English

• 0.   Introduction

  Metal chalcogenide cluster-based framework materials have shown promising application prospects in the fields of ion exchange^[1-5], photocatalysis^[6-8], and fast ion conduction^[9-11], which is attributed to their combination of semiconductor and porous material properties. The larger size of the Q (Q=S, Se) atoms compared to oxygen can easily extend their coordination number up to four. This makes it tend to form {MQ₄} (M=Mn, Cu, Zn, Ga, In, Ge, Sn) tetrahedra in an arrangement similar to a cubic ZnS lattice when combined with metals, ultimately forming super tetrahedral (Tn) clusters with different sizes and compositions^[12-15]. As is well known, structural diversity is an important foundation for studying the structure-performance relationship of a class of materials and improving their performance applications. However, due to the specific tetrahedral coordination pattern of metal and sulfur atoms in metal chalcogenide Tn clusters, it is very difficult for them to show refreshing variations in cluster structure.

  The group 15 metals M (M³⁺=Sb³⁺, Bi³⁺) exhibit high stereo activity, which is attributed to the lone pair of electrons in their outermost electron layer. They tend to form asymmetric geometries when coordinated with sulfur elements, such as pseudo-tetrahedral {MS₃} and pseudo-trigonal bipyramidal {MS₄}. These constituent units bring more fresh structures to the metal chalcogenide cluster^[16-19]. Moreover, the group 15 metal sulfides often have strong light absorption coefficients and controllable band gaps, and have received increasing attention in the fields of photo-electrochemistry, such as photocatalysis and solar energy conversion^[20-22]. In recent years, Huang and co-workers developed a series of structurally novel metal sulfur cluster materials using group 15 metals, which not only exhibited excellent metal ion exchange performance but also attracted attention to their demonstrated optoelectronic properties, such as [CH₃NH₃]₂₀Ge₁₀Sb₂₈S₇₂·7H₂O and [(CH₃CH₂CH₂)₂ NH₂]₃Ge₃Sb₅S₁₅·0.5(C₂H₅OH)^[23], (Me₂NH₂)₂(Ga₂Sb₂S₇)·H₂O and (Et₂NH₂)₂(Ga₂Sb₂S₇)·H₂O^[24]. However, an undeniable issue is that compared to a large number of oxide materials that have already been developed and applied, the structural types of metal chalcogenide clusters are still very lacking. This will make it difficult for such materials to significantly improve their performance and application through sufficient research models. The enrichment of new structures for such cluster materials has become an urgent issue to be addressed.

  In this work, two metal chalcogenide cluster compounds [Sb₄S₅(S₃)]·C₅H₁₁N (1) and (C₅H₁₂N)₂[In₂Sb₂S₇] (2) were prepared by solvothermal synthesis. Compound 1 consists of Sb and S to form a linear 1D chain neutral skeleton with the molecular formula of [Sb₄S₅(S₃)]. Compound 2 is a 2D layered structure of In-Sb-S ternary metal sulfide. A series of electrocatalytic oxygen reduction reaction (ORR) performance studies showed that 2 has more excellent catalytic activity than 1.

  1.   Experimental

  1.1   Materials and measurements

  All starting reagents (AR grade) were commercially available and used as purchased without further purification. Powder X-ray diffraction (PXRD) patterns of the compounds were obtained using a Bruker Model D8 Advance powder diffractometer at room temperature with Cu Kα radiation (λ=0.154 18 nm). The operating tube voltage was 40 kV and the operating tube current was 25 mA. The patterns were recorded in a 2θ range of 5°-60° with a scanning step width of 0.02°. Elemental analysis of the compounds was performed on a VARIDEL Ⅲ elemental analyzer. The optical absorption properties of the compounds were analyzed using a UV-Vis spectrophotometer (EVOLUTION 220 UV-Vis-NIR). The photoresponse experiments were performed at the CHI 760E electrochemical workstation in a standard three-electrode configuration.

  1.2   Preparation of compounds 1 and 2

  A mixture of sulfur powder (48.0 mg, 1.50 mmol), Sb₂S₃ (29 mg, 0.085 mmol), and 2.0 mL piperidine was stirred in a 15-mL Teflon-lined stainless steel autoclave for 30 min. The vessel was sealed and heated at 180 ℃ for 8 d, and then the autoclave was cooled to room temperature naturally without any other operations. Red flake crystals of compound 1 were obtained with a few impurities. The raw products were washed three times with methanol and filtered off, and the resulting product contained a small amount of black particles, which were further purified by hand with a yield of 34.2 mg (48.6% based on Sb). Anal. Calcd. for C₅H₁₁NS₈Sb₄(%): C, 7.25; H, 1.34; N, 1.69. Found(%): C, 7.27; H, 1.44; N, 1.74.

  A mixture of In₂O₃ (35 mg, 0.126 mmol), Sb₂S₃ (29 mg, 0.085 mmol), sulfur powder (48.0 mg, 1.50 mmol), and 2.0 mL piperidine was stirred in a 15-mL Teflon-lined stainless steel autoclave for 30 min. The vessel was sealed and heated at 180 ℃ for 8 d, and then the autoclave was cooled to room temperature naturally without any other operations. Pale yellow-green block crystals of compound 2 were obtained. The raw products were washed three times with methanol and filtered off with a yield of 37.6 mg (50.9% based on Sb). Anal. Calcd. for C₁₀H₂₄In₂N₂S₇Sb₂(%): C, 13.81; H, 2.78; N, 3.22. Found(%): C, 13.85; H, 2.85; N, 3.18.

  1.3   ORR test

  A three-electrode system was used for relevant tests. The glassy carbon electrode with a diameter of 3 mm was used as the working electrode, the Ag/AgCl electrode was used as the reference electrode, and the Pt sheet was used as the working electrode. The electrocatalytic activity of the compounds was studied by cyclic voltammetry (CV) and linear scanning voltammetry (LSV) curves. All measured potentials were relative to the Ag/AgCl electrode and reversible hydrogen electrode (RHE).

  The working electrodes modified with compounds 1 and 2 were prepared by the following steps: 5 mg of the compound′s crystals and 5 mg of carbon black were weighed, mixed evenly, and thoroughly ground for 30 min. Subsequently, 3 mg of the mixed samples were taken to which 400 μL of water, 100 μL of anhydrous ethanol, and 20 μL of 5% Nafion were added, and the mixture was sonicated for 40 min to a homogeneous solution. Finally, 10 μL of the mixed solution was applied to the pre-prepared glassy carbon electrode and dried naturally in the air for 24 h for subsequent characterization.

  1.4   X-ray crystallography

  Single-crystal X-ray diffraction data of compounds 1 and 2 were collected on an Agilent Gemini Eos diffractometer by using a graphite monochromator utilizing Mo Kα radiation (λ=0.071 07 nm). The structures were solved by intrinsic phasing with the SHELXS and refined by full-matrix least-squares methods on F² by using the SHELXL-2018 program. A summary of the crystallographic data for compounds 1 and 2 is listed in Table 1.

  Table 1

  

  Table 1.  Crystallographic parameters of compounds 1 and 2

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  Parameter	1	2
  Formula	C5H11NS8Sb4	C10H24In2N2S7Sb2
  Formula weight	828.62	869.87
  Temperature / K	298	298
  Crystal system	Orthorhombic	Monoclinic
  Space group	Pbcm	I2/a
  a / nm	0.597 05(2)	1.638 24(5)
  b / nm	3.016 81(11)	0.689 89(2)
  c / nm	1.002 44(3)	2.166 03(8)
  β / (°)		99.034(3)
  V / nm3	1.805 58(10)	2.417 69(14)
  Z	4	4
  Dc / (g·cm-3)	3.045	2.390
  μ / mm-1	6.828	4.698
  F(000)	1 516.0	1 640.0
  Collected reflection	15 417	7 333
  Unique reflection (Rint)	2 105 (0.051 1)	3 985 (0.022 3)
  Completeness / %	99.8	99.7
  GOF on F2	1.199	1.166
  R1, wR2 [I > 2σ(I)]	0.090 2, 0.242 8	0.038 8, 0.070 3
  R1, wR2 (all data)	0.094 3, 0.245 1	0.053 8, 0.075 1

  2.   Results and discussion

  2.1   Crystal structure description

  X-ray single crystal diffraction analysis shows that compound 1 crystallizes in the Pbcm space group, consisting of a 1D neutral chain [Sb₄S₅(S₃)] and piperidine molecules. As shown in Fig. 1a, the asymmetric unit contains three Sb atoms, two of which have a space occupation of 0.5. Among the six S atoms, four have a space occupancy rate of 0.5, and in addition, there is also half a piperidine molecule in the structural unit. Among them, each Sb atom coordinates with three S atoms, forming an {SbS₃}^3- trigonal-pyramidal geometries with Sb—S bond lengths ranging from 0.236 8 to 0.249 7 nm. Subsequently, adjacent units {SbS₃}^3- were assembled through corner-sharing, forming a 1D chain skeleton consisting of two alternating ring structures, namely a four-membered [Sb(S₃)] ring and a six-membered [Sb₃S₃] ring (Fig. 1b). Observing along the b-axis direction, it can be seen that a large number of piperidine molecules are filled between the 1D chain structure of {Sb₄S₅(S₃)}, and they have interconnected through N—H…S and C—H…S hydrogen bonds (Fig. 1c).

  Figure 1

  

  Figure 1.  (a) Asymmetric unit of compound 1; (b) 1D chain structure of {Sb₄S₅(S₃)}; (c) Spatial stacking of 1D chains along the a‐axis direction

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  Compound 2 crystallizes in the I2/a space group of the monoclinic system. As shown in Fig. 2a, the asymmetric unit contains one Sb atom, one In atom, four S atoms (one S atom with a space occupation of 0.5), and a protonated piperidine cation. The {InS₄} tetrahedron and {SbS₃} trigonal-pyramidal geometry are obtained through four or three coordination forms of In atoms and Sb atoms with S atoms in compound 2, respectively. Subsequently, the {InS₄} and {SbS₃} units are alternately connected by a corner-sharing to assemble a 2D layered skeleton [In₂Sb₂S₇]^2- with two types of pores, i.e., the eight-membered ring {In₂Sb₂S₄} and the twelve-membered ring {In₄Sb₂S₆} (Fig. 2b). Observation of the spatial stacking pattern along the b-axis direction shows that there is a certain staggered distribution between the different layered anionic backbones, and a large number of protonated piperidinium cations are distributed in the interlayers, which enhances the stability of crystal structure (Fig. 2c).

  Figure 2

  

  Figure 2.  (a) Asymmetric unit of compound 2; (b) 2D layered skeleton [In₂Sb₂S₇]^2-; (c) Spatial stacking of 2D layers along the b‐axis direction

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  2.2   PXRD analyses and photoelectric characterization

  PXRD analyses of compounds 1 and 2 were carried out at room temperature. The experimental patterns were very consistent with the calculated patterns obtained from the crystal structure, indicating that the single crystal structures are representative of bulk materials, and the obtained samples are homogeneous phases (Fig. 3).

  Figure 3

  

  Figure 3.  PXRD patterns of compounds 1 (a) and 2 (b)

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  To study the optical band-gap of compounds 1 and 2, their UV-Vis diffuse reflectance spectra were analyzed. As shown in Fig. 4a, the optical bandgap of compound 1 was 1.85 eV, indicating that it can effectively absorb visible light, which matches its crystal color. The optical band gap of compound 2 was 2.26 eV, indicating a decrease in its visible light absorption range compared to compound 1, which may be attributed to changes in its metal composition (Fig. 4b). The photogenerated electron separation efficiency has a significant impact on the photocatalytic activity of a compound. Transient photocurrent (i-t) testing showed that 1 and 2 exhibited intense signal responses with changes in light sources (Fig. 4c). The photocurrent density of 1 was as high as 0.84 μA·cm^-2, significantly higher than compound 2 (0.45 μA·cm^-2). These results indicate that compound 1 may have superior photocatalysis properties.

  Figure 4

  

  Figure 4.  Tauc plots derived from UV‐Vis diffuse reflectance spectra of compounds 1 (a) and 2 (b); (c) Photoelectric response versus time (i‐t) curves of compounds 1 and 2

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  2.3   Electrocatalytic ORR test

  ORR is one of the two half-reactions essential in new energy storage and conversion systems such as fuel cells and metal-air batteries. In recent years, researchers have found that metal chalcogenide cluster-based materials can exhibit certain ORR properties^[25-28]. In the ORR performance studies of compounds 1 and 2, the catalytic activity of both compounds was analyzed using CV.

  As shown in Fig. 5, no characteristic current signals of blank electrode, compounds 1 and 2 were observed in the KOH solution saturated with N₂. However, after placing a series of working electrodes in an O₂-saturated KOH solution, 1 and 2 exhibited significant reduction signals, with reduction peak potentials of 0.56 and 0.58 V, respectively. This was better than the 0.54 V of the blank electrode, indicating that 1 and 2 have certain ORR catalytic activity. Subsequently, to study the ORR kinetics of 1 and 2, the LSV curves of the compounds were further tested. As the electrode speed gradually increased, the current density of the rotating disc electrodes (RDEs) made of 1 and 2 also gradually increased (Fig. 6a and 6b). At an electrode rotational speed of 2 500 r·min^-1, 2 had a higher limit current density and a larger half-wave potential than 1, indicating better ORR performance (Fig. 6c). In addition, at the same electrode rotational speed, the limit current densities and half-wave potentials of 1 and 2 were significantly better than those of the blank electrode. It was worth noting that the peak at 0.33 V in the LSV curve of the blank electrode may come from the characteristics of the electrode itself (Fig. 6c).

  Figure 5

  

  Figure 5.  CV curves of the blank electrode, compounds 1 and 2 in N₂‐/O₂‐saturated KOH solution

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  Figure 6

  

  Figure 6.  LSV curves at different rotation rates for RDEs made of compounds 1 (a) and 2 (b); (c) LSV curves at 2 500 r·min-1 for the blank electrode, compounds 1 and 2

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  The Koutecky-Levich (K-L) plots (Fig. 7) showed that the catalytic processes of compounds 1 and 2 were significantly different from -0.35 to -0.50 V. The electron transfer number of 1 in the catalytic process was 1.9 (Fig. 7a), which seems to indicate that its catalytic process is mainly dominated by the two-electron pathway. The two-electron process of the ORR is as follows:

  $ \mathrm{O}_2+\mathrm{H}_2 \mathrm{O}+2 \mathrm{e}^{-} \rightarrow \mathrm{HO}_2^{-}+\mathrm{OH}^{-} $

  (1)

  Figure 7

  

  Figure 7.  K‐L curves of compounds 1 (a) and 2 (b)

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  On the contrary, the electron transfer number of compound 2 was as high as 3.6, indicating that the four-electron pathway plays a major role in catalytic processes (Fig. 7b). In fuel cells, the four-electron process can provide greater power, and its reaction process is as follows:

  $ \mathrm{O}_2+4 \mathrm{e}^{-}+2 \mathrm{H}_2 \mathrm{O} \rightarrow 4 \mathrm{OH}^{-} $

  (2)

  3.   Conclusions

  In general, two metal chalcogenide cluster compounds [Sb₄S₅(S₃)]·C₅H₁₁N (1) and (C₅H₁₂N)₂[In₂Sb₂S₇] (2) have been synthesized. They are composed of asymmetric triangular cone elements {SbS₃} and highly symmetric tetrahedral elements {InS₄} through vertex-sharing. A series of ORR performance studies have shown that compound 2 constructed with the participation of mixed metals exhibits better catalytic ability. In addition, the porous 2D layered structure of compound 2 may make it valuable for applications in ion exchange, ionic conduction, and so on. This work not only develops the structural diversity of metal chalcogenide cluster-based materials but also inspires expanding this type of cluster-based materials by utilizing group 15 metals with highly stereochemically active.

  
  
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• 

  Figure 1  (a) Asymmetric unit of compound 1; (b) 1D chain structure of {Sb₄S₅(S₃)}; (c) Spatial stacking of 1D chains along the a‐axis direction

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  Figure 2  (a) Asymmetric unit of compound 2; (b) 2D layered skeleton [In₂Sb₂S₇]^2-; (c) Spatial stacking of 2D layers along the b‐axis direction

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  Figure 3  PXRD patterns of compounds 1 (a) and 2 (b)

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  Figure 4  Tauc plots derived from UV‐Vis diffuse reflectance spectra of compounds 1 (a) and 2 (b); (c) Photoelectric response versus time (i‐t) curves of compounds 1 and 2

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  Figure 5  CV curves of the blank electrode, compounds 1 and 2 in N₂‐/O₂‐saturated KOH solution

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  Figure 6  LSV curves at different rotation rates for RDEs made of compounds 1 (a) and 2 (b); (c) LSV curves at 2 500 r·min-1 for the blank electrode, compounds 1 and 2

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  Figure 7  K‐L curves of compounds 1 (a) and 2 (b)

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  Table 1.  Crystallographic parameters of compounds 1 and 2

  Parameter	1	2
  Formula	C5H11NS8Sb4	C10H24In2N2S7Sb2
  Formula weight	828.62	869.87
  Temperature / K	298	298
  Crystal system	Orthorhombic	Monoclinic
  Space group	Pbcm	I2/a
  a / nm	0.597 05(2)	1.638 24(5)
  b / nm	3.016 81(11)	0.689 89(2)
  c / nm	1.002 44(3)	2.166 03(8)
  β / (°)		99.034(3)
  V / nm3	1.805 58(10)	2.417 69(14)
  Z	4	4
  Dc / (g·cm-3)	3.045	2.390
  μ / mm-1	6.828	4.698
  F(000)	1 516.0	1 640.0
  Collected reflection	15 417	7 333
  Unique reflection (Rint)	2 105 (0.051 1)	3 985 (0.022 3)
  Completeness / %	99.8	99.7
  GOF on F2	1.199	1.166
  R1, wR2 [I > 2σ(I)]	0.090 2, 0.242 8	0.038 8, 0.070 3
  R1, wR2 (all data)	0.094 3, 0.245 1	0.053 8, 0.075 1

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