Photosensitive metal-organic coordination nanocage material and preparation and application thereof

Abstract

The invention discloses a photosensitive metal-organic coordination nanocage material as well as preparation and application thereof. The photosensitive metal-organic coordination nanocage material comprises a photosensitive ligand, metal ions and counter anions. According to the metal-organic coordination nanocage material, pure water can be decomposed into hydrogen and hydrogen peroxide only through ultrasound and illumination under the condition that a sacrificial agent is not added, and the metal-organic coordination nanocage material has efficient piezoelectric electro-catalytic performance.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and in particular to a photosensitive metal-organic coordination nanocage material and its preparation and application. Background Art

[0002] With the continuous increase in global energy demand and the increasingly serious environmental problems, the development of efficient and clean energy conversion technologies has become a hot topic in current research. Photocatalytic water splitting hydrogen production technology has attracted much attention because it can directly convert solar energy into chemical energy. However, traditional photocatalytic materials often require sacrificial agents to promote the reaction, which not only increases the cost but also limits its widespread use in practical applications. In recent years, metal-organic coordination nanocages (MOC) materials have shown great potential in the field of photocatalysis due to their unique structure and controllable photoelectric properties. In particular, MOC materials with piezoelectric properties can generate internal electric fields under mechanical stress (such as ultrasound), further enhancing photocatalytic activity. Although some studies have reported the application of MOC materials in photocatalysis, most materials still rely on the presence of sacrificial agents, and their piezoelectric photocatalytic properties have not yet been developed. Summary of the Invention

[0003] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present invention aims to provide a photosensitive metal-organic coordination nanocage material and its preparation and application.

[0004] In order to achieve the above object, the technical solution adopted by the present invention is:

[0005] The first aspect of the present invention provides a metal-organic coordination nanocage material, the chemical formula of which includes at least one of the compounds of formula (I), formula (II) or formula (III):

[0006] Formula (I) [M] 3 (An) 2 (X) 6;

[0007] Formula (II)[M]6(Bn)8(X) 12 ;

[0008] Formula (III) [M]2(Cn)4(X)4;

[0009] Wherein, M is a metal ion, and each M is independently selected from Pd 2+ , Pt 2+ 、Co 2+ 、Zn 2+ 、Cu 2+ ;

[0010] X is a counter anion, and each X is independently selected from BF4 - 、NO3- PF4 - ;

[0011] An, Bn, and Cn are photosensitizing ligands; An is Bn is Cn is

[0012] Each R1 is independently selected from

[0013] Each R2 is selected from hydrogen, hydroxyl, C1-C6 alkoxy, polyether group;

[0014] R3 is selected from hydrogen, C1-C4 alkyl, C1-C4 alkyl alcohol, C1-C4 aldehyde, carboxyl, and amino.

[0015] In some embodiments of the present invention, each R2 is independently selected from hydrogen, hydroxy, methoxy, ethoxy, hexyloxy,

[0016] In some embodiments of the present invention, R3 is selected from hydrogen, methyl, methyl alcohol, aldehyde, carboxyl, and amino.

[0017] In some embodiments of the present invention, in formula (I), An comprises In some embodiments of the present invention, in formula (II), Bn includes At least one of.

[0018] In some embodiments of the present invention, in formula (III), Cn comprises At least one of.

[0019] In some embodiments of the present invention, the metal-organic coordination nanocage material comprises at least one of a compound of formula (I), a compound of formula (II), or a compound of formula (III):

[0020] Formula (I) [M] 3 (An) 2 (X) 6; wherein M is Pd 2+ ; X is NO3 - ;An

[0021]

[0022] Formula (II)[M]6(Bn)8(X) 12 ; Where M is Pd 2+ ; X is BF4 - ; Bn is

[0023] Formula (III) [M]2(Cn)4(X)4; wherein M is Pd 2+ ; X is BF4 - ; Cn is

[0024] The second aspect of the present invention provides a method for preparing the metal-organic coordination nanocage material, comprising the following steps:

[0025] The photosensitive ligand is reacted with a salt containing M and X to prepare the metal-organic coordination nanocage material.

[0026] In some embodiments of the present invention, the reaction temperature is 40-80° C., such as 50-70° C. or 60° C.; the reaction time is 2-5 h, such as 2-4 h or 3 h.

[0027] The third aspect of the present invention provides a use of the metal-organic coordination nanocage material in catalyzing water decomposition.

[0028] In some embodiments of the present invention, the catalysis comprises catalysis under light irradiation and / or ultrasound.

[0029] In some embodiments of the present invention, the illumination comprises illumination with visible light and / or ultraviolet light.

[0030] In some embodiments of the present invention, the wavelength of the visible light is 380 nm to 760 nm, such as 400 nm to 760 nm, or 420 nm to 760 nm.

[0031] In some embodiments of the present invention, the wavelength of the ultraviolet light is 10 nm to 380 nm, such as 50 to 380 nm.

[0032] In some embodiments of the present invention, the intensity of the light is 50 to 150 W / m 2 .

[0033] In some embodiments of the present invention, the frequency of the ultrasound is 20 kHz to 60 kHz.

[0034] In some embodiments of the present invention, the water decomposition includes decomposing water into at least one of hydrogen, oxygen, and hydrogen peroxide.

[0035] A fourth aspect of the present invention provides a method for catalyzing water decomposition, comprising using the metal-organic coordination nanocage material to catalyze water decomposition.

[0036] The beneficial effects of the present invention are:

[0037] The metal-organic coordination nanocage material of the present invention can decompose pure water into hydrogen and hydrogen peroxide only by ultrasound and light irradiation without adding a sacrificial agent, and has efficient piezoelectric photocatalytic performance.

[0038] In-situ pressurized ultraviolet-visible absorption spectrum research of the metal-organic coordination nanocage material of the present invention shows that its band gap changes significantly with changes in external pressure, and has the performance of changing light absorption capacity under pressure. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of A-3 in Example 1 of the present invention.

[0040] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of MOC-FA3 in Example 1 of the present invention.

[0041] Figure 3 Measured (top) and simulated (bottom) mass spectra of MOC-FA3 in Example 1 of the present invention.

[0042] Figure 4 Cyclic voltammograms of (A) ferrocene and (B) MOC-FA3 in Example 1 of the present invention; (C) UV-visible spectrum and fluorescence spectrum of MOC-FA3 in dimethyl sulfoxide; (D) energy level diagram of MOC-FA3.

[0043] Figure 5 The catalytic performance of MOC-FA3 under different conditions in Example 1 of the present invention is shown.

[0044] Figure 6 ] are the resonance peaks of MOC-FA3 under different applied voltages in Example 1 of the present invention.

[0045] Figure 7 1 and 2 are the phase hysteresis loop and amplitude butterfly loop of MOC-FA3 in Example 1 of the present invention.

[0046] Figure 8 In situ pressurized solid UV-visible absorption spectra of MOC-FA3 in Example 1 of the present invention: (A) spectrum when pressure is applied, (B) spectrum when pressure is released; (C) relationship between the band gap of MOC-FA3 and pressure and the corresponding UV-visible image.

[0047] Figure 9 This is the hydrogen nuclear magnetic resonance spectrum of B-3 in Example 2 of the present invention.

[0048] Figure 10 This is the hydrogen nuclear magnetic resonance spectrum of MOC-FB3 in Example 2 of the present invention.

[0049] Figure 11These are the measured (top) and simulated (bottom) mass spectra of MOC-FB3 in Example 2 of the present invention.

[0050] Figure 12 Cyclic voltammograms of (A) ferrocene and (B) MOC-FB3 in Example 2 of the present invention; (C) UV-visible spectrum and fluorescence spectrum of MOC-FB3 in dimethyl sulfoxide; (D) energy level diagram of MOC-FB3.

[0051] Figure 13 The catalytic performance of MOC-FB3 under different conditions in Example 2 of the present invention is shown.

[0052] Figure 14 ] are the resonance peaks of MOC-FB3 under different applied voltages in Example 2 of the present invention.

[0053] Figure 15 These are the phase hysteresis loop and amplitude butterfly loop of MOC-FB3 in Example 2 of the present invention.

[0054] Figure 16 This is the hydrogen nuclear magnetic resonance spectrum of C-3 in Example 3 of the present invention.

[0055] Figure 17 This is the hydrogen nuclear magnetic resonance spectrum of MOC-FC3 in Example 3 of the present invention.

[0056] Figure 18 Measured (top) and simulated (bottom) mass spectra of MOC-FC3 in Example 3 of the present invention.

[0057] Figure 19 Cyclic voltammograms of (A) ferrocene and (B) MOC-FC3 in Example 3 of the present invention; (C) UV-visible spectrum and fluorescence spectrum of MOC-FC3 in dimethyl sulfoxide; (D) energy level diagram of MOC-FC3.

[0058] Figure 20 The catalytic performance of MOC-FC3 under different conditions in Example 3 of the present invention is shown.

[0059] Figure 21 This is a diagram showing the mechanism of the metal-organic coordination nanocage material of the present invention for photolysis of water to produce hydrogen and hydrogen peroxide. DETAILED DESCRIPTION

[0060] The present invention is further described in detail below using specific examples. Unless otherwise specified, the raw materials, reagents, and apparatus used in the examples and comparative examples are available from conventional commercial sources or by conventional methods. Unless otherwise specified, all experimental or testing methods are conventional in the art.

[0061] In the embodiment of the present invention, the application test conditions of photocatalysis are described as follows:

[0062] Photolysis of water to produce hydrogen and hydrogen peroxide: 2 mg of metal-organic coordination nanocage material was added to a quartz reactor, followed by 20 mL of pure water. The reactor was subjected to light / ultrasound / light and ultrasound, and a certain amount of gas was taken at regular intervals to detect hydrogen in a gas chromatograph, and a certain amount of liquid was used to detect hydrogen peroxide.

[0063] Measurement of hydrogen peroxide amount: Quantification of hydrogen peroxide was accomplished by TMB-H2O2-HRP enzymatic assay using horseradish peroxidase as a transient catalyst for the reaction between hydrogen peroxide and tetramethylbenzidine.

[0064] Prepare 3,3',5,5'-tetramethylbenzidine (TMB) solution by dissolving 0.015 g of TMB in 0.3 mL of dimethyl sulfoxide. Add 5 mL of glycerol and 45 mL of deionized water containing 0.02 g of ethylenediaminetetraacetic acid and 0.095 g of citric acid. Bring the solution to a final volume of 500 mL with deionized water.

[0065] Preparation of horseradish peroxidase (HRP) solution: Dissolve 0.002 g of HRP in 10 μL of deionized water.

[0066] The calibration curve was constructed as follows: 200 μL of TMB solution and 10 μL of HRP solution were added to a hydrogen peroxide solution of known concentration. After 3 minutes, 10 μL of hydrochloric acid was added, and the resulting solution was analyzed by UV-visible spectroscopy at a wavelength of 450 nm. The linear relationship between signal intensity and hydrogen peroxide concentration was used to estimate the hydrogen peroxide concentration in the sample.

[0067] Example 1

[0068] This example prepares a metal-organic coordination nanocage MOC-FA3, and the specific process is as follows:

[0069] 1.1 Synthesis and characterization of organic ligand A-3:

[0070]

[0071] Under an argon atmosphere, A-3 (112.7 mg, 0.1 mmol), 3-pyridineboronic acid (73.4 mg, 0.6 mmol), tetrakis-(triphenylphosphine)palladium (34.6 mg, 0.03 mmol), dioxane (20 mL), and aqueous potassium carbonate (2 mL, 1.5 mol / L) were added to a 100 mL round-bottom flask. The reaction mixture was stirred at 95°C and the reaction progress was monitored by thin-layer chromatography (TLC). After cooling to room temperature, the mixture was rotary evaporated and extracted with chloroform. The organic phase was dried, and the crude product was purified by silica gel column chromatography to obtain 95.2 mg of A-3 as a red solid. Yield: 85%.

[0072] 1 H NMR (400MHz, Chloroform-d) δ (ppm): 9.00 (s, 3H), 8.56 (d, J = 4.8Hz, 3H), 8.16 (d, J = 3.8Hz, 3H), 8.01 (d, J = 7.9Hz, 12 H),7.79(d,J=7.5Hz,3H),7.50(d,J=3.9Hz,3H),7.45(d,J=8.2Hz,6H),7.37(dd,J=8.0,4.9Hz,3H).ESI-MS(m / z):C 63 H 36 N 10 S6Calculated:1125.1449([M+H] + ),found:1125.1513([M+H] + ).

[0073] A-3 1 H NMR spectrum Figure 1 .

[0074] 1.2. Synthesis and characterization of the molecular cage MOC-FA3

[0075]

[0076] A-3 (22.5 mg, 0.02 mmol) and tetramethylethylenediamine palladium nitrate (10.5 mg, 0.03 mmol) were dissolved in dimethyl sulfoxide (1.5 mL) and stirred at 60° C. for 3 h. The reactant was precipitated with ethyl acetate, filtered, and then dried in vacuo at 60° C. to obtain 24.5 mg of MOC-FA3 as a dark brown solid. Yield: 75%.

[0077] 1H NMR (400MHz, DMSO-d6) δ (ppm): 9.80 (s, 6H), 9.04 (d, J = 4.0Hz, 6H), 8.47 (d, J = 5. 5Hz,6H),8.12(d,J=6.6Hz,6H),8.05-7.84(m,24H),7.74(d,J=2.0Hz,6H),7.64 -7.48(dd,J=15.5,1.2Hz,6H),7.25(d,J=12.4Hz,12H),3.08(s,12H),2.76-2.69(m,36H).ESI-MS(m / z):[Pd3(A-3)2(NO3)4] 2+ Calculated:1583.1747,found:1583.1748.

[0078] MOC-FA3 1 H NMR spectrum Figure 2 , mass spectrum see Figure 3 .

[0079] In order to clarify the thermodynamic process of electron transfer in MOC-FA3, cyclic voltammetry tests were first performed. The results are as follows: Figure 4 As shown in (A) and (B), the first oxidation peak of MOC-FA3 appears at 1.04V vs NHE. Then, the UV-visible absorption and fluorescence emission of MOC-FA3 were measured. The results are shown in Figure 4 As shown in (C), the E of MOC-FA3 is obtained. 0-0 The value is 2.16eV. Therefore, the LUMO value of MOC-FA3 is -1.13V vs NHE, and the band structure is as follows Figure 4 As shown in (D).

[0080] 1.3. MOC-FA3 piezoelectric photocatalytic results

[0081] The piezoelectric photocatalytic performance of MOC-FA3 was tested under the conditions of ultrasound and light without sacrificial agent. The results showed that under visible light (λ>420nm, 100W / m 2 ) irradiation, 2mg MOC-FA3 in 20mL pure water, its hydrogen production efficiency is 334.3μmol / g / h and hydrogen peroxide production efficiency is 203.6μmol / g / h; under the condition of only ultrasound (40kHz), its hydrogen production efficiency is 186.8μmol / g / h and hydrogen peroxide production efficiency is 182.0μmol / g / h (see Figure 5 ).

[0082] 1.4 Characterization of MOC-FA3 piezoelectric photocatalysis

[0083] In order to study its piezoelectric properties, a piezoelectric force microscope was used. MOC-FA3 exhibits a clear resonance peak at 195 kHz (see Figure 6 ), which indicates that voltage-induced piezoelectric vibration occurs inside the material. At the same time, a significant linear correlation between the vibration amplitude and the applied excitation voltage can be observed, confirming the linear piezoelectric properties of these materials. In addition, the butterfly-shaped amplitude loop and phase curve (see Figure 7 ) further demonstrates their strong piezoelectricity. Under a sweeping bias voltage from -5 to 5 V, the maximum effective piezoelectric coefficient of MOC-FA3 was measured to be approximately 1.06 nm·V⁻¹. These results demonstrate that MOC-FA3 possesses strong intrinsic piezoelectricity.

[0084] In piezoelectric materials, the generated piezoelectric potential establishes an internal electric field that regulates the energy distribution of charge carriers and induces band bending. This effect can further enhance the redox activity of the material. To investigate the potential band gap changes in the material, we performed in situ UV / visible absorption spectroscopy measurements ( Figure 8 ).like Figure 8 As shown in (A) and (B), under the application of pressure from 0 to 15.1GPa, the absorption edge of MOC-FA3 gradually redshifts, and the band gap decreases significantly from 2.03eV to 1.27eV. When the pressure is released, the band gap almost returns to its initial value. The photos taken when the pressure is applied and released show that the material has a significant color change. As the pressure increases, the color changes from orange to black, and as the pressure is released, it changes from black back to orange ( Figure 8 (C)).

[0085] Example 2

[0086] This example prepares a metal-organic coordination nanocage MOC-FB3, and the specific process is as follows:

[0087] 2.1 Synthesis and characterization of organic ligand B-3:

[0088]

[0089] Under an argon atmosphere, B-1 (96.00 mg, 0.3 mmol), tris(4-boronic acid pinnesyl ester phenyl)amine (62.30 mg, 0.1 mmol), tetrakis-(triphenylphosphine) palladium (17.30 mg, 0.015 mmol), N,N-dimethylformamide (10 mL) and aqueous potassium carbonate solution (1.5 mL, 2 mol / L) were added to a 50 mL round-bottom flask. The reaction mixture was stirred at 100°C and the reaction progress was monitored by thin layer chromatography (TLC). After cooling to room temperature, the mixture was rotary evaporated and extracted with chloroform. The organic phase was dried and the crude product was purified by silica gel column chromatography to obtain 120 mg of a red solid B-2 (Scheme 3). Yield: 34%.

[0090] 1 H NMR (400MHz, DMSO-d6) δ (ppm): 8.81 (s, 1H), 8.39 (s, 1H), 8.09 (m, 3H), 8.00 (d, J = 7.8Hz, 2H), 7.37 (d, J = 8.3Hz, 2H), 3.95 (s, 3H). ESI-MS (m / z): C 54 H 36 N 10 O3S3 Calculated:968.2134([M+H] + ),found:968.2116([M+H] + ).。

[0091] B-3 1 H NMR spectrum Figure 9 .

[0092] Synthesis and characterization of the molecular cage MOC-FB3

[0093]

[0094] B-3 (19.38 mg, 0.02 mmol) and palladium tetrafluoroborate tetraacetonitrile (6.65 mg, 0.015 mmol) were dissolved in dimethyl sulfoxide (1.0 mL) and stirred at 60° C. for 12 h. The reactant was precipitated with ethyl acetate, filtered, and then dried in vacuo at 60° C. to obtain 16.50 mg of MOC-FB3 as a dark brown solid. Yield: 79%.

[0095] 1H NMR (400MHz, DMSO-d6) δ (ppm): 9.70 (s, 1H), 9.06 (s, 1H), 8.30 (d, J = 6.4Hz, 2H ),8.23(m,3H),7.31(d,J=8.2Hz,3H),4.09(s,3H).ESI-MS(m / z):[Pd6(B-3)8] 12+ Calculated:699.2614,found:699.2662.

[0096] MOC-FB3 1 H NMR spectrum Figure 10 , mass spectrum see Figure 11 .

[0097] In order to clarify the thermodynamic process of electron transfer in MOC-FB3, cyclic voltammetry test was first performed. The results are as follows Figure 12 As shown in A and B. The first oxidation peak of MOC-FB3 appears at 0.89V vs NHE. Then, the UV-visible absorption and fluorescence emission of MOC-FB3 were measured. The results are as follows Figure 12 As shown in C, the E of MOC-FB3 is obtained. 0-0 The value is 2.16eV. Therefore, the LUMO value of MOC-FB3 is -1.12V vs NHE, and the band structure is as follows Figure 12 As shown in D.

[0098] 2.3 MOC-FB3 piezoelectric photocatalytic results

[0099] The piezoelectric photocatalytic performance of MOC-FB3 was tested under the conditions of ultrasound and light without sacrificial agent. The results showed that under visible light (λ>420nm, 100W / m 2 ) irradiation, 2 mg of MOC-FA3 in 20 mL of pure water, its hydrogen production efficiency is 591.6 μmol / g / h and the hydrogen peroxide production efficiency is 351.2 μmol / g / h; under the condition of only ultrasound (40 kHz), its hydrogen production efficiency is 235.2 μmol / g / h and the hydrogen peroxide production efficiency is 200.2 μmol / g / h (see Figure 13 ).

[0100] 2.4 Characterization of MOC-FB3 piezoelectric photocatalysis

[0101] In order to study its piezoelectric properties, a piezoelectric force microscope was used. MOC-FB3 exhibits a clear resonance peak at 211 kHz (see Figure 14), which indicates that voltage-induced piezoelectric vibration occurs inside the material. At the same time, a significant linear correlation can be observed between the vibration amplitude and the applied excitation voltage, confirming the linear piezoelectric properties of these materials. In addition, the butterfly-shaped amplitude loop and phase curve further prove that they have strong piezoelectricity (see Figure 15 ).

[0102] Example 3

[0103] This example prepares a metal-organic coordination nanocage MOC-FC3, and the specific process is as follows:

[0104] 3.1 Synthesis and characterization of ligand C-3

[0105]

[0106] C-2 (59.5 mg, 0.1 mmol), 3-pyridineboronic acid (49.2 mg, 0.4 mmol), tetrakis-(triphenylphosphine)palladium (18.5 mg, 0.016 mmol), N,N-dimethylformamide (10 mL) and potassium carbonate aqueous solution (2.5 mL, 2.0 mol / L) were added to a 50 mL round-bottom flask under an argon atmosphere, stirred and heated to 100 ° C for reaction, and the reaction progress was monitored by thin layer chromatography (TLC). After the reaction was completed, the mixture was cooled to room temperature, and 50 mL of water and 30 mL of dimethyl chloride were added sequentially for extraction. The organic phase was collected, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain 46.1 mg of yellow solid C-3 with a yield of 78%.

[0107] 1 H NMR (400MHz, Chloroform-d) δ (ppm): 9.86 (s, 1H), 8.90 (s, 2H), 8.52 (d, J = 4.2Hz, 2H), 7.88 (d, J = 8.0Hz, 2H), 7.74 (d, J = 8.6Hz, 2 H),7.60(d,J=8.5Hz,4H),7.35(d,J=3.8Hz,2H),7.34-7.29(m,4H),7.20(d,J=8.5Hz,4H),7.16(d,J=8.5Hz,2H).ESI-MS(m / z):C 37 H 26 N3OS2 + Calculated:592.1512([M+H] + ),found:592.1514([M+H] + ).C-3 1 H NMR spectrum Figure 16 .

[0108] 3.2 Synthesis and characterization of molecular cage MOC-FC3

[0109]

[0110] C-3 (30.0 mg, 0.05 mmol) and palladium tetrafluoroborate tetraacetonitrile (Pd(BF4)2(MeCN)4) (13.5 mg, 0.03 mmol) were dissolved in dimethyl sulfoxide (1.5 mL) and stirred at 70°C for 0.5 h. After cooling, a large amount of ethyl acetate was added to precipitate the solid, which was centrifuged and dried in vacuo at 60°C for 6 h to afford MOC-FC3 as a yellow solid (27 mg, 73% yield).

[0111] 1 H NMR (400MHz, DMSO-d6) δ (ppm): 9.62 (s, 1H), 9.49 (s, 2H), 9.06 (d, J = 5.4Hz, 2H), 8.52 (d, J = 8.1Hz, 2H), 7.85-7.79 (m, 4H), 7 .76(d,J=3.6Hz,2H),7.71(d,J=8.3Hz,4H),7.62(d,J=8.5Hz,2H),6.99(t,J=7.9Hz,6H).ESI-MS(m / z):[Pd2(C-3)4(BF4)2] 2+ Calculated:1376.1968,found:1376.1977.

[0112] MOC-FC3 1 H NMR spectrum Figure 17 , mass spectrum see Figure 18 .

[0113] In order to clarify the thermodynamic process of electron transfer in MOC-FC3, cyclic voltammetry test was first performed. The results are as follows: Figure 19 As shown in (A) and (B), the first oxidation peak of MOC-FC3 appears at 0.89V vs NHE. Then, the UV-visible absorption and fluorescence emission of MOC-FC3 were measured. The results are as follows: Figure 19 As shown in (C), the E of MOC-FC3 was obtained. 0-0 The value is 2.83eV. Therefore, the LUMO value of MOC-FC3 is -1.96V vs NHE, and the band structure is as follows Figure 19 As shown in (D).

[0114] 3.3 MOC-FC3 piezoelectric photocatalytic results

[0115] The piezoelectric photocatalytic performance of MOC-FC3 was tested under the conditions of ultrasound and light irradiation without sacrificial agent. The results showed that under visible light (λ>420nm, 100W / m 2 ) irradiation, 2mg MOC-FC3 in 20mL pure water, its hydrogen production efficiency is 812.1μmol / g / h, the efficiency of hydrogen peroxide production is 480.7μmol / g / h; under the condition of only ultrasound (40kHz), its hydrogen production efficiency is 221.8μmol / g / h, the efficiency of hydrogen peroxide production is 137.6μmol / g / h (see Figure 20 ).

[0116] In summary, the photosensitive metal-organic coordination nanocage material of the present invention produces hydrogen and hydrogen peroxide by photolysis of water. Figure 21 shown.

[0117] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A metal-organic coordination nanocage material, characterized by: Its chemical formula includes at least one of the compound of formula (I), the compound of formula (II) or the compound of formula (III): Formula (I) [M] 3 (An) 2 (X) 6; Formula (II)[M]6(Bn)8(X) 12 ; Formula (III) [M]2(Cn)4(X)4; Wherein, M is a metal ion, and each M is independently selected from Pd 2+ , Pt 2+ 、Co 2+ 、Zn 2+ 、Cu 2+ ; X is a counter anion, and each X is independently selected from BF4 - 、NO3 - PF4 - ; An, Bn, and Cn are photosensitizing ligands; An is Bn is Cn is Each R1 is independently selected from Each R2 is selected from hydrogen, hydroxyl, C1-C6 alkoxy, polyether group; R3 is selected from hydrogen, C1-C4 alkyl, C1-C4 alkyl alcohol, C1-C4 aldehyde, carboxyl, and amino.

2. The metal-organic coordination nanocage material according to claim 1, characterized in that: Each R2 is independently selected from hydrogen, hydroxy, methoxy, ethoxy, hexyloxy, 3. The metal-organic coordination nanocage material according to claim 1, characterized in that: In formula (I), An includes At least one; and / or; In formula (II), Bn includes At least one; and / or, in formula (III), Cn includes At least one of.

4. The metal-organic coordination nanocage material according to claim 1, characterized in that: The metal-organic coordination nanocage material comprises at least one of the compounds of formula (I), formula (II) or formula (III): Formula (I) [M] 3 (An) 2 (X) 6; wherein M is Pd 2+ ; X is NO3 - ;An Formula (II)[M]6(Bn)8(X) 12 ; Where M is Pd 2+ ; X is BF4 - ; Bn is Formula (III) [M]2(Cn)4(X)4; wherein M is Pd 2+ ; X is BF4 - ; Cn is 5. A method for preparing the metal-organic coordination nanocage material according to any one of claims 1 to 3, characterized in that: The following steps are involved: The photosensitive ligand is reacted with a salt containing M and X to prepare the metal-organic coordination nanocage material.

6. Use of the metal-organic coordination nanocage material according to any one of claims 1 to 3 in catalyzing water decomposition.

7. The use according to claim 5, characterized in that: The catalysis includes catalysis under light irradiation and / or ultrasound.

8. The use according to claim 5, characterized in that: The illumination includes illumination of visible light and / or ultraviolet light.

9. The use according to claim 5, characterized in that: The water decomposition includes decomposing water into at least one of hydrogen, oxygen and hydrogen peroxide.

10. A method for catalyzing water decomposition, comprising catalyzing water decomposition using the metal-organic coordination nanocage material according to any one of claims 1 to 3.

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