novel Sulfide Framework Analogous to Zeolite Li-A(BW). Chem. Mater. 1997, 9, 807−811. (24) Li, H.; Laine, A.; O’Keeffe, M.; Yaghi, O. M. Supertetrahedral Sulfide Crystals with Giant Cavities and Channels. Science 1999, 283, 1145−1147. (25) Zheng, N.; Bu, X.; Wang, B.; Feng, P. Microporous and Photoluminescent Chalcogenide Zeolite Analogs. Science 2002, 298, 2366−2369. (26) Bu, X.; Zheng, N.; Wang, X.; Wang, B.; Feng, P. ThreeDimensional Frameworks of Gallium Selenide Supertetrahedral Clusters. Angew. Chem., Int. Ed. 2004, 43, 1502−1505.

(27) Li, H.; Kim, J.; Groy, T. L.; O’Keeffe, M.; Yaghi, O. M. 20 Å Cd4In16S3514‑ Supertetrahedral T4 Clusters as Building Units in Decorated Cristobalite Frameworks. J. Am. Chem. Soc. 2001, 123, 4867−4868. (28) Zheng, N.; Bu, X.; Feng, P. Nonaqueous Synthesis and Selective Crystallization of Gallium Sulfide Clusters into Three-Dimensional Photoluminescent Superlattices. J. Am. Chem. Soc. 2003, 125, 1138− 1139. (29) Wang, C.; Li, Y.; Bu, X.; Zheng, N.; Zivkovic, O.; Yang, C.-S.; Feng, P. Three-Dimensional Superlattices Built from (M4In16S33)10‑ (M = Mn, Co, Zn, Cd) Supertetrahedral Clusters. J. Am. Chem. Soc. 2001, 123, 11506−11507. (30) Bu, X.; Zheng, N.; Li, Y.; Feng, P. Pushing up the Size Limit of Chalcogenide Supertetrahedral Clusters: Two- and Three-Dimensional Photoluminescent Open Frameworks from (Cu5In30S54)13‑ Clusters. J. Am. Chem. Soc. 2002, 124, 12646−12647. (31) Wang, C.; Bu, X.; Zheng, N.; Feng, P. Indium Selenide Superlattices from (In10Se18)6‑ Supertetrahedral Clusters. Chem. Commun. 2002, 1344−1345. (32) Wang, L.; Wu, T.; Bu, X.; Zhao, X.; Zuo, F.; Feng, P. Coassembly between the Largest and Smallest Metal Chalcogenide Supertetrahedral Clusters. Inorg. Chem. 2013, 52, 2259−2261. (33) Feng, P.; Bu, X.; Zheng, N. The Interface Chemistry between Chalcogenide Clusters and Open Framework Chalcogenides. Acc. Chem. Res. 2005, 38, 293−303. (34) Han, X.; Xu, J.; Wang, Z.; Liu, D.; Wang, C. A Hybrid Linkage Mode between T2,2 and T3 Selenide Clusters. Chem. Commun. 2015, 51, 3919−3922. (35) Zhang, X.-M.; Sarma, D.; Wu, Y.-Q.; Wang, L.; Ning, Z.-X.; Zhang, F.-Q.; Kanatzidis, M. G. Open-Framework Oxysulfide Based on the Supertetrahedral [In4Sn16O10S34]12‑ Cluster and Efficient Sequestration of Heavy Metals. J. Am. Chem. Soc. 2016, 138, 5543−5546. (36) Du, C.-F.; Li, J.-R.; Zhang, B.; Shen, N.-N.; Huang, X.-Y. From T2,2@Bmmim to Alkali@T2,2@Bmmim Ivory Ball-Like Clusters: Ionothermal Syntheses, Precise Doping, and Photocatalytic Properties. Inorg. Chem. 2015, 54, 5874−5878. (37) Zhou, J.; Xiao, H.; Zou, H.-H.; Liu, X. A Novel 2-D Mn Selenidostannate(IV) Incorporating High-Nuclear Mn Clusters with Spin Canting Behavior. Dalton Trans. 2017, 46, 16009−16013. (38) Yue, C.-Y.; Lei, X.-W.; Feng, L.-J.; Wang, C.; Gong, Y.-P.; Liu, X.Y. [Mn2Ga4Sn4S20]8‑ T3 Supertetrahedral Nanocluster Directed by a Series of Transition Metal Complexes. Dalton Trans. 2015, 44, 2416− 2424. (39) Yue, C.-Y.; Lei, X.-W.; Ma, Y.-X.; Sheng, N.; Yang, Y.-D.; Liu, G.D.; Zhai, X.-R. [TM(en)3][SnSb4S9] (TM = Ni, Co): 3d Chiral Framework of Mixed Main-Group Metals and [Mn(dien)2]2Sb4S9: 1d Chains with Mixed-Valent Sb Centers. Cryst. Growth Des. 2014, 14, 101−109. (40) Lei, X.-W.; Yang, M.; Xia, S.-Q.; Liu, X.-C.; Pan, M.-Y.; Li, X.; Tao, X.-T. Synthesis, Structure and Bonding, Optical Properties of Ba4MTrQ6 (M = Cu, Ag; Tr = Ga, In; Q = S, Se). Chem. - Asian J. 2014, 9, 1123−1131. (41) Wang, W.; Yang, H.; Xue, C.; Luo, M.; Lin, J.; Hu, D.; Wang, X.; Lin, Z.; Wu, T. The First Observation on Dual Self-Closed and Extended Assembly Modes in Supertetrahedral T3 Cluster Based OpenFramework Chalcogenide. Cryst. Growth Des. 2017, 17, 2936−2940. (42) Li, H.; Kim, J.; O’Keeffe, M.; Yaghi, O. M. [Cd16In64S134]44−: 31 Å Tetrahedron with a Large Cavity. Angew. Chem., Int. Ed. 2003, 42, 1819− 1821. (43) Petersen, O. V.; Giester, G.; Brandstätter, F.; Niedermayr, G. Nabesite, Na2BeSi4O10·4H2O, a New Mineral Species from the Ilmaussaq Alkaline Complex, South Greenland. Can. Mineral. 2002, 40, 173−181. (44) Spek, A. Platon, an Integrated Tool for the Analysis of the Results of a Single Crystal Structure Determination. Acta Crystallogr. Sect, A 1990, 46, C34. (45) Wang, J.; Li, L.; Chen, X.; Lu, Y.; Yang, W. Monodisperse Cobalt Sulfides Embedded within Nitrogen-Doped Carbon Nanoflakes: An D

DOI: 10.1021/acs.inorgchem.7b03057 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry Efficient and Stable Electrocatalyst for the Oxygen Reduction Reaction. J. Mater. Chem. A 2016, 4, 11342−11350. (46) Wang, H.; Liang, Y.; Li, Y.; Dai, H. Co1−xS-Graphene Hybrid: A High-Performance Metal Chalcogenide Electrocatalyst for Oxygen Reduction. Angew. Chem., Int. Ed. 2011, 50, 10969−10972.

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