Core-shell type tungsten polyacid cluster compound based on 3d-4p dissimilar metal cluster substitution as well as preparation method and application of core-shell type tungsten polyacid cluster compound

Abstract

The invention discloses a core-shell type tungsten polyacid cluster compound based on substitution of 3d-4p dissimilar metal clusters as well as a preparation method and application of the core-shell type tungsten polyacid cluster compound. The molecular formula of the core-shell type tungsten polyacid cluster compound based on substitution of the 3d-4p dissimilar metal clusters is H29Na9 (H2O) 21 {Ca (H2O) 2 (at) Sb12O18 [Ni2 (OH) (A-alpha-SiW10O37)] 3} 2.40 H2O, the core-shell type tungsten polyacid cluster compound based on 3d-4p dissimilar metal cluster substitution is crystallized in a trigonal system, the space group is P-3, the crystal structure is divided into a {Ni2 (A-SiW10)} shell and a {Ca} at {Sb12} core, and the shell structure is composed of three two-vacancy {A-alpha-SiW10O37} located at three vertexes and three two-core {Ni2O10 (OH)} units located at the vacancy positions of the {A-alpha-SiW10O37}; the {Ca} (at) {Sb12} inner core with Td symmetry is composed of 12 SbO3 triangles and one {CaO6 (H2O) 2} dodecahedron, and the 12 SbO3 triangles are assembled into a spherical hollow {Sb12} cage by sharing oxygen atoms; the {Sb12} cage comprises four hexacyclic and four tricyclic windows, is cup-shaped, and encapsulates an octa-coordinated Ca < 2 + > ion into one of the hexacyclic windows to form a {Ca} at {Sb12} core.

Description

Technical Field

[0001] The invention belongs to the technical field of crystal materials and proton conductive materials, and specifically relates to a core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, and a preparation method and application thereof. Background Art

[0002] The widespread use of fossil fuels has led to a series of environmental problems and energy crises, prompting the rapid development of research on renewable energy. The intermittent and random nature of renewable energy has hindered its large-scale application. Accordingly, electrochemical energy storage and conversion devices have flourished due to their excellent efficiency. Among various electrochemical devices, proton exchange membrane fuel cells are considered to be potential candidates due to their ultra-low emissions, high power density and fast start-up characteristics. As an important component of proton exchange membrane fuel cells, proton exchange membranes must have high proton conductivity. Therefore, it is of great significance to develop functional materials with efficient proton transfer channels.

[0003] In recent years, many functional materials with high proton conductivity have been developed, including metal organic frameworks, porous coordination polymers and covalent organic frameworks, but they have stability problems. Polyoxometalates, referred to as polyacids, are metal-oxygen clusters, usually composed of early transition metals in high oxidation states (mainly V, Mo, W, Nb and Ta), whose oxygen-rich surfaces can provide more proton transfer sites and improve proton transfer efficiency. In particular, since the discovery of Keggin-type heteropolyacids, 12-tungstophosphoric acid hydrate has a high proton conductivity of 0.18 S cm at room temperature. -1 Since the high proton conductivity of polyacids was demonstrated, the research on polyacid-based proton conductive materials has attracted more and more attention. Subsequently, many polyacids with ideal proton conductivity properties have been reported.

[0004] Under certain conditions, Keggin-type polyacids can transform into metastable vacancy units with different vacancy numbers by losing one or more MO6 polyhedra, and act as multidentate oxygen ligands to induce 3d transition metal ions to cluster at their vacancies, thereby constructing novel structures with unique properties. At present, there are many reports on 3d transition metal ion substituted polyacids. However, there are few reports on 3d transition metal ion and 4p metal ion clustered co-substituted polyacids. Therefore, exploring 3d-4p substituted polyacids with high proton conductivity is an important and challenging research direction. Summary of the invention

[0005] To solve the above problems, the present invention proposes a core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, and a preparation method and application thereof. The preparation method of the present invention is simple, and the prepared tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution exhibits excellent single crystal proton conduction performance, and has good stability and recyclability.

[0006] The present invention adopts the following technical solutions:

[0007] A core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, wherein the molecular formula of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution is H 29 Na9(H2O) 21 {Ca(H2O)2@Sb 12 O 18 [Ni2(OH)(A-α-SiW 10 O 37 )]3}2·40H2O, where @ represents the core-shell structure, Ca 2+ Ions in {Sb 12} cage, A-α represents the configuration of the metal-oxygen cluster; the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution crystallizes in the trigonal system, the space group is P-3, and the crystal structure is divided into {Ni2(A-SiW 10 )} shell and {Ca}@{Sb 12 The core consists of two parts, the shell structure is composed of three divacant {A-α-SiW 10 O 37} and three dinuclear {Ni2O 10 (OH)} unit composition; with T d Symmetric {Ca}@{Sb 12 The core is composed of 12 SbO3 triangles and 1 {CaO6(H2O)2} dodecahedron. The 12 SbO3 triangles are assembled into a spherical hollow {Sb 12}cage; {Sb 12 The cage contains four six-ring and four three-ring windows and is cup-shaped, enclosing an eight-coordinated Ca 2+ ions are packaged into one of the six-ring windows to form {Ca}@{Sb 12}kernel.

[0008] Preferably, the unit cell parameters of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution are: α=β=90°, γ=120°, The calculated density is 3.829 g / cm 3 .

[0009] A method for preparing a core-shell type tungsten polyacid cluster based on 3d-4p heterometallic cluster substitution, the specific preparation process is: weighing the precursor Na 10 [A-α-SiW9O 34]·18H2O, nickel acetate tetrahydrate, antimony trichloride, and calcium chloride dihydrate are dissolved in a boric acid buffer solution of pH=9 and stirred thoroughly, then transferred into a glass bottle and placed in an oven for hydrothermal reaction. The hydrothermal reaction product is centrifuged and washed to obtain hexagonal crystals, that is, a core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution is obtained; the precursor Na 10 [A-α-SiW9O 34 ]·18H2O, nickel acetate tetrahydrate, antimony trichloride, calcium chloride dihydrate and boric acid buffer solution are added in a molar ratio of 2.2:4.0:3.8:8.5:1.5; the temperature of the hydrothermal reaction is 65°C and the reaction time is 5 days.

[0010] The invention discloses an application of a core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution. The core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution is used as a proton conduction material and is applied in the field of proton conduction.

[0011] After adopting the above technical scheme, the present invention has the following advantages compared with the background technology: the preparation method of the present invention is simple, and a high-yield pure sample of the product of Example 1 can be obtained in one step by a hydrothermal synthesis method. The product of Example 1 is a novel core-shell type tungsten polyacid cluster substituted by a heterometallic cluster composed of 3d transition metals and 4p metal ions. The prepared core-shell type tungsten polyacid cluster based on 3d-4p heterometallic cluster substitution exhibits relatively excellent powder proton conductivity performance. More specifically, it exhibits efficient single crystal proton conductivity performance and has good stability and recyclability. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 This is a crystal diagram of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of the product of Example 1 of the present invention;

[0013] Figure 2 This is a structural diagram of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, which is the product of Example 1 of the present invention;

[0014] Figure 3 This is a structural diagram of the asymmetric unit of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, the product of Example 1 of the present invention;

[0015] Figure 4 The two-dimensional double-layer structure diagram of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of the product of Example 1 of the present invention in different directions;

[0016] Figure 5 The powder diffraction pattern of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of the product in Example 1 of the present invention;

[0017] Figure 6 This is an infrared spectrum of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of the product in Example 1 of the present invention;

[0018] Figure 7 This is a solid ultraviolet diffuse reflectance image of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, which is the product of Example 1 of the present invention;

[0019] Figure 8 This is a thermogravimetric curve of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of the product of Example 1 of the present invention;

[0020] Fig. 9 This is a diagram of humidity-dependent conductivity of the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in powder proton conduction, which is the product of Example 1 of the present invention;

[0021] Fig.10 This is a temperature-dependent conductivity diagram of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in powder proton conduction of the product of Example 1 of the present invention;

[0022] Fig.11 This is the activation energy diagram of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in powder proton conduction of the product of Example 1 of the present invention;

[0023] Fig.12 This is a powder diffraction pattern of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of the product of Example 1 of the present invention after testing in powder proton conduction;

[0024] Fig.13 This is a crystal plane diagram of a hexagonal single crystal of a core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, which is the product of Example 1 of the present invention;

[0025] Fig.14 The humidity-dependent conductivity diagram of the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in single crystal proton conduction along the

[001] direction of the product of Example 1 of the present invention;

[0026] Fig.15 The humidity-dependent conductivity diagram of the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in single crystal proton conduction along the

[110] direction of the product of Example 1 of the present invention;

[0027] Fig.16 The humidity-dependent conductivity diagram of the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in single crystal proton conduction along the

[100] direction of the product of Example 1 of the present invention;

[0028] Fig.17The temperature-dependent conductivity diagram of the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in single crystal proton conduction along the

[001] direction of the product of Example 1 of the present invention;

[0029] Fig.18 The temperature-dependent conductivity diagram of the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in single crystal proton conduction along the

[110] direction of the product of Example 1 of the present invention;

[0030] Fig.19 The temperature-dependent conductivity diagram of the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in single crystal proton conduction along the

[100] direction of the product of Example 1 of the present invention;

[0031] Fig. 20 The two-dimensional layer structure diagram of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in the

[001] direction of the product of Example 1 of the present invention;

[0032] Fig.21 The two-dimensional layer structure diagram of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in the

[110] direction of the product of Example 1 of the present invention;

[0033] Fig. 22 The two-dimensional layer structure diagram of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in the

[100] direction of the product of Example 1 of the present invention;

[0034] Fig.23 The activation energy diagram of the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution in single crystal proton conduction along the

[001] ,

[110] and

[100] directions respectively, which is the product of Example 1 of the present invention. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0036] See also Figures 1 to 23 .

[0037] Example 1

[0038] H 29 Na9(H2O) 21 {Ca(H2O)2@Sb 12 O 18 [Ni2(OH)(A-α-SiW 10 O 37)]3}2·40H2OPreparation of core-shell tungsten polyacid clusters based on 3d-4p heterometallic cluster substitution

[0039] According to the molar ratio of 2.2:4.0:3.8:8.5, weigh the precursor Na 10 [A-α-SiW9O 34 ]·18H2O, nickel acetate tetrahydrate, antimony trichloride, and calcium chloride dihydrate were added to 2mL of boric acid buffer solution with pH = 9 and mixed evenly. After stirring for one hour, the resulting mixture was put into a 20mL glass bottle and placed in an oven for hydrothermal reaction. After reacting at 65°C for 5 days, the mixture was cooled to room temperature. After centrifugation and washing, a core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution was obtained, that is, the product of Example 1 is H 29 Na9(H2O) 21 {Ca(H2O)2@Sb 12 O 18 [Ni2(OH)(A-α-SiW 10 O 37 )]3}2·40H2O.

[0040] Example 2

[0041] Example 1 Detection of product

[0042] The crystal photo of the product of Example 1 based on the core-shell type tungsten polyacid cluster substituted with 3d-4p heterometallic cluster was taken, as shown in FIG. Figure 1 shown.

[0043] The sample of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of the product of Example 1 was characterized by X-ray single crystal diffraction. The results are as follows: Figure 2 As shown. The crystal belongs to the P-3 space group, and its unit cell parameters are: α=β=90°, γ=120°,

[0044] The sample structure of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of the product in Example 1 was analyzed by SHELX-2018 / 3, and the crystallographic parameters of the compound are shown in Table 1;

[0045] Table 1 Crystallographic parameters of core-shell tungsten polyacid clusters based on 3d-4p heterometallic cluster substitution

[0046]

[0047] a R1=Σ||Fo|-|Fc|| / Σ|Fo|, b wR2=[Σw(Fo 2 -Fc 2) 2 / w(Fo) 2 ] 1 / 2 ,w=1 / [σ 2 (Fo 2 )+(0.1035P) 2 +2714.6177P],whereP=(F 2 +2Fc 2 ) / 3.

[0049] The product of Example 1 is based on the structure of the core-shell type tungsten polyacid cluster compound substituted with 3d-4p heterometallic clusters, as shown in Figure 3 shown.

[0050] Example 1 The two-dimensional double-layer structure of the core-shell tungsten polyacid cluster compound substituted with 3d-4p heterometallic clusters in different directions is shown in FIG. Figure 4 shown.

[0051] Example 1 The product of the core-shell tungsten polyacid cluster substituted with 3d-4p heterometallic clusters was determined by X-ray powder diffraction (eg Figure 5 In addition, infrared spectroscopy (as shown) was also performed Figure 6 As shown), solid ultraviolet diffuse reflectance spectrum (as shown Figure 7 ) and thermogravimetric curves (as shown Figure 8 (as shown). The proton conductivity performance test is divided into two aspects: powder proton conductivity and single crystal proton conductivity. Powder proton conductivity performance test: Use a tablet press to make a sandwich-type three-layer cylindrical piece with carbon powder at both ends (about 70 mg each) and a sample in the middle (about 90 mg), and use sandpaper to polish the side of the cylindrical piece sample until there is no carbon powder from the appearance, and use a vernier caliper to record the thickness of the sample; connect the sample to the electrode in a constant temperature and humidity chamber, and use a zennium / IM6 impedance analyzer (set the test voltage to 50mV, the frequency range to 1Hz-10 MHz) to monitor its resistance changes with humidity and temperature. First, test its humidity-dependent conductivity at 25°C, as shown Fig. 9 As shown, the conductivity at 25°C and 55% relative humidity is 1.86×10 -4 S cm -1 When the temperature is kept constant at 25°C, the conductivity increases by one order of magnitude to 2.83×10 -3 S cm -1 , which indicates that under high humidity conditions, more water molecules enter the structure to participate in the transport of protons; then the humidity is kept constant at 98% relative humidity, and its temperature-dependent conductivity is tested, such as Fig.10 As shown in Figure 2, the conductivity increases by an order of magnitude when the temperature increases from 25°C to 85°C, reaching 3.00×10 -2 Scm-1 The phenomenon that the conductivity increases with the increase of temperature is attributed to the fact that the temperature increase process accelerates the transfer of protons in the channel. The conductivity of the core-shell tungsten polyacid cluster based on 3d-4p heterometallic cluster substitution at 85°C and 98% relative humidity is comparable to that of some reported excellent polyacid-based proton conducting materials. According to the Arrhenius formula (σT = σ0exp(-E a / k b T)), calculate its activation energy E a =0.38eV (such as Fig.11 The excellent proton conductivity is attributed to the presence of abundant proton carriers in the structure of the core-shell tungsten polyacid clusters substituted with 3d-4p heterometallic clusters, including water molecules and terminal oxygen atoms, which help to form a hydrogen bond proton "hopping" network. The powder diffraction pattern after the test confirmed that the structure of the core-shell tungsten polyacid clusters substituted with 3d-4p heterometallic clusters of the product of Example 1 remained intact after undergoing the proton conduction test (as shown in Figure 1). Fig.12 shown).

[0052] In order to gain a deeper understanding of the relationship between crystal structure and proton conduction, silver wires were carefully attached to the hexagonal single crystal of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, which is the product of Example 1, along the opposite sides using conductive silver paste, and the single crystal proton conductivity along the

[001] direction,

[110] direction and

[100] direction was measured by AC impedance. The crystal plane diagram of the hexagonal single crystal of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, which is the product of Example 1, is shown in FIG. Fig.13 As shown. First, the relative humidity-dependent conductivity of the single crystal was estimated along different directions. At 25°C and 55% relative humidity, the proton conductivity along the

[001] direction reached 6.61×10 -5 S cm -1 (like Fig.14 ), which is significantly higher than the values ​​of 1.51×10 -6 (like Fig.15 shown) and 2.26×10 -5 S cm -1 (like Fig.16 As shown in Figure 2, the conductivity along the

[001] direction increases by only 26 times to 1.72×10 -3 S cm -1 (like Fig.14Surprisingly, the values ​​along the

[110] and

[100] directions increase by nearly 6000 times and 200 times, respectively, showing excellent 8.82×10 -3 and 4.16×10 -3 S cm -1 The proton conductivity (such as Fig.15 and 16 These results indicate that water molecules play a vital role in improving proton conductivity under high relative humidity conditions, and the core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution of Example 1 is a highly anisotropic proton conductive material. In addition, higher proton conductivity indicates that proton diffusion is more favorable along the

[110] and

[100] directions.

[0053] The temperature-dependent proton conductivity of the hexagonal single crystal of the core-shell tungsten polyacid cluster substituted with 3d-4p heterometallic clusters, the product of Example 1, along different directions was further studied. As the temperature increases, the proton conductivity of the hexagonal single crystal of the core-shell tungsten polyacid cluster substituted with 3d-4p heterometallic clusters, the product of Example 1, increases in all directions, which is due to the acceleration of proton transfer in the channel. Specifically, in the

[001] direction, when the temperature rises from 25°C to 85°C and the relative humidity is 98%, the proton conductivity of the hexagonal single crystal of the core-shell tungsten polyacid cluster substituted with 3d-4p heterometallic clusters, the product of Example 1, increases from 1.72×10 -3 Increased to 1.53×10 -2 S cm -1 (like Fig.17 The proton conductivity at 85°C and 98% relative humidity reaches 1.11×10 -1 and 1.04×10 -1 S cm -1 (like Fig.18 and 19As shown), under the same conditions, these values ​​are about 10 times that of the hexagonal single crystals of the core-shell type tungsten polyacid clusters based on 3d-4p heterometallic clusters substituted by the product of Example 1 along the

[001] direction, indicating that the diffusion of protons along the

[110] and

[100] directions is more favorable. In addition, the proton conductivity of the hexagonal single crystals of the core-shell type tungsten polyacid clusters based on 3d-4p heterometallic clusters substituted by the product of Example 1 along the

[110] and

[100] directions increased by 12 times and 25 times, respectively, as the temperature increased from 25°C to 85°C, indicating that the proton diffusion of the hexagonal single crystals of the core-shell type tungsten polyacid clusters based on 3d-4p heterometallic clusters substituted by the product of Example 1 along the

[100] direction is most sensitive to temperature. The core-shell type tungsten polyacid clusters based on 3d-4p heterometallic clusters substituted by Na in the product of Example 1 along the

[001] ,

[110] and

[100] directions are composed of Na + The two-dimensional layer structure formed by ionic connection is as follows Figure 20-22 shown.

[0054] In addition, according to the Arrhenius formula (σT=σ0exp(-E a / k b T)), and estimate the activation energy E along the

[001] ,

[110] and

[100] directions a 0.33eV, 0.38eV and 0.49eV respectively (such as Fig.23 This indicates that proton conduction along the

[001] and

[110] directions belongs to the Grotthuss mechanism (<0.4 eV), and proton migration depends on the hydrogen bond network. The proton conduction process along the

[100] direction belongs to the Vehicular mechanism (>0.4 eV), and proton transfer depends on carrier transport.

[0055] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution, characterized in that: The molecular formula of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution is H 29 Na9(H2O) 21 {Ca(H2O)2@Sb 12 O 18 [Ni2(OH)(A-α-SiW 10 O 37 )]3}2·40H2O, where @ represents the core-shell structure, Ca 2+ Ions in {Sb 12 } cage, A-α represents the configuration of the metal-oxygen cluster; the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution crystallizes in the trigonal system, the space group is P-3, and the crystal structure is divided into {Ni2(A-SiW 10 )} shell and {Ca}@{Sb 12 The core consists of two parts, the shell structure is composed of three divacant {A-α-SiW 10 O 37 } and three dinuclear {Ni2O 10 (OH)} unit composition; with T d Symmetric {Ca}@{Sb 12 The core is composed of 12 SbO3 triangles and 1 {CaO6(H2O)2} dodecahedron. The 12 SbO3 triangles are assembled into a spherical hollow {Sb 12 }cage; {Sb 12 The cage contains four six-ring and four three-ring windows and is cup-shaped, enclosing an eight-coordinated Ca 2+ ions are packaged into one of the six-ring windows to form {Ca}@{Sb 12 }kernel.

2. A core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution according to claim 1, characterized in that: The unit cell parameters of the core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution are: α=β=90°, γ=120°, The calculated density is 3.829 g / cm 3 .

3. A method for preparing a core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution according to any one of claims 1 to 2, characterized in that: The specific preparation process is as follows: weigh the precursor Na 10 [A-α-SiW9O 34 ]·18H2O, nickel acetate tetrahydrate, antimony trichloride, and calcium chloride dihydrate are dissolved in a boric acid buffer solution of pH=9 and stirred thoroughly, then transferred into a glass bottle and placed in an oven for hydrothermal reaction. The hydrothermal reaction product is centrifuged and washed to obtain hexagonal crystals, that is, a core-shell tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution is obtained; the precursor Na 10 [A-α-SiW9O 34 ]·18H2O, nickel acetate tetrahydrate, antimony trichloride, calcium chloride dihydrate and boric acid buffer solution are added in a molar ratio of 2.2:4.0:3.8:8.5:1.5; the temperature of the hydrothermal reaction is 65°C and the reaction time is 5 days.

4. An application of a core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution as claimed in any one of claims 1 to 2, characterized in that: The core-shell type tungsten polyacid cluster compound based on 3d-4p heterometallic cluster substitution is used as a proton conducting material and is applied in the field of proton conduction.

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