Article pubs.acs.org/IC
Synthesis of a Ternary Thiostannate with 3D Channel Decorated by Hydronium for High Proton Conductivity Dan Zhang, Guangshe Li, Yu Peng, and Liping Li* State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130000, P. R. China S Supporting Information *
ABSTRACT: Metal chalcogenides with various channel structures feature a number of interesting properties including fast-ion conductivity and selective ion exchange. Most of these compounds are popularly prepared based on the templates of organic amines that play the part of a structure directing agent and even structure-building units, while it still remains a challenge as to the organotemplate-free synthesis for these compounds. Here, a new ternary thiostannate (H3O)4Cu8Sn3S12 was synthesized through a facile, efficient, and organotemplate-free route under hydrothermal conditions. The framework of (H3O)4Cu8Sn3S12 consists of [Cu8Sn6S24]8− building units and possesses a 3D interconnected 8-ring channel structure decorated by pure hydroniums, which not only balance the charges but also facilitate the proton conductivity. The proton conductivity reaches as high as 1.03 × 10−3 S cm−1 at 393 K under anhydrous conditions, which is 2 orders of magnitude higher than that of (H3O)2(enH2)Cu8Sn3S12, a similar channel structure compound prepared by using ethylenediamine as an organic template.
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INTRODUCTION In recent years, extensive attention has centered on openframework metal chalcogenides because of the attractive structure varieties and their potential value in many aspects.1−8 Among these compounds, porous metal chalcogenides with various channel structures appear to be most important due to their great potentials for fast-ion conductivity and selective ion exchange.9−15 Till now, most of such sulfide phases (e.g., GeCuS-1,16 A4Cu8Ge3S12 (A = K, Rb),17 (H2en)2Cu8Sn3S12,18 (C2N2H10)(C2N2H9)2Cu8Sn3S1219) are popularly based on the templates of organic amines that serve as a structure directing agent and even structure-building units. However, the employ of organic amines increases the preparative expense. What’s worse is that organic amines cause environmental contamination resulting from the emission of reaction wastes. To decrease the synthetic cost and environmental pollution, it is highly necessary to explore an organotemplate-free method for the synthesis of porous metal chalcogenides with various channel structures. The recent examples are those for a number of aluminosilicate zeolites and aluminophosphate molecular sieves.20−25 Unfortunately, for metal chalcogenides, the progress of organotemplate-free synthesis is very slow. At 2003, Zheng et al. prepared a sequence of porous metal chalcogenides with alkali or alkaline earth metal cations (for example, Li+, Na+, Ca2+) as extra framework cations through employing an organotemplate-free approach under hydrothermal conditions.26 However, after that, organotemplatefree synthesis has been rarely reported for porous metal © XXXX American Chemical Society
chalcogenides with various channel structures, and no success has been made for organotemplate-free preparation of porous metal chalcogenides with pure hydronium as extra framework cations thus far, possibly because the structures of these compounds are strongly depended on organic amines. Herein, we reported on the preparation of a new isotypic ternary thiostannate (H3O)4Cu8Sn3S12 (denoted as HCTS) with pure hydronium as extra framework cations by a facile, efficient, and organotemplate-free route under hydrothermal conditions. The framework of (H3O)4Cu8Sn3S12 displays 3D interconnected 8-ring channels, similar to that of (H3O)2(enH2)Cu8Sn3S12 (denoted as CTS)27 as synthesized by using ethylenediamine as the template. Notably, pure hydroniums in the channels endow HCTS with a high proton conductivity and specific ion exchange.
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EXPERIMENTAL SECTION
Sample Synthesis. Synthesis of HCTS. Sample (H3O)4Cu8Sn3S12 (HCTS) was prepared by a hydrothermal method in the reaction system of Cu-Sn-(NH2)2CS-NaOH-H2O. Typically, a mixture of (NH2)2CS (15.224 g, 200 mmol), Cu powder (0.635 g, 10 mmol), Sn powder (0.594 g, 5 mmol), NaOH (16 g, 400 mmol), and 20 mL of distilled H2O was directly put into a Teflon liner (95 mL), which was sealed into a Teflon-lined stainless steel autoclave and heated at 200 °C for 1 day after being stirred for 10 min by a glass bar. The crystal products were washed with distilled water and alcohol a couple of Received: August 22, 2016
A
DOI: 10.1021/acs.inorgchem.6b02012 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry times and dried at 70 °C for 6 h. The relative contents of Cu, Sn, and S determined by energy-dispersive spectroscopy (EDS) on several crystals gives an average composition of Cu8.3Sn3.1S12.0, as shown in Figure S1. Elemental analysis (wt %) for HCTS, calc, C: 0.00, H: 0.91 N: 0.00; found, C: 0.02, H: 0.88 N: 0.03. For comparison, the crystals of (H3O)2(enH2)Cu8Sn3S12 (CTS) were also synthesized under hydrothermal conditions according to ref 21. Preparation of NH4-HCTS and K-HCTS. NH4+ exchanged HCTS was obtained through soaking 0.2 g of HCTS crystals in 40 mL of 1 M NH4Cl solution at 60 °C for 2 h (denoted as NH4-HCTS). K+ exchanged HCTS was obtained through soaking 0.2 g of HCTS crystals in 40 mL of 0.1 M KCl solution at 20 °C (denoted as KHCTS-a) and 1 M KCl solution at 60 °C (denoted as K-HCTS-b) for 2 h, respectively. The exchanged samples were washed sufficiently with distilled water and dried at 70 °C for 6 h. Elemental analysis (wt %) for NH4-HCTS (C: 0.03, H: 0.89 N: 1.28) confirms the composition of (H3O)2.7(NH4)1.3Cu8Sn3S12. EDS analysis on several crystals shows that both K-HCTS-a and K-HCTS-b have an average composition of K2.1Cu7.9Sn3.1S12.0 and K3.9Cu8.1Sn2.8S12.0, respectively, as indicated in Figures S2 and S3. Sample Characterization. Powder X-ray diffraction (PXRD) results of the samples were determined from a Rigaku D/max-2550 diffractometer using Cu Kα radiation (λ = 1.5418 Å). Elemental analysis was conducted from a PerkinElmer 2400 elemental analyzer. Energy-dispersive spectroscopy (EDS) analysis was conducted on a HITACHI SU8020 analyzer. Thermogravimetric analysis (TG) results were obtained from a TA Q500 analyzer under a N2 atmosphere with a heating rate of 10 °C min−1 from room temperature to 800 °C. The IR absorption spectrum between 400 and 4000 cm−1 was obtained from a Nicolet 6700 FT-IR spectrometer by using KBr as the sample’s background. Several tablets of CTS, HCTS, K-HCTS-a, and K-HCTSb (10 mm in diameter, 1 mm in thickness) were obtained through pressing the fully grinding products on a tableting machine for the proton conductivity analyses. The measurement was carried out via impedance spectroscopy on a Solartron 1260 impedance analyzer over the frequency range from 10 Hz to 1 MHz and an applied AC voltage of 100 or 200 mV. The tablets were determined under an anhydrous N2 atmosphere between 293 and 393 K. Conductivities were obtained employing the following equation:
Table 1. Crystal Data and Structure Refinement of HCTS (H3O)4Cu8Sn3S12 empirical formula Fw temp (K) wavelength (Å) cryst system space group unit cell dimensions a (Å) volume (Å3) Z density (calcd) (Mg·m−3) Abs coeff (mm−1) F(000) cryst size (mm) θ range of data collection (deg) index ranges
reflections collected/unique R(int) data/restraints/parameters GOF on F2 final R indices [I > 2σ(I)] R indices (all data) largest diff. peak and hole (e·Å−3)
H12Cu8Sn3O4S12 1325.12 293(2) 0.71073 cubic F43̅ c 17.878(2) 5714.1(12) 4 1.452 4.631 2296 0.391 × 0.203 × 0.132 3.22−27.40 −22 ≤ h ≤ 22 −22 ≤ k ≤ 22 −20 ≤ l ≤ 22 11978/557 0.0381 557/0/18 1.008 R1 = 0.0326, wR2 = 0.1214 R1 = 0.0346, wR2 = 0.1255 0.456 and −0.780
synthetic process by using an organotemplate for isotypic compound CTS. Single-crystal diffraction result demonstrates that HCTS crystallizes in the cubic space group F4̅3c, and detailed crystallographic information is shown in Table 1. HCTS has the same group space with CTS, but the cell volume of HCTS was reduced to ca. 156.9 Å3, which is closely related with its pure hydronium feature (H3O+ has the smaller radius than (enH2)2+). The asymmetric unit for HCTS includes two crystallographically different Cu sites and one Sn site, as shown in Figure S4. All of the Cu atoms are in CuS3 planar trigonal environments, while the Sn atom is four-coordinated to form SnS4 tetrahedra. The Cu−S bond distances vary in the range of 2.232(2)−2.264(2) Å and the Sn−S bond distance is 2.4029(13) Å (Table S1). Similar Cu−S and Sn−S bond lengths are also reported in other ternary thiostannates.18,19,27 The connection of trigonal-planar CuS3 group and SnS4 tetrahedra in HCTS constructs an open framework. This framework is featured by [Cu8Sn6S24]8− building units (Figure 1a), which are formed by the connection of one Cu8S12 cluster (Figure S5) and six SnS4 tetrahedra. Adjacent [Cu8Sn6S24]8− are interconnected by sharing SnS4 tetrahedra to constitute a
σ = l /(R s × S) In the equation, l and S represent the thickness (cm) and crosssectional area (cm2) for the pellet, respectively, and Rs is the bulk resistance for the sample (Ω), which were extracted straightforwardly from the impedance spectra. Crystallographic Data Determination. An appropriate single crystal of HCTS was picked for single-crystal X-ray diffraction determination. The intensity results were obtained from a Bruker SMART CCD APEX II diffractometer employing graphite-monochromated Mo−Kα radiation (λ = 0.71073 Å) at a temperature of 293 ± 2 K. Data processing was finished by using the SAINT processing program.28 Its framework was obtained from direct methods and refined through the full-matrix least-squares technique by using the SHELXTL crystallographic software package.29 The Cu, Sn, and S locations of the structure could be unambiguously determined. The O locations of water molecules and associated H atoms were not located due to the high disorder. The detailed results of crystal determinations for HCTS are listed in Table 1. The selected bond distances and bond angles are listed in Table S1.
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RESULTS AND DISCUSSION Synthesis and Crystal Structure Description. Single crystals of HCTS were prepared through the hydrothermal route from a mixture of (NH2)2CS, Cu powder, Sn powder, NaOH, and distilled H2O heated at 200 °C for 1 day in 95 mL Teflon-lined stainless steel autoclaves, giving 72% yields based on Cu (1.2 g). The method in the present work has great advantages comparing to the two-step and time-consuming
Figure 1. (a) [Cu8Sn6S24]8− building unit. (b) Crystal structure for HCTS along the [001] direction. Color: Sn, green; Cu, red; S, yellow. B
DOI: 10.1021/acs.inorgchem.6b02012 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry 3D open framework. The framework of HCTS includes 3D interconnected 8-ring channels along the [001] (Figure 1b), [100], and [010] directions (Figure S6). The disordered hydroniums instead of (enH2)2+ are located in the channels as charge-balanced species. The pore sizes are estimated to be 5.6 × 5.6 Å (O···O distance) for HCTS, smaller than 5.8 × 5.8 Å for CTS. The smaller pore size of HCTS is in agreement with the reduced unit cell, which further confirms this change result from the smaller radius of H3O+ in the channels instead of (enH2)2+. It is worth mentioning that, although HCTS and (H2en)2Cu8Sn3S12 have the same formula of the anion [Cu8Sn3S12]4−, their structural characteristics are obviously different. The thermogravimetric spectrum of HCTS exhibits a weight loss of 5.4 wt % from room temperature to 250 °C, which is related to the emission of four water molecules in the channels (calcd 5.4 wt %) (Figure S7). In addition, the C, H, and N analysis in the Experimental Section further confirms four hydroniums in one unit cell. However, the locations of hydroniums could not be confirmed because of the high disorder. The stretching bands at 3409, 3127, and 1630 cm−1 also indicate the existence of a large amount of H3O+ groups in HCTS, as shown in Figure S8.30,31 PXRD and Ion Exchange of the Compounds. The pure phase of the compounds was confirmed by PXRD. As illustrated in Figure 2 and Figure S9, the pattern of the powder
Figure 3. XRD patterns for (a) experimental HCTS, (b) experimental K-HCTS-b, and calcined K-HCTS-b at (c) 100 °C, (d) 200 °C under a N2 atmosphere.
structure of HCTS might facilitate proton conductivity. The impedance measurements of CTS and HCTS were performed on pellets under an anhydrous N2 atmosphere from 293 to 393 K, and the resultant Nyquist plots are displayed in Figure 4.
Figure 2. XRD patterns for (a) simulated HCTS, (b) experimental HCTS, and calcined HCTS at (c) 100 °C, (d) 200 °C under a N2 atmosphere.
samples for CTS and HCTS match well with that simulated from the single-crystal structural data. PXRD studies at different temperatures show that CTS and HCTS can be stable until 200 °C under a N2 atmosphere (Figure 2 and Figure S9). Ionexchange experiments indicate that H3O+ in HCTS could be readily replaced by NH4+ (33.3% of ion-exchange degree) and K+ ion (52.5% of ion-exchange degree for K-HCTS-a, 97.5% of ion-exchange degree for K-HCTS-b), while keeping the framework intact (Figure 3 and Figure S10). Comparatively, other ions (Li+, Na+, Rb+, Cs+) could not be exchanged at all. The high ion-exchange ability and selectivity to specific ions such as NH4+ and K+ ions for HCTS may be mainly resulted from its channels with a particular size and shape in the openframework structure.32 PXRD studies at different temperatures show that K-HCTS-b can also be stable until 200 °C under a N2 atmosphere, as shown in Figure 3. Ionic Conductivities of the Compounds. Notably, the pure hydroniums in the 3D interconnected 8-ring channel
Figure 4. AC impedance plots for CTS (a) and HCTS (b) at different temperatures.
Proton conductivity was calculated by the ZView program. HCTS exhibited good proton conduction. For example, the conductivity (σ) of HCTS is 2.72 × 10−5 S cm−1 at 293 K, almost 2 times higher than 1.58 × 10−5 S cm−1 for CTS at the same temperature. Most importantly, when the temperature increased to 393 K, the conductivity of HCTS reached up to 1.03 × 10−3 S cm−1, 2 orders higher than that of 3.57 × 10−5 S cm−1 for CTS. Such a high proton conductivity for HCTS results from the small steric hindrance of H+/H3O+. Namely, H+/H3O+ moves faster than (enH2)2+ in the 8-ring channels. Moreover, the pure hydroniums are easier to form H-bonds along the channels, which could connect the hydroniums and C
DOI: 10.1021/acs.inorgchem.6b02012 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
activation energy of K-HCTS-b is about 0.17 eV (Figure 7). The TG curve of K-HCTS-b underwent much more weight
facilitate proton conductivity. As listed in Table S2, the proton conductivity of HCTS is comparable to that reported for many other proton conducting materials. The plots of the bulk conductivity [log(óT)] vs reciprocal temperature (1000/T) for CTS and HCTS are exhibited in Figure 5. The data are well-
Figure 7. Arrhenius plot for K-HCTS-b. Figure 5. Arrhenius plots for CTS and HCTS.
loss (ca. 7.0%) than as-synthesized HCTS, as shown in Figure S12. This indicates that the existence of K+ ions in the channels favors the adsorption of more water molecules in the ionexchanged products of K-HCTS-b.35 The conductive property of NH4-HCTS was also studied, as shown in Figure S13. The conductivities of NH4-HCTS were 1.91 × 10−5 S cm−1 at 293 K and 2.29 × 10−4 S cm−1 at 393 K, which are higher than that of K-HCTS-a, but lower than that of HCTS under the same conditions. These differences can be understood in terms of the fact that the partly replaced hydroniums with NH4+ has less impact on the H-bonds of structure comparing to that with K+ because new H-bonds could be formed between NH4+ and hydroniums.
fitted to the Arrhenius expression [ó = ó0 exp(−E/kT), where ó0 represents a preexponential factor, E represents the activation energy, and k represents the Boltzmann constant]. On the basis of Arrhenius plots [ln(óT) vs 1000 T−1], the calculated activation energy (Ea) of the proton transfer is 0.21 eV for HCTS (Figure 5), indicating that the proton conduction process follows the Grotthuss mechanism, as reported in other systems.33,34 The lower activation energy of 0.09 eV for CTS may be mainly attributed to the larger channel size. To further understand the proton conductivity of HCTS, the proton conduction performance for ion-exchanged products of K-HCTS-a and K-HCTS-b was comparatively investigated. The proton conductivities of K-HCTS-a were 6.56 × 10−6 S cm−1 at 293 K and 3.47 × 10−5 S cm−1 at 393 K, respectively (Figure S11). These values are obviously much lower than that of the as-synthesized HCTS under the same condition, which suggests that the partial K+ instead of hydroniums would hinder the proton conductivity due to the broken H-bonds system between hydroniums. The results from Nyquist plots (Figure 6) showed that the conductivities of K-HCTS-b were 2.14 ×
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CONCLUSIONS We have successfully synthesized a new isotypic ternary thiostannate (H3O)4Cu8Sn3S12 with pure hydronium as extra framework cations by a facile, efficient, and organotemplate-free route under hydrothermal conditions. The structure of HCTS constructed by trigonal-planar CuS3 group and SnS4 tetrahedra possesses 3D interconnected 8-ring channels along the [001], [100], and [010] directions. Hydroniums are occupied in the channels, which endow HCTS with high proton conductivity up to 2.72 × 10−5 S cm−1 (293 K) and 1.03 × 10−3 S cm−1 (393 K) under anhydrous conditions. The material possesses supreme selectivity and capacity of NH4+ and K+ ions. This work provides more opportunities for the exploration of new open-framework metal chalcogenides materials with excellent proton conductivity properties.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b02012. A list of bond distances and bond angles, IR data, powder X-ray diffraction patterns, TGA curves, EDS data, AC impedance plots, and a list of proton conductors (PDF) Crystallographic data for HCTS (CCDC 1471571) (CIF)
Figure 6. AC impedance plots for K-HCTS-b at different temperatures.
10−5 S cm−1 at 293 K and 3.59 × 10−4 S cm−1 at 393 K, which are all obviously higher than that of K-HCTS-a under the same condition. This observation indicates K+ conductivity when most of hydroniums in the compounds were replaced by K+. The lower conductivities for K-HCTS-b than those for HCTS at the same condition could be attributed to the bigger radius of K+ than proton H+, which moves faster than K+. The calculated
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. D
DOI: 10.1021/acs.inorgchem.6b02012 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry ORCID
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Liping Li: 0000-0002-6732-4902 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was financially supported by NSFC (Grants 21571176, 21271171, and 21025104). REFERENCES
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DOI: 10.1021/acs.inorgchem.6b02012 Inorg. Chem. XXXX, XXX, XXX−XXX
