Preparation, crystal structure and photocatalytic activity of a zinc-potassium substituted sandwiched antimonotungstate

TIAN Xuemeng, SHI Fangying, PANG Jingjing, LUO Jie

(Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, Henan, China)

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Preparation, crystal structure and photocatalytic activity of a zinc-potassium substituted sandwiched antimonotungstate

TIAN Xuemeng, SHI Fangying, PANG Jingjing, LUO Jie*

(HenanKeyLaboratoryofPolyoxometalateChemistry,CollegeofChemistryandChemicalEngineering,HenanUniversity,Kaifeng475004,Henan,China)

A zinc-potassium substituted sandwich-type antimonotungstate Na9[Zn3K3(H2O)9] [B-α-SbW9O33]2·44H2O (1) was synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic space groupC2/cwitha= 1.399 93(12) nm,b= 2.317 6(2) nm,c= 3.208 8 (3) nm,β= 98.804 0(10)°,V= 10.288 0(15) nm3,Z= 4,Dc= 3.930 g/cm3,GOOF= 1.026,R1= 0.043 6 andwR2= 0.103 5. X-ray crystal structural analysis reveals that the molecular unit of 1 is constructed from two trivacant [B-α-SbW9O33]9-building blocks sandwiching a hexagon zinc-potassium [Zn3K3(H2O)9]9+core via twelve lacunary oxygen atoms. The photocatalytic measurements illustrate that 1 can partly inhibit the photodegradation of azophloxine.

polyoxometalate; antimonotungstate; sandwich-type compound

Polyoxometalates (POMs), as a family of anionic metal-oxygen clusters with vast structural diversities and noticeable properties, have attracted great attention and endowed them with great opportunities to distinguish themselves in many domains covering environment, materials, energy, health and molecular electronics[1-4]. Among them, transition-metal substituted POMs (TMSPs) are the vital and rapid-growing member of the family. In various structural types of TMSPs, one of important subclass is sandwich-type TMSPs[5], which can be obtained by two main synthetic strategies: i) using simple raw materials under hydrothermal conditions; ii) using the reaction of lacunary POM precursors with transition-metal cations in conventional aqueous solution. To our knowledge, the tetrahedral heteroatom [XW9O34]n-(X = SiIV, GeIV, PV, AsV) anions have four isomers of A-α, A-β, B-α, B-βwhile the pyramidal heteroatom [XW9O33]n-(X = AsIII, SbIII, BiIII, SeIV) anions have two isomers of B-α, B-β. Since WEAKLEY et al[6]found the first sandwich-type phosphotungstate [Co4(H2O)2(PW9O34)2]10-in 1973, a large number of Keggin-type TMSPs based on [XW9O34]n-fragments have been synthesized such as [Cs2K(H2O)7Pd2WO(H2O) (A-α-SiW9O34)2]9-[7], [Nb2K(H2O)4(A-α-SiW9O34)2]9-[8], [M4(H2O)2(PW9O34)2]10-(X = PV, SiIV, AsV, GeIV; M = MnII, CoII, NiII, CuII, ZnII)[9-18]etc. However, the reports on Keggin-type TMSPs based on [XW9O33]n-fragments were very limited. The structure of [(WO2)4(OH)2(XW9O33)2]12-(X = SbIII, BiIII) was first discovered by KREBS et al in 1997[19-20], then several similar derivatives were reported sequentially such as [Cu3(H2O)2(α-AsW9O33)2]12-, [M3(H2O)3(α-XW9O33)2]n-(n= 12, X = AsIII, SbIII, M = Mn2+, Co2+, Ni2+, Cu2+, Zn2+;n= 10, X= SeIV, TeIV, M = Cu2+)[21-23]. As far as we know, the majority of sandwich-type Keggin-type compounds based on [SbW9O33]9- fragments contain one type of transition-metal ions in the sandwich belt while the related reports on the sandwich belt consists of transition-metal and alkali metal ions are very rare. For example, ZHAO et al reported an organic-inorganic hybrid sandwich-type tungstoantimonate [Cu(en)2(H2O)]4[Cu(en)2(H2O)2][Cu2Na4(α-SbW9O33)2]·6H2O, in which a hexagonal {Cu2Na4} cluster are located in the sandwich belt[24]. In this paper, a zinc-potassium substituted sandwich-type antimonotungstate Na9[Zn3K3(H2O)9][B-α-SbW9O33]2·44H2O (1) (CCDC 1537821) was obtained by using trivacant Keggin [ B-α- SbW9O33]9-precursor with Zn2+and K+cations via the conventional solution method and was characterized by IR spectra and X-ray crystal structural analysis.

1 Experimental

1.1 Reagents and physical measurements

Na9[B-α-SbW9O33]·19.5H2O was prepared according to the literature[19]and was confirmed by IR spectra. All reagents were obtained from commercial resources and used without further purification. Inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses were performed on a Jobin Yvon ultima 2 spectrometer. The IR spectrum was recorded from a sample powder palletized with KBr on a Nicolet170 SXFT-IR spectrometer over the range of 4 000-400 cm-1. Photocatalysis of 1 was carried out on an XPA photoreactor (Xujiang Electromechanical Plant, Nanjing, China) and a 300 W mercury lamp was used as the light source, which was placed into the cylindrical reactor, surrounded by a circulating water system to cool the lamp.

1.2 Synthesis of 1

Na9[B-α-SbW9O33]·19.5H2O (1.50 g, 0.52 mmol), Zn(OAc)2·2H2O (0.15 g, 0.26 mmol),L-tartrate (0.05 g, 0.33 mmol) andL-alanine (0.10 g, 1.12 mmol) were dissolved in NaOAc-HOAc (20 mL pH = 6.0) buffer solution, to which Er(NO3)3·6H2O(0.20 g, 0.43 mmol) and KCl (0.10 g, 1.34 mmol) was added under stirring. The resulting solution was stirred for 4 h and heated at 80 ℃ for 2 h. After cooling to room temperature, the solution was filtered and the filtrate was left to evaporate at room temperature. Colorless prismatic crystals were obtained after four weeks. Yield:ca. 40% (based on Zn(OAc)2·2H2O). Ana. calcd. for 1 (%): Zn, 3.23; Sb, 4.00; W, 54.39; K, 1.93. Found (%): Zn, 3.14; Sb, 4.17; W, 54.23; K, 1.85. Obviously, there are no organic molecules and Er3+ions in the structure of 1 althoughL-alanine,L-tartrate and Er(NO3)3·6H2O were used as the starting materials. Thus, the parallel experiments were made whenL-alanine,L-tartrate and Er(NO3)3·6H2O were removed away from the reactants, 1 was not obtained. These results indicate thatL-alanine,L-tartrate and Er(NO3)3·6H2O play a synergistic action with other components in the formation of 1, although their specific roles are not well understood in the reaction processes.

1.3 X-ray crystallography

A good single crystal for 1 was carefully selected under an optical microscope and glued at the tip of a thin glass fiber with cyanoacrylate adhesive. Intensity data were collected on Bruker APEX-II CCD detector at 296(2) K with Mo Kαradiation (λ= 0.071 073 nm). Intensity data were corrected for Lorentz and polarization effects as well as for empirical absorption. The structure was solved by direct methods and refined by the full-matrix least-squares method onF2using the SHELXTL-97 package[25]. The remaining atoms were found from successive full-matrix least-squares refinements onF2and Fourier syntheses. All the non-hydrogen atoms were refined anisotropically. Those hydrogen atoms attached to lattice water molecules were not located. The crystallographic data and structural refinements for 1 are shown in Table 1.

Table 1 Crystallographic data and structural refinements of 1

2 Results and discussion

2.1 Description of crystal structure

Single-crystal X-ray diffraction indicates that 1 crystallizes in the monoclinic space groupC2/cand its structural unit consists of one {[Zn3K3(H2O)9][B-α-SbW9O33]2}9-polyoxoanion, nine Na+ions and forty-four crystallization water molecules. The {[Zn3K3(H2O)9][B-α-SbW9O33]2}9-polyoxoanion is built by one [Zn3K3(H2O)9]9+(Fig.1a) cluster and two [B-α-SbW9O33]9-fragments (Fig.1b). The structure of {[Zn3K3(H2O)9][B-α-SbW9O33]2}9-is shown in Fig.1c. The [B-α-SbW9O33]9-fragment displays a conventional trivacant Keggin-type structure, in which the SbIIIatom is embedded in the center and three groups of trinuclear {W3O13} clusters mutually connect each other via sharing vertexes. The [B-α-SbW9O33]9-fragment is also deemed as a derivative from the hypotheticalα-Keggin structure {α-SbW12O40} unit by removing a trinuclear {W3O13} cluster. Notably, this structure is also identical with other polyoxotungstates showing the same type of [XW9O33]n-, such as [Cu(en)2(H2O)]4[Cu(en)2(H2O)2][Cu2Na4(α-SbW9O33)2]·6H2O[24], which is discriminative from [XW9O34]n-(X = SiIV, GeIV, PV, AsV). Moreover, the Sb-O distances range from 0.198 3(9) to 0.198 6(9) nm and the distances between the terminal oxygen atoms and W atoms are in the range of 0.178 6(9)-0.181 5(10) nm, which are slightly shorter than those between the W atoms and the bridging oxygen atoms [0.191 0(9)-0.231 3(9) nm]. As shown in Fig.1a, three Zn2+and three K+ions in the central belt display the penta-coordinate tetragonal pyramid geometry and the hexa-coordinate trigonal prism geometry, respectively. To the best of our knowledge, the five-coordinate Zn2+complex is very rare. Four coordinate oxygen atoms connecting the Zn2+and K+ions derives from two [B-α-SbW9O33]9-fragments and one oxygen atom is from the water molecule in the tetragonal pyramid of Zn2+ions while two oxygen atoms are from water molecules in the trigonal prism of K+ions. The Zn-O bond distances are in the range of 0.200 9(10)-0.204 1(9) nm for Zn1 and 0.199 9(10)-0.203 5(9) nm for Zn2 and the O-Zn-O bond angles range from 85.8(4)° to 155.1(6)° and 86.5(4)° to 154.2(4)° respectively for Zn1 and Zn2; The K-O bond distances are 0.239 4(10)-0.241 0(11) nm for K1, 2.369(10)-2.445(11) nm for K2 and the O-Zn-O bond angles are from 71.1(3)° to 122.0(4)° for K1, and 70.9(3)° to 120.6(6)° for K2.

Fig.1 (a) [Zn3K3(H2O)9]9+ cluster in 1. (b) Ball-and-stick and polyhedral representation of the [B-α-SbW9O33]9- fragments. (c) The molecular structural unit of 1. Lattice water molecules and Na+ ions are omitted for clarity. Symmetry code A: 2-x, y, 0.5-z

2.2 IR spectra

IR spectra of the precursor Na9[B-α-SbW9O33]·19.5H2O and 1 (Fig.2) have been recorded using a solid sample palletized with KBr in the range of 4 000-400 cm-1in favor of identifying characteristic vibration bands. The characteristic vibration patterns derived from the Keggin-type framework appear in the low wavenumber region from 1 100-700 cm-1. Four cha-racteristic vibration absorption bands attributable to terminalν(W-Ot),ν(Sb-Oa), corner-sharingν(W-Ob) and edge-sharingν(W-Oc) are at 925, 770, 892, and 704 cm-1for the precursor and 946, 777, 883, and 731 cm-1for 1[19，26-27]. In comparison with the IR spectrum of the precursor, vibration peaks of 1 have different shifts with blue shifts forν(W-Ot),ν(Sb-Oa) andν(W-Oc) and the red shift forν(W-Ob), which presumably attributed to the incorporation of Zn2+cations and K+cations into the vacancy of two [B-α-SbW9O33]9-fragments. Vibration absorption bands observed at 3 436 and 1 623 cm-1are attributed to the stretching vibration and bending vibration of water molecules, respectively. In short, the results of the IR spectrum are fully coincident with those of X-ray diffraction structural analysis.

Fig.2 (a) IR spectrum of the precursor Na9[B-α-SbW9O33]·19.5H2O. (b) IR spectrum of 1

2.3 Photocatalytic activity

Recently, many POMs have attracted increasing attention because of their photocatalytic properties to the degradation of organic dyes under UV irradiation[28-30]. To investigate the photocatalytic activity of 1, the photocatalytic degradation of azophloxine has been examined using of 1 as the photocatalyst. In the first place, the dye aqueous solution containing 4 mL of the initial concentration of azophloxine of 4 × 10-5mol/L with 3.3 × 10-6mol (based on [B-α-SbW9O33]9-) catalyst of 1 was diluted to volume of 50 mL and irradiated under 300 W mercury lamp at ambient temperature and stirring continually. For comparison, the photocatalytic degradation of the azophloxine solution in the absence of 1 was also performed under the same conditions. Apparently, the photodegradation rate of azophloxine in the presence of 1 became much slower than that in the absence of 1 (Fig.3a and 3b). The photocatalytic result illustrates that 1 can portly inhibit the photodegradation of azophloxine. This finding is much unexpected and obviously different from those reports that POMs can facilitate the photodegradation experiment of azophloxine[28-29]. The dominating reasons that 1 can partly inhibit the photodegradation of azophloxine may be involved in the following aspects: the presence of 1 might act as an absorber of the Hg lamp irradiation resulting in the deceasing of absorbance of azophloxine and the hydrogen-bonding interactions between donors and acceptors in azophloxine (-SO-3, -OH, -CONH ) and 1 (en, surface oxygen atoms of POMs) enhanced the chemical stability of azophloxine substrate in the solution[31], which resulted in the slow photodegradation of azophloxine substrate. Furthermore, the curves of the conversion of azophloxine (y) versus the reaction time (t) are shown in Fig. 3c, in whichA0represents the absorbance of the characteristic absorption band of azophloxine at 530 nm at the initial time (t= 0) andAtis the absorbance of the characteristic absorption band of azophloxine at the given time (t). The conversion of azophloxine can be drawn as the formula ofy= (A0-At)/A0. Obviously, the conversion in the presence of 1 is lower than that in the absence of 1, which verifies that 1 can to some extent inhibit the photodegradation of azophloxine.

Fig.3 UV-visible absorption spectral changes for the azophloxine solutions at various irradiation times: (a) in the absence of 1; (b) in the presence of 1; (c) The conversion of azophloxine versus the reaction time both in the ab-sence and presence of 1

3 Conclusions

In summary, a zinc-potassium substituted sandwich-type antimonotungstate 1 was successfully prepared, in which the [Zn3K3(H2O)9]9+cluster is implanted to the vacancy positions of two [B-α-SbW9O33]9-fragments. The photocatalytic measurements indicate that 1 can to some extent inhibit the photodegradation of azophloxine. The synthesis of this zinc-potassium sandwiched antimonotungstate provides a synthe-tic route for preparing the main-group-transition-metal substituted POMs in the following time.

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一種Zn-K取代夾心型銻鎢酸鹽的制備、晶體結(jié)構(gòu)和光催化活性

田雪蒙,史芳瑛,龐晶晶,羅 婕*

(河南省多酸化學(xué)重點(diǎn)實(shí)驗(yàn)室,河南大學(xué) 化學(xué)化工學(xué)院,河南 開封 475004)

合成了一種Zn-K取代的夾心型銻鎢酸鹽Na9[Zn3K3(H2O)9][B-α-SbW9O33]2·44 H2O (1)，并借助元素分析、紅外光譜和X射線單晶衍射等方法對其進(jìn)行了表征. 標(biāo)題化合物屬于單斜晶系,C2/c空間群,晶胞參數(shù):a= 1.399 93(12) nm,b= 2.317 6(2) nm,c= 3.208 8(3) nm,β= 98.804 0(10)°,V= 10.288 0(15) nm3,Z= 4,Dc= 3.930 g/cm3,GOOF= 1.026,R1= 0.043 6,wR2= 0.103 5. X 射線單晶衍射結(jié)構(gòu)分析表明，化合物1分子結(jié)構(gòu)由2個三缺位銻鎢構(gòu)筑塊[B-α-SbW9O33]9-通過12個缺位氧原子與1個六邊形鋅鉀簇[Zn3K3(H2O)9]9+相連而成. 光催化結(jié)果表明,化合物1在一定程度上可以抑制偶氮熒光桃紅的光降解.

多金屬氧酸鹽; 銻鎢酸鹽; 夾心型化合物

Supported by the Foundation of Education Department of Henan Province (16A150027) and the Students Innovative Pilot Plan of Henan University (16NA005).

, E-mail:Luojie@henu.edu.cn.

O614.3 Document code： A Article ID： 1008-1011(2017)03-0314-07

Received date： 2017-03-21.

Biography： TIAN Xuemeng (1996-), female, majoring in molecule-based functional materials.*