New 2D Assemblage of Supertetrahedral Chalcogenide Clusters with

Jun 7, 2019 - Reported here are two new layered chalcogenide frameworks built from tetravalent-metal-induced triconnected supertetrahedral T3-InSnS ...
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Cite This: Cryst. Growth Des. 2019, 19, 4151−4156

New 2D Assemblage of Supertetrahedral Chalcogenide Clusters with Tetravalent-Metal-Induced Interrupted Sites Zhou Wu, Min Luo, Chaozhuang Xue, Jiaxu Zhang, Jing Lv, Xiang Wang, and Tao Wu* College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China

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S Supporting Information *

ABSTRACT: Reported here are two new layered chalcogenide frameworks built from tetravalent-metal-induced triconnected supertetrahedral T3-InSnS clusters. This work demonstrates the significant role of tetravalent metal ion in building new 2D chalcogenide frameworks with the interrupted sites. Moreover, both chalcogenide materials show good performance on the photodegradation of methyl blue (MB).

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have different effect on Mn2+-related red emission.29 Although some 2D metal chalcogenide cluster-based frameworks were successfully developed (Table 1), it to some extent suffers from

INTRODUCTION Open-framework metal chalcogenides have attracted tremendous attention during the past two decades due to the integration of porosity with semiconducting property that may find applications in areas ranging from gas adsorption1,2 to ion exchange,3−5 host−guest chemistry with energy transfer involved,6,7 and photocatalytic H2 evolution.8−11 Structurally speaking, metal chalcogenide open frameworks can be regarded as “bottom-up” self-assembly of tetrahedrally shaped nanoscale clusters with precisely defined size and compositions. Typically, such nanosized tetrahedral clusters are usually tetra-connected through sharing corner chalcogenide (such as μ2-Q2−, μ3-Q2−, μ4-Q2−, Q = S or Se)2,10,12−14 and further assemble into three-dimensional (3D) superlattice with various topologies (such as SOD,15 dia,16 CrB4,17 qzh,18 etc.). However, two-dimensional (2D) materials composed of supertetrahedral clusters are far less reported. 2D materials with unique electron structures and high specific surface areas have been widely investigated in the field of photocatalysis and electrocatalysis.19−22 Therefore, it is believed that the creation of 2D structures based on supertetrahedral clusters is one of the prominent ways to enrich the potential applications of the layered metal chalcogenides. During the past two decades, crystalline 2D chalcogenide frameworks have emerged as promising materials in many areas. For instances, the layered structures of K2xMxSn3‑xS6 (KMS-123 and KMS-224,25) and (Me2NH2)4/3(Me3NH)2/3(Sn3S7) (FJSM-SnS26,27) show excellent ion-exchanging abilities toward the removal of heavy metal ions and radioactive Cs+. A 2D superlattice with the largest supertetrahedral oxychalcogenide clusters assembled via BTC linkers demonstrates good electric conductivity due to the unique structure.28 In addition, the intercluster torsion stress occurring in two 2D layered chalcogenide frameworks © 2019 American Chemical Society

Table 1. Topology of Cluster-Based 2D Chalcogenide Frameworks Compound

Formula

SBUs

Topology

Ref

IOS-1 HCF-1 CIS-52 UCR-16 OCF-61 OCF-98 OCF-99 SOF-23 SOF-24

[(In35S48O8)(BTC)]10‑ [In12S24]12‑ [Cu5In30GeS63]27‑ [Cu5In30S54]13‑ [Sn42O16Se77]18‑ [Zn4In16S33]10‑ [Zn4In16S33]10‑ [In35Sn5S74]23‑ [In19SnS37]13‑

T5 T2-P1 T2-T5 T5 T3 T4 T4 T3 T3

hcb hcb hcb sql sql sql sql fes hcb

28 30 31 32 33 29 29 This work This work

randomness for building such materials. The controllable synthesis for 2D frameworks based on supertetrahedral chalcogenide clusters remains a challenge. Theoretically, 2D cluster-based layered structures could be constructed by incompletely connected or interrupted clusters as secondary building units (SBUs). Introduction of triconnected clusters is believed to be one of strategies for guiding supertetrahedral cluster-based 2D frameworks. However, tetrahedrally shaped clusters with highly negative charge are always inclined to share each other via the four corner chalcogen sites for the purpose of lowering the negative charge,34−36 and further assemble into 3D frameworks. Received: May 7, 2019 Revised: June 4, 2019 Published: June 7, 2019 4151

DOI: 10.1021/acs.cgd.9b00605 Cryst. Growth Des. 2019, 19, 4151−4156

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Then, the vessel was heated at 190 °C for 7 days and then taken out from the oven. The autoclave was subsequently allowed to cool at room temperature and pale-yellow crystals were obtained with a few impurities. The samples were washed by ethanol three times, filtered off, dried in air, and further purified by hand. Single Crystal X-ray Diffraction. Single-crystal X-ray diffraction (SC-XRD) measurements were performed on Bruker Photon II CPAD diffractometer with nitrogen-flow temperature controlled using Mo Kα (λ = 0.71073 Å) and Cu Kα (λ = 1.54178 Å) radiation at 100 K. The structure was solved by direct method using SHELXS-2014 and the refinement against all reflections of the compound was performed by using SHELXL-2014. Not all the protonated organic amine molecules and solvent molecules located in the void space of the framework can be identified owing to their serious disorder. The SQUEEZE subroutine in PLATON was used to treat the data. A summary of general crystal data, intensity data collection, and refinement parameters for SOF-23 and SOF-24 are presented in Table S1. Powder X-ray Diffraction. Powder X-ray diffraction (PXRD) data were collected on a desktop diffractometer (D2 PHASER, Bruker, Germany) using Cu Kα (λ = 1.54056 Å) radiation operated at 30 kV and 10 mA. The samples were ground into fine powders for several minutes before the test. As displayed in Figures S1 and S2, the experimental patterns match well with the simulated one from singlecrystal structure analysis of SOF-23 and SOF-24, indicating the phase purity of the two samples after manual screening. Elemental Analysis. Energy dispersive spectroscopy (EDS) analysis was performed on scanning electron microscope (SEM). An accelerating voltage of 25 kV and 40 s accumulation time were applied. EDS results clearly confirmed the presence of In, Sn, and S (Figures S3 and S4). Elemental analysis (EA) of C, H, and N were performed on VARIDEL III elemental analyzer, and the analysis results were displayed in Table S2. Thermogravimetric Measurement (TG). A Shimadzu TGA-50 thermal analyzer was used to measure the TG curve by heating the sample from room temperature to 600 °C with heating rate of 5 °C/ min under nitrogen flow. TGA analysis reveals that these two materials show high thermal stability; the frameworks collapse beginning at 270 °C as shown in Figure S5. UV−vis Absorption. Room-temperature solid-state UV−vis diffusion reflectance spectra of crystal samples were measured on a SHIMADZU UV-3600 UV−vis-NIR spectrophotometer coupled with an integrating sphere by using BaSO4 powder as the reflectance reference. The absorption spectra were calculated from reflectance spectra by using the Kubelka−Munk function: F(R) = α/S = (1 − R)2/2R, where R, α, and S are the reflection, the absorption, and the scattering coefficient, respectively. Fourier Transform Infrared Absorption. Fourier transforminfrared spectral (FTIR) analysis was performed on a Thermo Nicolet Avatar 6700 FT-IR spectrometer with cesium iodide optics allowing the instrument to observe from 600 to 4000 cm−1. FT-IR spectrum (Figure S6) displayed the characteristic peaks of templated organic amines. Preparation of SOF-23/ITO Film by Electrophoretic Deposition. Typical preparation of film of SOF-23 on indium−tin oxide (ITO) electrode: 5.0 mg of ground SOF-23 powder was dispersed in 10 mL isopropanol with the presence of 1.0 mg of Mg(NO3)2·6H2O. The sealed mixture suspension was continuously stirred for 24 h, and then was ultrasonically vibrated for an hour before electrophoretic deposition. The clean and sleek Pt plate electrode was used as anode, and the ITO conductive glass as cathode. Constant working voltage was set up to 30 V. The whole electrodeposition process lasted for 30 min. The obtained ITO electrode decorated with SOF-23 film on its surface was finally washed with ethanol to remove residual isopropanol and Mg(NO3)2 salt left in suspension. SOF-24 modified ITO film was fabricated followed the same process, except the SOF23 crystal powder was substituted by SOF-24. Photoelectric Response Experiment. The photoelectric response experiments were performed on a CHI760E electrochemistry workstation in standard three-electrode configuration,

Recently, our group emphasized the important role of triconnected supertetrahedral clusters with tetravalent M4+ ion involved in the construction of chalcogenide frameworks.37 It is plausible that the introduction of tetravalent M4+ ions to replace partial M3+ ions can decrease the high negative charge of the corner site of clusters, so that the possibility of formation of the interrupted clusters could be dramatically increased (as shown in Scheme 1). Scheme 1. Construction of Triconnected Clusters by Adding M4+ Ions into M3+-S Reaction System

Herein, we create two interrupted 2D chalcogenide frameworks through superbase-oriented solvothermal method, which are denoted as SOF-23 and SOF-24 with the framework formula of [In8.75Sn1.25S18.5] and [In9SnS18.5], respectively. Both structures are constructed by the interrupted T3-InSnS clusters, but with different numbers of the interrupted sites. To the best of our knowledge, compounds such as these two with interrupted sites have never been observed before in the family of T3 cluster-based chalcogenide frameworks.

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EXPERIMENTAL SECTION

Materials. Indium (In, 99%, powder), hydrated indium nitrate (In(NO3)3·xH2O, 99%, powder), trimesic acid (H3BTC, 99%, powder), sublimed sulfur (S, 99%, powder), thiourea (99%, powder), tin(II) chloride dihydrate (SnCl2, 99%, powder), tin (Sn, 99%, powder), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU, 99%, liquid), N,N-dimethylformamide (DMF, 99%, liquid), (R)-(−)-2-amino-1butanol (2-AB, 99%, liquid), and distilled water. All analytical grade chemicals employed in this work were commercially available and used without further purification. Synthesis of SOF-23 [In8.75Sn1.25S18.5]·2.5(H+-DBU)·3.25(H+Me2NH). A mixture of In(NO3)3·xH2O (124 mg), H3BTC (121 mg), thiourea (164 mg) and SnCl2·2H2O (24 mg) was mixed with the solvents of DMF (2 mL) and 1,8-diazabicyclo[5.4.0]-7-undecene (3 mL) in a 23 mL Teflon-lined stainless autoclave and was left under vigorous stirring for 30 min. Then, the vessel was sealed and heated at 180 °C for 9 days and then taken out from the oven. The autoclave was subsequently allowed to cool to room temperature, and paleyellow octahedral crystals were obtained. The crystals were washed by ethanol, dried in air, and further filtered off. The phase purity was identified by powder X-ray diffraction measurements. Notably, Me2NH species were from the decomposition of DMF during the solvothermal process.38 It should be noted that trimesic acid is vital in the crystallization of SOF-23 even though it was not observed in the resulting frameworks. Synthesis of SOF-24 [In9SnS18.5]·4.1(H+-DBU)·1.9(H+-AB). A mixture of indium powder (115 mg), sulfur powder (96 mg), SnCl2 (76 mg), distilled water (1 mL), (R)-(−)-2-amino-1-butanol (1 mL), and 1,8-diazabicyclo[5.4.0]-7-undecene (3 mL) was mixed in a 23 mL Teflon-lined stainless autoclave under vigorous stirring for 30 min. 4152

DOI: 10.1021/acs.cgd.9b00605 Cryst. Growth Des. 2019, 19, 4151−4156

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SOF-23/ITO and SOF-24/ITO as the working electrode, a Pt plate as the auxiliary electrode, and a saturated calomel electrode (SCE) as the reference electrode. The light source is a 150 W high pressure xenon lamp, located 20 cm away from the surface of the ITO electrode. Sodium sulfate aqueous solution (0.5 M, 100 mL) was used as the supporting electrolyte. Electrochemical Impedance Spectroscopy Measurement. The electrochemical impedance spectroscopy (EIS) measurement was performed under operating conditions on a CHI760E electrochemistry workstation in standard three-electrode configuration. The initial electric potential was set as −0.005 V vs RHE for direct comparison. A sinusoidal voltage with an amplitude of 5 mV and scanning frequency values ranging from 100 kHz to 1 Hz were applied to carry out the measurements. Sodium sulfate aqueous solution (0.5 M, 100 mL) was used as the supporting electrolyte. Photocatalytic Degradation of MB. The photocatalytic reactions under full-spectra (200−800 nm) irradiation for the degradation of MB were performed in a glass bottle. A 300 W Xe lamp was used as illuminating source. Crystalline SOF-23 and SOF24 photocatalyst (1 mg) were added into 10 mL MB aqueous solution (1.25 × 10−4) and stirring for 45 min in the dark condition to reach the adsorption/desorption equilibrium, respectively. The resulting solution was analyzed by UV-1800 UV−vis spectrophotometer every 10 min. The degradation efficiency was calculated as Ct/C0, where Ct and C0 represent the main peak of absorption at each irradiated time interval and the concentration of MB after adsorption/desorption equilibrium.

10 metal ions and 20 chalcogenide atoms. Among these 20 sulfide ions, 19 of them are bicoordinated or tricoordinated, and the remaining one sulfide ion at corner acts as a terminal site to connect to only one metal ion in T3 cluster. The distance of two adjacent dangling S sites from adjacent clusters is around 4.7446 Å (Figure S10). Although the location of In and Sn cannot be accurately designated, it is believed that the high-valent Sn4+ are more likely to connect to the interrupted S2− ion according to the local charge balancing rules.39 Another structural feature of SOF-23 is that two different 2D networks can be realized when taking different building units as nodes. On one hand, a uniform fes topology can be obtained when each interrupted μ3-T3 cluster is regarded as a node (Figure 2a). On the other hand, sql net (Figure 2b) could

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Figure 2. (a) Three-connected fes net in SOF-23 when T3 clusters are treated as nodes; (b) sql net in SOF-23 when T3,2 clusters are treated as nodes.

RESULTS AND DISCUSSION Single-Crystal Structure of SOF-23. SC-XRD analysis suggests that SOF-23 crystallizes in a highly symmetric space group of P42/nmc with a large cell volume around 16 513 Å3. SOF-23 consists of supertetrahedral μ3-T3-InSnS clusters as SBUs (Figure 1a). As shown in Figure 1b, each T3 cluster is

also be achieved if considering the interrupted T3,2 clusters as nodes. It is common that triconnected SBUs tend to form layered structures with hcb nets. It is the first case of the layered superlattice with a fes net composed of triconnected supertetrahedral clusters with exposed interrupted sites. Single-Crystal Structure of SOF-24. SOF-24 also consists of the interrupted μ3-T3-InSnS cluster (Figure 3a). Each T3 cluster is bonded to three adjacent T3 clusters through sharing bicoordinated sulfide (Figure 3b) with the T3S-T3 angle of 110.3°, 110.3°, and 110.8° (Figure S8). These T3 clusters are further assembled into six-membered rings and result in a 2D honeycomb (hcb) net (Figure 3c,d). The

Figure 1. (a) Triconnected (μ3-T3) cluster in SOF-23; (b) each μ3T3 cluster connects to three other μ3-T3 clusters; (c) view of the crystal packing down the c axis.

connected to three adjacent T3 clusters through corner sharing mode with T3-S-T3 bond angles of around 109.6°, 109.6°, and 120.7° (Figure S7), leaving the fourth dangled corner interrupted, which is caused by the occupation of high-valent Sn4+ ion. These T3 clusters are further assembled into a 2D structure (Figure 1c). Interestingly, four adjacent T3 clusters are coassembled into a coreless super-supertetrahedral T3,2 cluster with two of six edges interrupted, which is first observed in the system of super-supertetrahedral clusters. Actually, the structure of SOF-23 is similar to OCF-61 reported by Feng et al., in which the linkage at edges were occupied by Se2− and [Sn2Se6]4− units (Figure S9).33 Each μ3-T3 cluster consists of

Figure 3. (a) Triconnected (μ3-T3) cluster in SOF-24; (b) each μ3T3 cluster connects to three other μ3-T3 clusters; (c) view of the crystal packing down the c axis; (d) hcb net in SOF-24 when T3 clusters are treated as nodes. 4153

DOI: 10.1021/acs.cgd.9b00605 Cryst. Growth Des. 2019, 19, 4151−4156

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adjacent layers of hcb nets are packed in staggered arrangement along b axis. All the tetrahedral cluster nodes are triconnected, leaving the fourth corner sulfide site interrupted. The dangling site has distance of 8.7618 Å away from the bridging sulfur site at adjacent hcb layer (Figure S11). Metal chalcogenide frameworks with hcb net have ever been documented in IOS-1,28 CIS-52,31 and HCF-1,30 which were constructed by the SBUs of T5 (Figure S12), T2-T5 (Figure S13), and T2-P1 (Figure S14), respectively. SOF-24 represents the first metal chalcogenide framework with hcb net based on T3 clusters only. Optical Absorption. The solid-state UV−vis diffusereflectance spectra of SOF-23 and SOF-24 were investigated, as illustrated in Figure 4. The optical band gap of both two Figure 5. Photocatalytic activity of SOF-23 and SOF-24 as suggested by MB concentration versus irradiation time.

To demonstrate the reason for high photocatalytic degradation performance of SOF-23 in relation to SOF-24, photoelectric response and electrochemical impedance spectroscopy were measured. Figure 6a clearly demonstrates that SOF-23-

Figure 4. Tauc plots of SOF-23 and SOF-24 derived from UV−vis diffuse-reflectance spectra.

compounds are determined to be ∼3.2 eV, which is close to that of T3-InSnS cluster-based metal chalcogenide open frameworks, demonstrating that SOF-23 and SOF-24 are broad-band semiconductors. Photocatalytic Degradation of MB Solution. Photocatalytic degradation of MB in aqueous solution was investigated in the presence of SOF-23 and SOF-24 under ultraviolet irradiation. For comparison, the similar degradation process was also performed on a control experiment, in which there is no addition of above compounds. All experiments experienced a magnetic stirring process in the dark for 45 min, which made equilibrated adsorption before each irradiation. As shown in Figure 5, less than 30% MB slowly decomposed in 80 min without the addition of any photocatalysts under the irradiation of full light spectra. However, when SOF-24 was added, MB molecules could be degraded over 60% during the same period. Even more remarkably, the degradation efficiency is the highest with less than 10% of MB molecules left in the aqueous solution after 80 min while photocatalyst of SOF-23 was introduced. The catalytic performance of SOF-23 is comparable to some other hybrid microporous materials.40−45 Noticeably, although SOF-23 and SOF-24 have a similar light response, SOF-23 showed much higher degradation efficiency toward MB solution. Furthermore, the PXRD patterns of recollected solid samples after photocatalytic tests match well with the synthesized samples, indicating the recyclability of these photocatalysts (Figures S15 and S16). Photoelectric Response and EIS Measurements. It is generally accepted that high efficiency in electron−hole separation contributes to good activity in photocatalysis.46,47

Figure 6. (a) Photoelectric response of SOF-23 and SOF-24 with 0 V applied voltage; (b) EIS Nyquist plots of SOF-23 and SOF-24 electrodes.

decorated ITO photoelectrode gives the photocurrent density of 0.5 μA cm−2 without biased potential, which is 2.5 times larger than that of SOF-24-decorated photoelectrode, suggesting the higher separation efficiency of photogenerated charge carriers. In addition, EIS measurement was carried out to further confirm charge transfer efficiency. EIS analysis (Figure 6b) reveals that SOF-23 exhibits smaller Nyquist plot diameter than SOF-24, indicating the lower charge transfer resistance. All these results prove that SOF-23 shows better 4154

DOI: 10.1021/acs.cgd.9b00605 Cryst. Growth Des. 2019, 19, 4151−4156

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performance on the photoexcited charge-separation and charge-transfer efficiency than SOF-24. Obviously, such a different catalytic performance between SOF-23 and SOF-24 may be to a great extent related to 2D connection mode of the interrupted T3-InSnS clusters.

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CONCLUSION In summary, we report two new 2D chalcogenide frameworks built from the interrupted T3-InSnS cluster. Among these two structures, SOF-23 represents the first case of fes topology based on triconnected supertetrahedral cluster, and SOF-24 fills the blank of hcb net based on T3 clusters. In addition, these two compounds show good performance on degradation toward MB aqueous solution. It is worth noting that T3 clusters with the interrupted sites were successfully constructed by adding tetravalent metal ions. The introduction of noncompletely connected clusters offers great potential for the creation of other new 2D chalcogenide frameworks, which may function as potential catalysts for electrocatalysis and photocatalysis.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.9b00605. Experimental characterizations, additional structural presentations, EDS, PXRD patterns, and C/H/N elemental analysis (PDF) Accession Codes

CCDC 1914004−1914005 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.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Xiang Wang: 0000-0001-7354-6491 Tao Wu: 0000-0003-4443-1227 Notes

The authors declare no competing financial interest.

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

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REFERENCES

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Crystal Growth & Design

Article

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DOI: 10.1021/acs.cgd.9b00605 Cryst. Growth Des. 2019, 19, 4151−4156