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Bismuth-based metal organic framework material as well as preparation method and application thereof

An organic framework and metal-based technology, applied in organic chemical methods, bismuth organic compounds, organic chemistry, etc., can solve the problems of poor electronic conductivity and unfavorable electron transfer of related MOFs, and achieve good photocatalytic reduction performance, low cost, The effect of high yield

Active Publication Date: 2021-03-19
SHANDONG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The inventors found that the reported Bi-based MOFs mainly contain carboxylic acid groups in the organic ligands, and the carboxylic acid groups are generally considered to be unfavorable for electron transfer, resulting in poor electronic conductivity of the related MOFs

Method used

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  • Bismuth-based metal organic framework material as well as preparation method and application thereof
  • Bismuth-based metal organic framework material as well as preparation method and application thereof
  • Bismuth-based metal organic framework material as well as preparation method and application thereof

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preparation example Construction

[0031] In yet another specific embodiment of the present invention, the preparation method includes: adding triphenylbismuth and 4-mercaptobenzoic acid into an organic solvent, adding benzoic acid at the same time, mixing evenly, and heating to reflux to obtain the product. In the preparation method, using triphenylbismuth as the Bi source can effectively avoid the hydrolysis of Bi.

[0032] In yet another specific embodiment of the present invention, the organic solvent includes xylene, toluene, carbon tetrachloride, etc., preferably xylene;

[0033] In yet another specific embodiment of the present invention, the molar ratio of the triphenylbismuth, 4-mercaptobenzoic acid and benzoic acid is 1:1~5:1~5; more preferably 1:2.18:2.18; by controlling The dosage ratio of each raw material can speed up the reaction and effectively improve the yield.

[0034] In yet another specific embodiment of the present invention, the specific conditions for heating to reflux are: react at 50-...

Embodiment 1

[0049] A preparation method of Bi-based metal-organic framework (Bi-MBA), the steps are as follows:

[0050] Add triphenylbismuth (51.6mg, 0.117mmol) and 4-mercaptobenzoic acid (39.2mg, 0.255mmol) into xylene (18mL), stir for 30min, and reflux at 60°C for 24h. Adding benzoic acid (31.1mg, 0.255mmol) as a regulator during the synthesis can obtain high-quality single crystals. After the reaction was sufficient, the yellow product was collected after cooling, filtering, washing (3 times with methanol and acetone), and drying (drying in an oven at 120° C. for 24 h). The yield was 82.3%.

[0051] Such as figure 1 As shown, Bi-MBA along the crystallographic a-axis is a one-dimensional Bi 2 S 4 Characterized by the crystal structure of the long chain, crystallized in the orthonormal space group Cmcm. Each Bi(III) is coordinated to one benzene ring of triphenylbismuth as a Bi source and four sulfur atoms in four ligand molecules, and Bi is pentacoordinated in Bi-MBA. Along the [...

Embodiment 2

[0055] Photoelectrochemical test:

[0056] The tests were performed in three-electrode mode using a 300 W xenon arc lamp (CEL-HFX300, CEAULIGHT) equipped with an AM1.5 filter as the light source. Catalyst-covered fluorine-doped tin oxide (FTO) glass, platinum sheet, Ag / AgCl and Na 2 SO 4 Solution (0.2mol L -1 ) as the working electrode, counter electrode, reference electrode and electrolyte, respectively. 50mg Bi-MBA samples were dispersed in 5mL ethanol, the suspension was spin-coated on FTO glass, and then dried at 70°C for 6h, the photocurrent density and electrochemical impedance spectroscopy were measured at 0V (vs Ag / AgCl) bias potential (EIS).

[0057] Such as Figure 5 As shown, under cut light and zero bias, Bi-MBA exhibits anodic photocurrent with a photocurrent density of about 0.03 μAcm -1 , indicating that Bi-MBA is an n-type semiconductor. It can be seen from the electrochemical impedance spectrum that the radius of Bi-MBA under light is smaller than that ...

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Abstract

The invention provides a bismuth-based metal organic framework material and a preparation method and application thereof, and belongs to the technical field of metal organic framework material preparation and photocatalysis. The preparation method of the bismuth-based metal organic framework material (namely Bi-MBA) provided by the invention is simple, and has the advantages of mild reaction conditions, low cost, high yield and the like; meanwhile, the prepared Bi-MBA single crystal belongs to an orthogonal space group Cmcm and is structurally characterized by being a Bi2S4 long chain; the photo-induced electron-holes of the Bi-MBA can be effectively separated; the electronic structure has the characteristics that an organic ligand mainly occupies a conduction band, so that the conductionband potential reaches -1.38 eV; and thus, the Bi-MBA exhibits good photocatalytic reduction properties, including reduction of O2, Cr(VI) and CO2, and the reaction conditions are all at room temperature. Therefore, good practical application value is achieved.

Description

technical field [0001] The invention belongs to the technical field of metal organic framework material preparation and photocatalysis, and specifically relates to a bismuth-based metal organic framework material and its preparation method and application. Background technique [0002] The information disclosed in this background section is only intended to increase the understanding of the general background of the present invention, and is not necessarily taken as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to those skilled in the art. [0003] In recent years, the energy shortage and environmental problems caused by the endless consumption of fossil energy (coal, oil, and natural gas, etc.) have received close attention from all over the world. The most effective way to solve the above problems today is to find ideal energy sources to replace fossil fuels. Abundant and clean solar energy makes it one of the bes...

Claims

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Application Information

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IPC IPC(8): C08G83/00C07F9/94B01J31/22B01J35/00C01B32/40C02F1/30C02F101/30C02F101/22
CPCC08G83/008C07F9/94B01J31/1691B01J31/226B01J31/2295C01B32/40C02F1/30C07B2200/13B01J2231/60B01J2531/54C02F2101/308C02F2101/22B01J35/39
Inventor 黄柏标雷龙飞刘媛媛王泽岩王朋郑昭科程合锋张晓阳张倩倩
Owner SHANDONG UNIV
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