CN116425996A - Metal organic framework material and ligand thereof and application of metal organic framework material in photocatalytic hydrogen production - Google Patents

Metal organic framework material and ligand thereof and application of metal organic framework material in photocatalytic hydrogen production Download PDF

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CN116425996A
CN116425996A CN202310691463.6A CN202310691463A CN116425996A CN 116425996 A CN116425996 A CN 116425996A CN 202310691463 A CN202310691463 A CN 202310691463A CN 116425996 A CN116425996 A CN 116425996A
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organic framework
metal organic
framework material
hydrogen production
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CN116425996B (en
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赵礼义
李衍初
曹宇
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Jilin Zhuo Cai Xin Yan Technology Co ltd
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a metal organic framework material, a ligand structure thereof and application thereof in photocatalytic hydrogen production, and belongs to the technical field of photocatalytic water splitting hydrogen production. The invention prepares a ligand structure and applies the ligand structure to the synthesis of a novel metal organic framework material MOF-ET19, the MOF-ET19 material can be used as a raw material for preparing a photocatalyst, and the V prepared by using the metal organic framework material is tested 2 O 5 the/MOF-ET 19 catalyst has excellent photocatalytic activity and high hydrogen production rate, and the hydrogen production rate is 70.25mmol ‧ g ‑1 ‧h ‑1 Has outstanding application prospect and development potential in the field of catalytic hydrogen production. In addition, the metal organic framework material synthesis method provided by the invention has the advantages of simple process, mild conditions and the like.

Description

Metal organic framework material and ligand thereof and application of metal organic framework material in photocatalytic hydrogen production
Technical Field
The invention relates to a metal organic framework material, a ligand structure thereof and application thereof in photocatalytic hydrogen production, and belongs to the technical field of photocatalytic water decomposition hydrogen production.
Background
Hydrogen energy is an important choice for solving the problem of social energy in the future by virtue of the advantages of abundant resources and wide application, so that the hydrogen production technology is developed on a large scale all over the world. The common hydrogen production technologies mainly comprise fossil energy reforming hydrogen production, electrolytic water hydrogen production and photocatalysis hydrogen production, but the electrolytic water hydrogen production consumes a large amount of electric energy, the fossil energy reforming hydrogen production also causes a certain environmental pollution, and has no potential for sustainable development, and the photocatalysis hydrogen production is converted into chemical energy through a photocatalysis process, is environment-friendly and has low energy consumption, and is considered as a very effective solution for solving the current energy crisis and environmental pollution problems.
Photocatalytic hydrogen production is to produce hydrogen by catalytically decomposing water under light conditions, and the reaction rate of generating hydrogen is mostly dependent on the type and amount of photocatalyst in the system. In the past decades, photocatalysts for producing hydrogen by photolysis of water are mainly semiconductors such as titanium dioxide and zinc oxide, but because the traditional semiconductors are weak in light absorption, the separation of photo-generated carriers is poor, and the efficiency of photocatalytic hydrogen production is greatly limited, so that in order to more effectively utilize solar spectrum, searching for a cheap, active, rich, efficient and stable photocatalyst is a main challenge at present.
The metal organic framework material (Metal Organic Framework, MOF) is a novel porous material formed by coordination with metal ions or organic ligands as connection points, and has wide application in the fields of catalysis, energy storage, separation and the like. The porous structure of the MOF is beneficial to the diffusion of reaction substrates and products, the transmission distance of carriers from the electrolyte to the active sites on the surface of the MOF can be shortened, and in addition, the exposed unsaturated metal sites can be used as the active sites to participate in the photocatalytic reaction, so that the aim of promoting the photocatalytic reaction can be fulfilled. However, the photocatalytic activity of the existing metal-organic framework material is still limited by the narrow light absorption range and poor separation efficiency of photo-generated carriers, so that the novel metal-organic framework material is provided, and is applied to the preparation of a photocatalyst, so that the photocatalyst can effectively inhibit the recombination of the photo-generated carriers, thereby adjusting the charge property of MOF and greatly improving the hydrogen production rate.
Disclosure of Invention
The invention provides a metal organic frame material and a preparation method thereof, and the metal organic frame material is used as a photocatalyst, so as to effectively inhibit the recombination of photo-generated carriers and greatly improve the hydrogen production rate.
The technical scheme of the invention is as follows:
one of the objects of the present invention is to provide a metal organic framework material, abbreviated as MOF-ET19, of the formula [ Ti (L) 4 ]Wherein L is C 28 H 32 N 2 O 6 。
The second object of the present invention is to provide a method for preparing the above metal organic framework material, which comprises the following steps:
adding ligand, tetraisopropyl titanate, N-dimethylformamide and methanol into a three-mouth bottle, continuously stirring the mixture until the mixture is completely dissolved, pouring the mixture into a polytetrafluoroethylene-lined test tube, then placing the test tube into an autoclave, heating the test tube in an oven at 150 ℃ for 15 hours, centrifugally collecting a product, washing the product with the N, N-dimethylformamide and the methanol for 3 times, and drying the product in vacuum overnight to obtain the MOF-ET19.
It is still another object of the present invention to provide a ligand for preparing the above metal organic framework material, the ligand having the structure:
Figure SMS_1
。
the fourth object of the present invention is to provide a method for preparing a ligand of the above metal organic framework material, comprising the steps of:
s1, adding 1, 4-phenyldibutyl alcohol and iodine into a three-mouth bottle, then dropwise adding bromine into the three-mouth bottle, stirring the mixture at 25 ℃ for 48 hours, adding sodium hydroxide aqueous solution after the reaction is finished, extracting the aqueous phase with diethyl ether for three times, washing the combined organic phase with water, and drying the organic phase with magnesium sulfate to obtain white solid, namely an intermediate 1;
s2, adding the intermediate 1, the pinacol diboronate, DPPF palladium dichloride and potassium acetate into a three-port bottle, vacuumizing for three times, adding dry N, N-dimethylformamide under the protection of nitrogen, and stirring the reaction mixture at 85 ℃ for reaction for 18 hours. After the reaction is finished, slowly cooling the reaction system to 25 ℃, adding water, extracting with dichloromethane three times, washing an organic phase with water for three times, drying with sodium sulfate, removing an organic solvent under reduced pressure, and finally performing silica gel column chromatography purification by taking n-hexane/ethyl acetate as an eluent to obtain a white solid, namely an intermediate 2;
s3, adding a mixture of water and 1, 4-dioxane into a three-mouth bottle, adding an intermediate 2, 2-amino-4-bromobenzoate and cesium fluoride, introducing argon for 30min, adding DPPF palladium dichloride, stirring the reaction system under the protection of argon for reaction for 24h, slowly cooling the reaction system to 25 ℃, washing an organic phase with water, extracting with dichloromethane, washing the combined organic phase with saline, drying on sodium sulfate, finally removing an organic solvent in vacuum, and performing silica gel column chromatography purification by taking n-hexane/ethyl acetate as an eluent to obtain a yellow solid, namely an intermediate 3;
s4, dissolving the intermediate 3 in a mixed solution of tetrahydrofuran and methanol, adding sodium hydroxide, heating and refluxing reactants for 24 hours, after the reaction is finished, slowly cooling a reaction system to 25 ℃, removing an organic solvent in vacuum, adding hydrochloric acid into an aqueous solution, adjusting the pH to 5, centrifuging, taking out a supernatant, washing a precipitate with water, and drying in vacuum to obtain a light brown solid, namely the ligand.
The fifth object of the present invention is to provide the use of the above metal-organic framework material, in particular for the preparation of photocatalysts.
The sixth object of the present invention is to provide a method for preparing V from the above metal organic framework material 2 O 5 Method of preparing/MOF-ET 19 photocatalystThe method comprises the following steps: dispersing MOF-ET19 and vanadium pentoxide in acetonitrile, ultrasonic treating, drying the suspension in an oven at 85deg.C, and grinding the dried solid into powder to obtain V 2 O 5 /MOF-ET19。
The invention also provides an application of the photocatalyst prepared by the method, and the photocatalyst is particularly used for preparing hydrogen by photocatalytic decomposition of water.
The invention has the following beneficial effects:
the invention prepares a ligand structure and applies the ligand structure to the synthesis of novel metal organic framework materials, the MOF materials can be used as raw materials for preparing photocatalyst, and the V prepared by using the metal organic framework materials is tested 2 O 5 The catalyst of the MOF-ET19 has excellent photocatalytic activity and high hydrogen production rate, and the hydrogen production rate is 70.25m mol ‧ g -1 ‧h -1 Has outstanding application prospect and development potential in the field of catalytic hydrogen production. In addition, the metal organic framework material synthesis method provided by the invention has the advantages of simple process, mild conditions and the like.
Drawings
FIG. 1 is a synthetic route for preparing ligands for metal organic framework materials;
FIG. 2 is a diagram of intermediate 1 prepared in example 1 1 H-NMR spectrum;
FIG. 3 is a diagram of intermediate 1 prepared in example 1 13 C-NMR spectrum;
FIG. 4 is a mass spectrum of intermediate 1 prepared in example 1;
FIG. 5 is a diagram of intermediate 2 prepared in example 1 1 H-NMR spectrum;
FIG. 6 is a diagram of intermediate 2 prepared in example 1 13 C-NMR spectrum;
FIG. 7 is a mass spectrum of intermediate 2 prepared in example 1;
FIG. 8 is a diagram of intermediate 3 prepared in example 1 1 H-NMR spectrum;
FIG. 9 is a diagram of intermediate 3 prepared in example 1 13 C-NMR spectrum;
FIG. 10 is a mass spectrum of intermediate 3 prepared in example 1;
FIG. 11 shows the ligand prepared in example 1 1 H-NMR spectrum;
FIG. 12 is a diagram of the ligands prepared in example 1 13 C-NMR spectrum;
FIG. 13 is a mass spectrum of the ligand prepared in example 1;
FIG. 14 is a graph of photoelectrochemical test results for different photocatalysts;
FIG. 15 is a graph showing electrochemical impedance test results for different photocatalysts;
FIG. 16 is a graph showing the results of hydrogen production rate tests for different photocatalysts.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
1, 4-Benzenedictanol (starting material 1, CAS:21240-37-9), pinacol ester of biboron (starting material 2, CAS:73183-34-3), methyl 2-amino-4-bromobenzoate (starting material 3, CAS:135484-83-2) used in the examples below were all obtained by direct purchase from Sigma-Aldrich company.
The elemental analysis of the following examples was performed using a german Elementar UNICUBE elemental analyzer.
Example 1:
the process for preparing the metal organic framework material MOF-ET19 of this example is as follows:
(1) As shown in fig. 1, the ligand was synthesized:
(1) synthetic intermediate 1:
1, 4-Benzenedictanol (72.03 g,324 mmol) and iodine (819 mg,3.23 mmol) were added to a three-necked flask, and then bromine (33.05 mL, 640 mmol) was added dropwise thereto. Subsequently, the mixture was stirred at 25℃for 48h. After the reaction, 10mL of 20% strength by mass aqueous sodium hydroxide solution was added, and the aqueous phase was extracted three times with diethyl ether. Finally, the combined organic phases were washed with water and dried over magnesium sulfate to give 108g of white solid, intermediate 1, in 88% yield.
The intermediate 1 obtained was structurally characterized:
<1> nuclear magnetic characterization results:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO):δ7.33 (s, 2H), 3.84 (s, 2H), 3.64 (m, 4H), 2.81 (m, 4H), 1.72 (m, 4H), 1.62 (m, 4H), as shown in FIG. 2.
Carbon spectrum: 13 C NMR (100 MHz, DMSO):δ145.04, 134.69, 127.88, 62.44, 36.00, 31.61, 27.83 as shown in fig. 3.
<2> mass spectrometry characterization results:
ESI(m/z): [M+H] + theoretical calculation C 14 H 20 Br 2 O 2 380.12; actual measurement 381.09. As shown in fig. 4.
<3> elemental analysis test results:
theoretical calculation C 14 H 20 Br 2 O 2 C, 44.24, H, 5.30, O, 8.42; actual measurements of C, 45.13, H, 6.12, O, 9.07.
In summary, the structure of the intermediate 1 obtained is as follows:
Figure SMS_2
。
(2) synthesis of intermediate 2:
to a three-necked flask was added intermediate 1 (1.95 g,5.14 mmol), pinacol biborate (3 g,11.8 mmol), DPPF palladium dichloride (226 mg,0.308 mmol) and potassium acetate (3.02 g,30.8 mmol), followed by three vacuums. Then, 80mL of dried N, N-dimethylformamide was added under nitrogen protection, and the reaction mixture was stirred at 85℃for 18 hours. After the reaction was completed, the reaction system was slowly cooled to 25 ℃, 100mL of water was added, and extraction was performed three times with 50mL of dichloromethane each time. The organic phase was washed three times with 100mL of water each time, then dried over sodium sulfate and the organic solvent was removed under reduced pressure. Finally, silica gel column chromatography purification is carried out by taking normal hexane/ethyl acetate (volume ratio is 20:1) as an eluent, and 1.56g of white solid is obtained, namely intermediate 2, and the yield is 64%.
The intermediate 2 obtained was structurally characterized:
<1> nuclear magnetic characterization results:
hydrogen spectrum: 1 H NMR (400 MHz, CDCl 3 ):δ7.35 (m, 2H), 3.88 (m, 4H), 2.80 (m, 6H), 1.81 (m, 8H), 1.23 (s, 24H), as shown in FIG. 5.
Carbon spectrum: 13 C NMR (100 MHz, CDCl 3 ):δ135.46, 134.08, 87.49, 62.44, 36.15, 31.61, 27.83, 24.70 as shown in fig. 6.
<2> mass spectrometry characterization results:
ESI(m/z): [M+H] + theoretical calculation C 26 H 44 B 2 O 6 474.25; actual measurement 475.02. As shown in fig. 7.
<3> elemental analysis test results:
theoretical calculation C 26 H 44 B 2 O 6 C, 65.85, H, 9.35, O, 20.24; actual measurements of C, 66.73, H, 10.19, O, 10.16.
In summary, the structure of the intermediate 2 obtained is as follows:
Figure SMS_3
。
(3) synthetic intermediate 3:
to a three-necked flask was added 80mL of a mixture of water and 1, 4-dioxane (volume ratio 1:1), intermediate 2 (1.85 g,3.9 mmol), methyl 2-amino-4-bromobenzoate (2.3 g,10 mmol) and cesium fluoride (3.7 g,24 mmol). Argon was purged for 30min and DPPF palladium dichloride (230 mg,0.3 mmol) was added. And stirring the reaction system under the protection of argon for reaction for 24 hours. After the reaction was completed, the reaction system was slowly cooled to 25 ℃. The organic phase was then washed with 100mL of dichloromethane, then 50mL of brine, and dried over sodium sulfate. Finally, the organic solvent was removed in vacuo and purified by column chromatography on silica gel using n-hexane/ethyl acetate (volume ratio 10:1) as eluent to give 1.56g of yellow solid as intermediate 3 in 76.9% yield.
The intermediate 3 obtained was structurally characterized:
<1> nuclear magnetic characterization results:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO):δ8.12 (m, 4H), 7.28 (m, 2H), 7.12 (m, 2H), 6.63 (s, 4H), 3.98 (s, 6H), 3.73 (s, 2H), 3.55 (m, 4H), 2.76 (m, 4H), 1.72 (m, 4H), 1.56 (m, 4H), as shown in FIG. 8.
Carbon spectrum: 13 c NMR (100 MHz, DMSO): 169.05, 150.00, 144.74, 142.35, 140.40, 126.69, 122.73, 118.09, 109.24, 62.44, 52.08, 34.82, 31.61, 27.83, as shown in FIG. 9.
<2> mass spectrometry characterization results:
ESI(m/z): [M+H] + theoretical calculation C 30 H 36 N 2 O 6 520.63; actual measurement 521.55. As shown in fig. 10.
<3> elemental analysis test results:
theoretical calculation C 30 H 36 N 2 O 6 C, 69.21, H, 6.97, O, 18.44; actual measurements of C, 70.13, H, 7.69, O, 19.36.
In summary, the structure of the obtained intermediate 3 is as follows:
Figure SMS_4
。
(4) synthesizing a ligand:
intermediate 3 (1.56 g,3 mmol) was dissolved in 60mL of a mixture of tetrahydrofuran and methanol (1:1 by volume) and sodium hydroxide solution (1.2 g,30 mL) was added. The reaction was then heated and refluxed for 24h. After the reaction was completed, the reaction system was slowly cooled to 25 ℃, and then the organic solvent was removed in vacuo. Then 1mol/L hydrochloric acid was added to the aqueous solution until the pH was 5. Centrifuging and removing the supernatant. The precipitate was again washed 3 times with 40mL of water and dried in vacuo to give 1.33g of a pale brown solid in 90% yield.
Structural characterization of the ligand obtained:
<1> nuclear magnetic characterization results:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO):δ8.24 (m, 2H), 7.94 (s, 2H), 7.34 (m, 2H), 7.17 (m, 2H), 6.28 (s, 4H), 3.79 (s, 2H), 3.60 (m, 4H), 2.76 (m, 4H), 1.70 (m, 4H), 1.58 (m, 4H), as shown in FIG. 11.
Carbon spectrum: 13 C NMR (100 MHz, DMSO):δ170.77, 147.19, 144.74, 142.59, 140.40, 128.28, 123.09, 116.17, 111.54, 62.44, 34.82, 31.61, 27.83 as shown in fig. 12.
<2> mass spectrometry characterization results:
ESI(m/z): [M+H] + theoretical calculation C 28 H 32 N 2 O 6 492.57; actual measurement 493.46. As shown in fig. 13.
<3> elemental analysis test results:
theoretical calculation C 28 H 32 N 2 O 6 C, 68.28, H, 6.55, O, 19.49; actual measurements of C, 69.13, H, 7.32, O, 20.13.
In summary, the structure of the ligand obtained is as follows:
Figure SMS_5
。
(2) Synthetic metal organic framework material MOF-ET19:
to a three-necked flask, 600mg of ligand, 0.53mL of tetraisopropyl titanate, 15mL of N, N-dimethylformamide and 15mL of methanol were added, and after the mixture was continuously stirred until completely dissolved, it was poured into a polytetrafluoroethylene-lined test tube, and then placed in an autoclave, and heated in an oven at 150℃for 15 hours. Finally, centrifugally collecting a product, washing the product with N, N-dimethylformamide and methanol for 3 times, and drying the product in vacuum overnight to obtain the MOF-ET19.
The obtained MOF-ET19 was subjected to structural characterization:
<1> the synthesized MOF-ET19 crystals were stored in glass capillaries and tested for crystal structure using single crystal X-rays, the instrument was a Bruker-Apex type ii CCD detector, and were acquired using a Cu ka (λ= 1.54178 a) X-ray source. The data are that the SADABS program corrects for absorption, and not extinction or decay. The solution was directly performed using the SHELXTL software package and the test results are shown in Table 1.
TABLE 1
Figure SMS_6
This example uses the metal organic framework material MOF-ET19 obtained above to prepare V 2 O 5 The specific preparation process of the MOF-ET19 photocatalyst is as follows:
dispersing 50mg of MOF-ET19 and 2mg of vanadium pentoxide in 3mL of acetonitrile, carrying out ultrasonic treatment, drying the suspension in an oven at 85 ℃, and grinding the dried solid into powder to obtain V 2 O 5 /MOF-ET19。
For V obtained 2 O 5 The performance of the/MOF-ET 19 photocatalyst was tested and the test procedure and results were as follows:
first, photoelectrochemical (PEC) test
The instrument used for the test was a CHI 760E electrochemical workstation, a standard three-electrode configuration was used, and an aqueous solution of sodium sulfate (0.1 mol/L) was used as the electrolyte. Will 3mg V 2 O 5 mixing/MOF-ET 19 photocatalyst, 1.5mL ethanol and 10 μL Nafion 117 to form suspension, ultrasonic treating, and dripping 50 μL of the mixture on ITO conductive glass (working area of electrode is 2.0X12.0 cm) 2 ). Then, using the sampleThe ITO glass of (C) is used as a working electrode. The reference electrode and the counter electrode are Ag/AgCl electrode and platinum electrode respectively. The light source is a 300W Xe lamp with an ultraviolet cut-off filter>380 nm). Photocurrent measurements were tested at a bias potential of +0.4v.
As shown in FIG. 14, when the material is de-excited by light energy, electrons in the valence band are excited to transition to the conduction band, and under the action of an electric field, the conduction band electrons move directionally to form a current, wherein V 2 O 5 The density of photocurrent of the/MOF-ET 19 was 0.85. Mu.A/cm 2 Higher than Pt/UiO-66-NH 2 And MoO 3 /MIL-125-NH 2 The higher the photocurrent density, the better the separation effect of photo-generated electron-hole pairs, the less recombination, and thus the corresponding higher photocatalytic activity, thus indicating V 2 O 5 the/MOF-ET 19 has higher photocatalytic activity.
Second, electrochemical impedance testing
The ITO glass with the sample is used as a working electrode, the Ag/AgCl electrode and the platinum electrode are respectively a reference electrode and a counter electrode, the alternating current impedance test frequency range is 100 KHz-10 MHz, and the alternating current disturbance signal is 5mV.
As shown in FIG. 15, the radius of the arc obtained from the test represents the resistance of the electrode/electrolyte interface, and the smaller the radius, the lower the charge transfer resistance, and therefore the value of V 2 O 5 The electrode of which/MOF-ET 19 is a photocatalyst has smaller charge transfer resistance, indicating that the composite electrode/electrolyte interface charge transfer resistance is compared with Pt/UiO-66-NH 2 And MoO 3 /MIL-125-NH 2 Smaller.
Third, photocatalytic Hydrogen production Rate testing
Into a 100mL airtight quartz glass reactor was charged 10mg V 2 O 5 MOF-ET19 catalyst, 30mL acetonitrile, 200. Mu.L deionized water and 600. Mu.L triethylamine. Before the irradiation, the reaction solution was bubbled with high-purity nitrogen for 20min to remove air, and a 300W Xe lamp was used as a full-wavelength light source, equipped with a cut-off filter (400 nm<λ<780 nm). Continuously stirring the reaction solution under irradiation of visible light, and maintaining the temperature by circulating cooling water to1h is a fixed time interval, the gas product was evaluated by gas chromatography (GC, shimadzu GC-2014) and compared with MoO 3 /MIL-125-NH 2 、Pt/UiO-66-NH 2 A comparison was made for the photocatalyst.
The test results are shown in FIG. 16, V 2 O 5 MOF-ET19 exhibits excellent hydrogen production performance at a hydrogen production rate of 70.25mmol ‧ g -1 ‧h -1 ，Pt/UiO-66-NH 2 The hydrogen production rate of the photocatalyst is 46mmol ‧ g -1 ‧h -1 Is made of Pt/UiO-66-NH 2 1.53 times of the hydrogen production rate of the photocatalyst and exceeds that of the photocatalyst in MoO 3 /MIL-125-NH 2 Is the hydrogen production rate of the photocatalyst.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (5)

1. A metal organic framework material is characterized in that the material is simply called MOF-ET19, and the chemical formula is [ Ti (L) ] 4 ]Wherein L is C 28 H 32 N 2 O 6 。
2. A ligand for preparing the metal organic framework material of claim 1, characterized by the structure:
Figure QLYQS_1
。
3. use of a metal organic framework material according to claim 1 for the preparation of a photocatalyst.
4. V (V) 2 O 5 The MOF-ET19 photocatalyst is characterized in that the photocatalyst is prepared by taking the metal organic framework material as the raw material in claim 1.
5. V as claimed in claim 4 2 O 5 The application of the MOF-ET19 photocatalyst is characterized in that the photocatalyst is used for preparing hydrogen by photocatalytic decomposition of water.
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CN111346611A (en) * 2020-03-13 2020-06-30 吉林中科研伸科技有限公司 Novel porous metal organic framework material and preparation method and application thereof
US20210162388A1 (en) * 2019-12-02 2021-06-03 Center for Innovative Materials and Architectures METAL ORGANIC FRAMEWORKS (MOFs) AND METHODS OF SYNTHESIZING AND USING THE SAME
CN115232327A (en) * 2022-09-22 2022-10-25 吉林中科研伸科技有限公司 Metal organic framework material and preparation method and application thereof
CN116143618A (en) * 2023-04-19 2023-05-23 吉林省卓材新研科技有限公司 Metal organic frame material for water-based zinc ion battery, ligand and application

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CN111346611A (en) * 2020-03-13 2020-06-30 吉林中科研伸科技有限公司 Novel porous metal organic framework material and preparation method and application thereof
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