Three-Dimensional Superlattices Based on Unusual Chalcogenide

Communication Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX

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Three-Dimensional Superlattices Based on Unusual Chalcogenide Supertetrahedral In−Sn−S Nanoclusters Wei Wang,†,‡ Xiang Wang,† Jiaxu Zhang,† Huajun Yang,† Min Luo,† 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, Sichuan 610064, China

‡

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S Supporting Information *

by tuning the size and shape of the supertetrahedral clusters. However, the types of supertetrahedral clusters are still limited. There are only five members in the Tn-type cluster (T2−T6), two in the Pn-type cluster (P1 and P2), and three in the Cn-type cluster (C1−C3).8 Furthermore, Pn and Cn clusters often exist in the isolated form, which just leads to the molecular superlattices rather than open frameworks.8f,9 It is desirable to create new families of supertetrahedral clusters, which are expected as new types of SBUs to enrich the cluster-based chalcogenide open frameworks. Different from Tn-, Cn-, and Pn-type of clusters, the TOn cluster (where “T” denotes tetrahedral and “O” denotes octahedral) belongs to a new type of supertetrahedral cluster, which can potentially serve as a SBU candidate to build clusterbased chalcogenide open frameworks. Unfortunately, there was only one case of TO2-based metal chalcogenide (denoted as OCF-41 with the framework formula of [In40S66(H2O)8]) reported earlier,10 in which the fascinating TO2 cluster ([In38S65(H2O)6]16−) only assembled into a 2D-layered structure rather than a 3D open framework. This is possibly caused by the fact that it is difficult to balance the highly negative charge of the TO2-InS cluster (−16) by the typically used templates, which further limits the possibility of high-dimensional coassembly because the charge and size matching are two vital factors in the assembly chemistry. A reasonable design strategy to address this issue is to reduce the negative charge of the TO2-InS cluster by introducing a high-valent metal ion (such as Ge4+ and Sn4+). In fact, by virtue of such a synthetic strategy, we ever successfully prepared the first 3D superlattice with a supersupertetrahedral T3,2-InSnS cluster11 as a SBU and a zeolite-analogous chalcogenide framework with a T3-InSnSbased spiro-5 unit (donated as lov in zeolite) as a SBU.12 Here, we report two new metal-chalcogenide-based open frameworks composed of supertetrahedral TO2 clusters with the In−Sn−S compositions. The coassembly of such TO2-InSnS clusters leads to double- and triple-interpenetrated dia nets, respectively, when TO2 clusters are treated as the nodes. Also, this is the first observation of a 3D coassembly of supertetrahedral TO2 clusters. Besides, they also display good performance on the electrocatalytic oxygen reduction reaction (ORR). The title In−Sn−S superlattices were prepared by the solvothermal reaction of indium powder, stannous chloride,

ABSTRACT: Reported here are two novel metal chalcogenide superlattices built from unusual supertetrahedral TO2-InSnS clusters. With regard to only one previously reported case of a TO2-InS-based 2D-layered structure, such a combination of In−Sn−S components is thought to be reasonable for leading to the first observation of 3D superlattices based on TO2-InSnS clusters. Besides, these title semiconducting materials also display good performance on the electrocatalytic oxygen reduction reaction.

S

earching for novel crystalline open-framework materials is always a hot topic in materials science, which is boosted by the strong incentive related to the vital roles in various applications, such as adsorption, separation, catalysis, ion exchange, etc.1 However, it still remains an elusive goal in designing a priori crystalline open frameworks with the specified structure and function. So far, one of the most attractive approaches on the targeted open frameworks is to realize the coassembly of secondary build units (SBUs) with well-defined function and/or unique structure characteristics.2 Such an idea was ever applied in germanate systems based on oxogermanium clusters, such as Ge7, Ge9, Ge10, and [email protected] Furthermore, great progress has been made in the field of metal−organic frameworks (MOFs) by virtue of metal-oxide-based building blocks as SBUs or synthetic modules, which is beneficial to designing and predicting the resulting MOF structure.4 Recently, great interest has been aroused in the design of crystalline metal-chalcogenide-based open-framework materials that naturally integrate the porosity and semiconducting property. Such interesting and intriguing semiconducting materials present some extensive applications in gas adsorption, ion exchange, photoluminescence, electrochemiluminescence, and photo/electrocatalysis.5 It is straightforward to tailor these functionalities by choosing SBUs with different components and structure characteristics. So far, metal chalcogenide supertetrahedral clusters, such as basic (Tn), penta (Pn), and capped (Cn) series, are superb SBU candidates to construct the chalcogenide-based open frameworks because of the inherent tetrahedral coordination modes.6 Various of 4-connected zeolite-analogous frameworks (such as ABW, SOD, BCT, and quartz) and 3,4-connected frameworks (such as cubic C3N4 and boracite) have been reported.7 The structural diversity and functional versatility of such open frameworks could be enriched © XXXX American Chemical Society

Received: September 10, 2018

A

DOI: 10.1021/acs.inorgchem.8b02574 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

because of their similar scattering factors. The Sn/In ratio was measured to be 0.101 for SOF-25 and 0.0734 for SOF-28 by inductively coupled plasma atomic emission spectroscopy analysis. As a result, the formula of the TO2-InSnS cluster was determined as [In34.5Sn3.5S65(H2O)6]12.5− for SOF-25 and [In35.4Sn2.6S65(H2O)6]13.4− for SOF-28. To determine the distribution of Sn4+ ions in the TO2-InSnS cluster, the bond valence sums (BVSs) of all metal sites (originally treated as In3+ ions) were calculated based on the bond information from the crystallographic data (Tables S3− S7). Toward the metal sites at the core and faces of the TO2 cluster, the BVSs of the TO2-InSnS cluster in SOF-25 and SOF28 are similar to that of the TO2-InS cluster in OCF-41. However, the metal sites at the vertexes of the TO2-InSnS cluster show a little higher BVSs than those in the TO2-InS cluster, which indicates that some metal sites at the vertexes are possibly occupied by tetravalent Sn4+ cations. Replacing In3+ by Sn4+ obviously decreases the local negative charges of the TO2InSnS cluster, which is beneficial to the high-dimensional coassembly of TO2 clusters. Thus, different from the layered arrangement of the TO2-InS clusters in OCF-41,10 TO2-InSnS clusters finally assembled into a double- (SOF-25) and tripleinterpenetrated (SOF-28) framework with diamond topology (Figures 1b and S6 and S7). SOF-25 shows a circular channel with a size of 11.3 Å × 12.5 Å along the b axis, and SOF-28 shows a stripped channel with a size of 7.9 Å × 39.3 Å along the c axis (Table S8). The protonated organic templated molecules in SOF-25 and SOF-28 disorderedly locate within the pore or channel of the framework, which are not capable of being determined exactly through a SCXRD technique. The large void space is calculated as 61.2% for SOF-25 and 56.9% for SOF-28 with the program PLATON.13 Solid-state UV−vis diffuse-reflectance spectra of SOF-25 and SOF-28 were also measured (Figure S9). The optical band gap was calculated as 3.1 eV for SOF-25 and SOF28 by using Kubelka−Munk methods, demonstrating that these materials are broad-band semiconductors. The electrocatalytic ORR is one of the key procedures for the realization of renewable applications.14 Although the ORR properties of transition-metal chalcogenides were investigated before, a few examples of cluster-based metal chalcogenides containing In and Sn components exhibit ORR properties.7f,12 Herein, the ORR properties of SOF-25/carbon black (CB)- and SOF-28/CB-modified glassy carbon electrodes were evaluated using cyclic voltammetry (CV) in a 0.1 M KOH solution. The CV curves in Figure 2 exhibited an obvious reduction peak for sample-decorated electrodes in O2-saturated solution, whereas no perceptible voltammetric current was observed in the presence of argon. Rotating disk electrode (RDE) voltammetry was further performed to investigate the kinetics of the

sulfur, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), (R)-(−)-2amino-1-butanol, and distilled water at 190 °C for 7 days (for the detail synthesis method and discussion, see the Supporting Information and Table S1). Controlling the molar ratio of Sn/ In/S and the amount of solvents finally leads to the formation of two novel In−Sn−S superlattices. Because the contrast experiments demonstrated that the superbase imine (DBU) plays an important role in the formation of the title compounds, they are denoted as SOF-25 and SOF-28 (SOF = superbaseoriented chalcogenide framework). Single-crystal X-ray diffraction (SCXRD) analysis (Table S2) indicated that SOF-25 and SOF-28 crystallize in orthorhombic and tetragonal systems with space groups of Pbca (No. 61) and I4̅2d (No. 122), respectively. The phase purities of these compounds were also confirmed by powder X-ray diffraction (PXRD; Figure S1). The weight loss (29.5% for SOF-25 and 26.8% for SOF-28) was attributed to the carbonization of templated molecules between 250 and 450 °C in thermogravimetric analysis (TGA) experiments under N2 conditions (Figure S2). In addition, the crystallinity of SOF-25 and SOF-28 was maintained even after calcination at 200 °C under a N2 flow (Figure S3). Both SOF-25 and SOF-28 feature the coassembly of unusual supertetrahedral TO2-InSnS clusters. Such a TO2-InSnS cluster could be recognized as a core−shell cluster with a NaCl-like core and a ZnS-like shell. The tetrahedron-shaped core contains 10 octahedrally coordinated metal sites. The core part in the TO2 cluster could also be recognized as the fused unit of four cubes (M4S4) through edge-sharing mode. There are four supertetrahedral T2 ([M4S10]) clusters at four corners and four hexagonal rings ([M3S3]) at four faces, which constitute the shell part of the TO2 cluster (Figures 1a and S4).

Figure 1. (a) Supertetrahedral TO2 cluster featured by the NaCl-like core. (b) Double- and triple-interpenetrated structures of SOF-25 and SOF-28, respectively.

Different from the known TO2-InS cluster in OCF-41, tetravalent Sn4+ ions were purposely introduced into TO2 clusters in SOF-25 and SOF-28. As shown in energy-dispersive spectrometry (EDS) mapping results, both the In and Sn components were observed to evenly distribute in the crystal (Figure S5). Notably, it was difficult to differentiate the absolute sites of In3+ and Sn4+ in the crystalline structure through SCXRD

Figure 2. CV curves of SOF-25/CB (a) and SOF-28/CB (b) in Ar- and O2- saturated 0.1 M KOH solutions. B

DOI: 10.1021/acs.inorgchem.8b02574 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

low extra volume is better than that of SOF-25 with high extra volume, which is demonstrated by the maximum current density (2.86 mA cm−2 for SOF-28/CB and −3.52 mA cm−2 for SOF28/CB). The framework material with higher conductivity may possess more electron-transfer pathways and faster electrontransfer rate, which is in favor of ORR processes. In summary, we for the first time successfully introduced tetravalent Sn4+ ions into the unusual supertetrahedral TO2-InS cluster. Different from the TO2-InS cluster in the only reported TO2-based compound with 2D-layered structure, TO2-InSnS clusters were observed to assemble into two 3D superlattices. Such open-framework semiconducting materials show doubleand triple-interpenetrated diamond topology if considering TO2-InSnS clusters as the nodes. In addition, the title compounds display good ORR electrocatalytic properties. Notably, targeting the 3D coassembly of the TO2 clusters is based on the successful synthetic strategy of introducing highvalent metal ions. This strategy may hold promising for the creation of novel open-framework chalcogenides based on largesized TOn clusters.

electrocatalytic ORR for SOF-25/CB and SOF-28/CB. As shown in Figure 3, the current density was stepwise-enhanced by

Figure 3. RDE voltammetry at different rotation rates of SOF-25/CB (a) and SOF-28/CB (b). Inset: Corresponding K−L plots at different potentials.

increasing the rotating rate. The corresponding Koutecky− Levich (K−L) plots exhibited good linearity over the potential range from −0.35 to −0.55 V. The electron-transfer number of SOF-25/CB was calculated to be about 2.2 from the K−L equation, and the peroxide species yield was about 60% (Figure S11). The electron-transfer number of SOF-28/CB was calculated to be about 2.6 from the K−L equation, and the peroxide species yield was about 50% by using a rotating ring disk electrode as the working electrode (Figure S11), indicating that the ORR occurring in these electrocatalytic materials adopted the mixed two- and four-electron pathways. The twoelectron process of the ORR is as follows:15 O2 + H 2O + 2e− → HO2− + OH−

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b02574. Experimental details, SCXRD data (CCDC 1841172 for SOF-25 and CCDC 1841171 for SOF-28), PXRD, elemental analysis, additional structural figures, UV−vis absorption spectra, and TGA (PDF)

(1)

Note that the stable In3+ cations are difficult to reduce as In+; thus, we consider that Snx+ ions (blending valences of Sn2+ and Sn4+) contribute to reduce the sequentially generated HO2− to OH−, which can be represented as follows: HO2− + H 2O + 2e− → 3OH−

ASSOCIATED CONTENT

S Supporting Information *

Accession Codes

CCDC 1841171−1841172 contain 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 [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

(2) 4+

Although Sn was determined to be tetravalent Sn cations in SOF-25 and SOF-28, the reduction reaction of Sn4+ to Sn2+ easily proceeds at the electrode surface.16 Also Sn2+ ions play the key role in the reduction reaction of HO2− because of their low potential of 0.15 V according to the literature,16 which leads to the partial four-electron pathway. To further confirm the role of Snx+, contrast experiments using only CB as the catalyst were carried out. The CB catalyst shows an electron-transfer number of around 2.0 and a peroxide species yield of 80% (Figure S11). Such an approximate twoelectron process and high yield of peroxide species demonstrate that CB cannot facilitate the catalysis of peroxide into hydroxide ions. Compared with the semiconducting framework materials, such as CuS (28 wt %)/HKUST-1,17 ε-MnO2/MIL-100(Fe),18 and the semiconducting layer MOF [Ni3(HITP)2]14c (Table S10), SOF-25/CB and SOF-28/CB show good ORR properties.19 It is necessary to compare the ORR properties of the two titled materials with different openness. The maximum current density of SOF-28/CB (−3.52 mA cm−2) is higher than that of SOF-25/ CB (2.86 mA cm−2; Table S10), and the electron-transfer number of SOF-28/CB (2.6) is more than that of SOF-25/CB (2.2). In addition, the peroxide yield of SOF-28/CB (∼50%) is lower than that of SOF-25/CB (∼60%; Figure S10). Thus, the ORR performance of SOF-28/CB is better than that of SOF-25/ CB. The possible reason is that the conductivity of SOF-28 with

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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 Min Luo: 0000-0001-8080-0881 Zhien Lin: 0000-0002-5897-9114 Tao Wu: 0000-0003-4443-1227 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grants 21671142 and 21875150), Jiangsu Province Natural Science Fund for Distinguished Young Scholars (Grant BK20160006), and the Priority Academic Program Development of Jiangsu Higher Education Institutions.

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DOI: 10.1021/acs.inorgchem.8b02574 Inorg. Chem. XXXX, XXX, XXX−XXX