CN112521618A - Bismuth-based metal organic framework material and preparation method and application thereof - Google Patents
Bismuth-based metal organic framework material and preparation method and application thereof Download PDFInfo
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- CN112521618A CN112521618A CN202011195071.3A CN202011195071A CN112521618A CN 112521618 A CN112521618 A CN 112521618A CN 202011195071 A CN202011195071 A CN 202011195071A CN 112521618 A CN112521618 A CN 112521618A
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- bismuth
- framework material
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 41
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 41
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- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 13
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 claims description 13
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
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- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/94—Bismuth compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a bismuth-based metal organic framework material and a preparation method and application thereof, belonging to the technical field of metal organic framework material preparation and photocatalysis. The preparation method of the bismuth-based metal organic framework material (Bi-MBA) provided by the invention is simpleThe method has the advantages of mild reaction conditions, low cost, high yield and the like; the Bi-MBA single crystal prepared at the same time belongs to an orthogonal space group Cmcm, and has the structural characteristic that Bi2S4Long chains; and the photoproduction electron-hole of the Bi-MBA can be effectively separated; the electronic structure is characterized in that the organic ligand mainly occupies a conduction band, so that the potential of the conduction band reaches-1.38 eV; thus, the Bi-MBA exhibits good photocatalytic reduction properties, including reduction of O2Cr (VI) and CO2And the reaction conditions were all at room temperature. Therefore, it has good practical application value.
Description
Technical Field
The invention belongs to the technical field of metal organic framework material preparation and photocatalysis, and particularly relates to a bismuth-based metal organic framework material as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, energy shortage and environmental problems due to endless consumption of fossil energy (coal, oil, natural gas, and the like) have received close attention all over the world. The most effective way to solve the above problems today is to find an ideal energy source to replace fossil fuels. The abundance and cleanliness of solar energy makes it one of the best candidates, and the conversion and utilization of solar energy has become a hot topic in recent years. In 1972, the first discovery of TiO in Tanzhong2The phenomenon that the single crystal electrode photocatalytically decomposes water reveals the possibility of directly decomposing water by utilizing solar energy, and opens up a research road in the field of photocatalysis.
Metal Organic Frameworks (MOFs) are an ordered porous solid material consisting of a metal center and organic ligands. Besides the characteristics of large specific surface area, high porosity, adjustable structural function, and the like, MOFs, as a semiconductor, can perform oxidation and reduction reactions under light irradiation, are receiving more and more attention. Many bismuth (Bi) -based compounds have proven to be effective photocatalysts, such as Bi2O3，Bi2S3,Bi2O2CO3,BiVO4,Bi2WO6,BiOIO3And BiOX (X ═ Cl, Br, I). However, although BiOBr containing oxygen vacancies is capable of converting N2Reduction to NH3Bi-based photocatalysts rarely report direct drive of reduction reactions, such as reduction of CO2And producing hydrogen. The main reason is the positive conduction band potential of Bi-based semiconductors. To make the conduction band potential more negative, the first and most common way is to reduce the size of the particles by quantum confinement effects. Recently, two Bi-based MOFs have been reported to be capable of performing photocatalytic hydrogen production reaction, which indicates that the combination of Bi and organic ligands may be an effective method for increasing the conduction band potential of Bi-based materials.
The inventors have found that Bi-based MOFs have been reported to contain carboxylic acid groups mainly in the organic ligands, which are generally considered to be unfavorable for electron transfer, resulting in poor electronic conductivity of the relevant MOFs. Furthermore, the light absorption of these reported MOFs relies mainly on the coupling of organic ligands.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a bismuth-based metal organic framework material and a preparation method and application thereof, which take triphenyl bismuth as a Bi source and 4-mercaptobenzoic acid as an organic ligand to design and synthesize a novel Bi-based MOFs (named Bi-MBA), and tests prove that the novel Bi-based MOFs has good photocatalytic reduction performance and thus has good practical application value.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a bismuth-based metal organic framework material, which comprises the steps of taking triphenyl bismuth as a Bi source and 4-mercaptobenzoic acid as an organic ligand, and obtaining the bismuth-based metal organic framework material by adopting a one-step condensation method. Wherein, benzoic acid is added as a regulator to obtain high quality single crystals.
In a second aspect of the present invention, there is provided a bismuth-based metal-organic framework material obtained by the above-mentioned preparation method.
In a third aspect of the invention, the application of the bismuth-based metal organic framework material in photocatalytic reduction is provided.
In a fourth aspect of the present invention, there is provided a photocatalyst comprising the above bismuth-based metal organic framework material.
In a fifth aspect of the present invention, there is provided a method for carrying out photocatalytic reduction, which comprises adding the above-mentioned bismuth-based metal-organic framework material and/or photocatalyst to a reaction. By adding the bismuth-based metal organic framework material and/or the photocatalyst, the photocatalytic reduction can be carried out at room temperature.
In a sixth aspect of the present invention, there is provided the use of the bismuth-based metal-organic framework material, the photocatalyst and/or the method for performing photocatalytic reduction described above in the treatment of environmental pollution. The environmental pollution abatement comprises degrading organic pollutants (such as rhodamine B) and/or reducing the toxicity of heavy metals (such as Cr (VI)).
The beneficial technical effects of one or more technical schemes are as follows:
the preparation method of the Bi-MBA provided by the technical scheme is simple, and has the advantages of mild reaction conditions, low cost, high yield and the like; the Bi-MBA single crystal prepared in the technical scheme belongs to an orthogonal space group Cmcm and has the structural characteristic that Bi2S4Long chains; and the photoproduction electron-hole of the Bi-MBA can be effectively separated; the electronic structure is characterized in that the organic ligand mainly occupies a conduction band, so that the potential of the conduction band reaches-1.38 eV; thus, the Bi-MBA exhibits good photocatalytic reduction properties, including reduction of O2Cr (VI) and CO2And the reaction conditions were all at room temperature. Therefore, it has good practical application value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic diagram of the crystal structure of Bi-MBA prepared in example 1 of the present invention;
FIG. 2 is a Bi-MBA powder XRD and fitted XRD pattern prepared in example 1 of the present invention;
FIG. 3 is an SEM image and a TEM image of Bi-MBA prepared in example 1 of the present invention; wherein (a) is a needle-like crystal and (b) is a flake-like crystal;
FIG. 4 is a UV-visible diffuse reflectance and valence band XPS spectrum of Bi-MBA prepared in example 1 of the present invention; wherein (a) is ultraviolet-visible diffuse reflectance; (b) is a valence band XPS spectrum;
FIG. 5 shows the measured Bi-MBA photocurrent density and Electrochemical Impedance Spectroscopy (EIS) of example 2; wherein (a) is the Bi-MBA photocurrent density; (b) is a Bi-MBA electrochemical impedance spectrum;
FIG. 6 is a density-of-states diagram obtained by the density-functional theory on Bi-MBA in example 3 of the present invention;
FIG. 7 shows the photocatalytic reduction of CO by Bi-MBA in example 4 of the present invention2The quartz reactor used;
FIG. 8 is a graph showing the results of photocatalytic reduction verification of Bi-MBA in example 4 of the present invention, wherein (a) and (B) are experiments of degradation and cyclic stabilization of Bi-MBA photocatalytic rhodamine B, respectively, (c) is an active species trapping experiment, (d) and (e) are experiments of reduction and cyclic stabilization of photocatalytic Cr (VI), respectively, (f) is photocatalytic CO2And (4) carrying out reduction experiments.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
As mentioned previously, Bi-based MOFs have been reported to contain carboxylic acid groups mainly in the organic ligands, which are generally considered to be unfavorable for electron transfer, resulting in poor electronic conductivity of the relevant MOFs. Furthermore, the light absorption of these reported MOFs relies mainly on the coupling of organic ligands.
Bi (III) exhibits hydrophilic properties, and Bi-S bonds are expected to be more favorable for electron transfer than Bi-OOC analogs. Meanwhile, when a Bi-based inorganic semiconductor is modified with a thiophenic acid salt, the formation of a Bi — S bond shows visible light absorption. This result provides a new approach to modulation of the optical response. In addition, bismuth is a soft lewis acid, and S is considered to be a soft lewis base. Thus, according to the theory of soft and hard acids and bases (HSAB), MOFs containing Bi-S bonds are stable.
In view of the above, the present invention provides a method for adjusting the conduction band potential of a Bi-based photocatalyst by combining with an organic ligand to make the conduction band potential of the Bi-based photocatalyst assume a negative value, thereby realizing the photocatalytic reduction performance, wherein the Bi-based MOF has one-dimensional Bi2S4The long-chain structure, excellent photocatalytic reduction performance, good stability and good application prospect.
In a specific embodiment of the invention, the preparation method of the bismuth-based metal organic framework material is provided, and the preparation method comprises the steps of taking triphenyl bismuth as a Bi source, taking 4-mercaptobenzoic acid as an organic ligand, adding the bismuth-based metal organic framework material into an organic solvent, and adopting a one-step condensation method to obtain the bismuth-based metal organic framework material. Preferably, benzoic acid is added simultaneously as a modifier in the preparation process to obtain a high quality single crystal.
In another embodiment of the present invention, the preparation method comprises: adding triphenyl bismuth and 4-mercaptobenzoic acid into an organic solvent, simultaneously adding benzoic acid, uniformly mixing, and heating and refluxing to obtain the bismuth tungstate. In the preparation method, triphenyl bismuth is used as a Bi source, so that the hydrolysis of Bi can be effectively avoided.
In still another embodiment of the present invention, the organic solvent includes xylene, toluene, carbon tetrachloride and the like, preferably xylene;
in another embodiment of the invention, the molar ratio of the triphenyl bismuth to the 4-mercaptobenzoic acid to the benzoic acid is 1:1 to 5; further preferred is 1:2.18: 2.18; by controlling the proportion of the raw materials, the reaction can be accelerated, and the yield is effectively improved.
In another embodiment of the present invention, the specific conditions of the heating reflux are as follows: reacting at 50-70 ℃ for 20-28h, preferably at 60 ℃ for 24 h.
In another embodiment of the invention, the bismuth-based metal organic framework material is obtained by purifying the reaction product.
In another embodiment of the present invention, the purification step comprises: and washing and drying the reaction product to obtain the catalyst.
In another embodiment of the present invention, the washing step comprises washing with methanol and acetone for 2-3 times, respectively;
in another embodiment of the present invention, the drying method comprises: drying at 100-120 ℃ for 20-28 h; preferably at 120 ℃ for 24 h.
In another embodiment of the present invention, there is provided a bismuth-based metal-organic framework material obtained by the above-mentioned preparation method. The bismuth-based metal-organic framework material (Bi-MBA) is a single crystal of Bi which is one-dimensional along the crystallographic a-axis2S4The long chains are characterized by a crystal structure and crystallize in the cross space group Ccm. Each of Bi (iii) coordinates to one benzene ring of triphenylbismuth as a Bi source and four sulfur atoms in four ligand molecules, and Bi is penta-coordinated in Bi-MBA. Along [011 ]]Direction, two adjacent Bi2S4The carboxyl (-COOH) functional groups on the chain are hydrogen bonded (as shown in figure 1).
The powder XRD pattern of the Bi-MBA was consistent with the results of the simulation, demonstrating the phase purity of the sample (as shown in fig. 2). (010) And (011) face corresponds to two distinct peaks at 6.2 and 11.5 degrees, indicating that the crystal is more inclined along [010 ]]And [011 ]]Directionally growing, and microscopically rod-shaped and flake-shaped. SEM images and TEM images also demonstrate that Bi-MBA exists in two morphologies (as shown in FIG. 3), namely needles (3 μm-6 μm) and flakes (0.6X 0.9 μm)2-8×14μm2)。
In another embodiment of the present invention, there is provided a use of the bismuth-based metal-organic framework material in photocatalytic reduction. The test proves that the photocatalyst has excellent photocatalytic reduction activity. The conduction band potential of the Bi-MBA is-1.38 eV, and O can be effectively reduced2Cr (VI) and CO2。
In another embodiment of the present invention, there is provided a photocatalyst comprising the above bismuth-based metal organic framework material.
In yet another embodiment of the present invention, there is provided a method for carrying out photocatalytic reduction, which comprises adding the above-mentioned bismuth-based metal-organic framework material and/or photocatalyst to the reaction. By adding the bismuth-based metal organic framework material and/or the photocatalyst, the photocatalytic reduction can be carried out at room temperature.
The species to be reduced includes but is not limited to O2Cr (VI) and CO2。
In yet another embodiment of the present invention, when reducing CO2When the photocatalyst is a compound of the bismuth-based metal organic framework material and Pd. Pd can improve the photocatalytic activity of Bi-MBA.
In another embodiment of the present invention, there is provided the use of the bismuth-based metal-organic framework material, the photocatalyst and/or the method for photocatalytic reduction described above in environmental pollution control. The environmental pollution abatement comprises degrading organic pollutants (such as rhodamine B) and/or reducing the toxicity of heavy metals (such as Cr (VI)).
The technical solution of the present invention will be described below with specific examples. The starting materials used in the following examples are all commercially available.
Example 1
A preparation method of a Bi-based metal organic framework (Bi-MBA) comprises the following steps:
triphenylbismuth (51.6mg,0.117mmol) and 4-mercaptobenzoic acid (39.2mg, 0.255mmol) were added to xylene (18mL), stirred for 30min and then refluxed at 60 ℃ for 24 h. Benzoic acid (31.1mg,0.255mmol) was added as a modifier during the synthesis process to obtain high quality single crystals. After the reaction was complete, the yellow product was collected by cooling, filtration, washing (3 times with methanol and acetone, respectively), drying (oven drying at 120 ℃ for 24 h). The yield was 82.3%.
As shown in FIG. 1, Bi-MBA is Bi one-dimensional along the crystallographic a-axis2S4The long chains are characterized by a crystal structure and crystallize in the cross space group Ccm. Each of Bi (iii) coordinates to one benzene ring of triphenylbismuth as a Bi source and four sulfur atoms in four ligand molecules, and Bi is penta-coordinated in Bi-MBA. Along [011 ]]Direction, two adjacent Bi2S4The carboxyl (-COOH) functional groups on the chain are hydrogen bonded.
The powder XRD pattern of the Bi-MBA was consistent with the results of the simulation, demonstrating the phase purity of the sample (as shown in fig. 2). (010) And (011) face corresponds to two distinct peaks at 6.2 and 11.5 degrees, indicating that the crystal is more inclined along [010 ]]And [011 ]]Directionally growing, and microscopically rod-shaped and flake-shaped. SEM images and TEM images also demonstrate that Bi-MBA exists in two morphologies (as shown in FIG. 3), namely needles (3 μm-6 μm) and flakes (0.6X 0.9 μm)2-8×14μm2)。
The absorption band edge of Bi-MBA is 500nm (shown in (a) in FIG. 4), and the corresponding forbidden band width is about 2.48 eV; the valence band XPS is characterized in that the valence band potential of Bi-MBA is 1.10eV (as shown in FIG. 4 (b)), and the conduction band potential thereof is calculated to be-1.38 eV, which is much more negative than that of the known Bi-based semiconductor.
Example 2
Photoelectrochemical testing:
the test was carried out in a three-electrode mode using a 300 watt xenon arc lamp (CEL-HFX300, ceuollight) equipped with an AM1.5 filter as light source. Catalyst coated fluorine doped oxygenTin Oxide (FTO) glass, platinum sheet, Ag/AgCl and Na2SO4Solution (0.2mol L)-1) Respectively as a working electrode, a counter electrode, a reference electrode and electrolyte. A50 mg sample of Bi-MBA was dispersed in 5mL of ethanol, the suspension was spin-coated on FTO glass, and then dried at 70 ℃ for 6h, and photocurrent density and Electrochemical Impedance Spectroscopy (EIS) were measured at a bias potential of 0V (vs Ag/AgCl).
As shown in FIG. 5, under the conditions of light-cutting and zero bias, Bi-MBA shows the anode photocurrent, and the photocurrent density is about 0.03 μ A cm-1It is shown that Bi-MBA is an n-type semiconductor. From the electrochemical impedance spectrogram, the radius of the Bi-MBA under illumination is smaller than that of the Bi-MBA under dark, which shows that the current carriers generated by light can be effectively separated under illumination. These results indicate that Bi-MBA exhibits semiconducting behavior and can act as a photocatalyst.
Example 3
And (4) theoretical calculation:
the electronic structure of Bi-MBA was calculated from the first principles density-functional theory (DFT) using a wiener de novo computation simulation software package (VASP). Valence nuclear electron interactions are treated with a Projective Amplified Wave (PAW) potential, and electron exchange-related interactions are described by Generalized Gradient Approximation (GGA). The wave-based energy cut-off was set to 400 eV. The geometric relaxation convergence criterion of each atom is set as
K points are sampled at 3X 1 by a Monkhorst-Pack grid. The DFT-D3 method is used to account for van der Waals interactions.
The electronic structure of the Bi-MBA was revealed by calculating the total state density (TDOS) and the local state density (PDOS) (as shown in FIG. 6). As can be seen from the TDOS plot, the band gap of Bi-MBA is calculated to be 2.5eV, which is very close to the UV-visible diffuse reflectance analysis. PDOS indicates that near the fermi level, the valence band is composed primarily of S3 p and carbon from the benzene ring and 4-mercaptobenzoic acid, with Bi also contributing a small amount to the valence band. At the same time, Bi 6p and C2 p of 4-mercaptobenzoic acid also dominate in the conduction band. These results indicate that the formation of Bi-S bonds plays an important role in light absorption. In addition, the contribution of 4-mercaptobenzoic acid to C2 p suggests that photogenerated electrons may delocalize and the presence of carboxylic acid groups may be further enhanced during the coupling of organic ligands. This delocalization facilitates the separation of photogenerated carriers. The significant contribution of 4-mercaptobenzoic acid to the conduction band further confirms that binding of organic ligands may shift the conduction band potential up, thereby increasing the reducing power.
Example 4
Testing the photocatalytic performance:
(1) degrading rhodamine B. Bi-MBA (25mg) powder photocatalyst was added to rhodamine B aqueous solution (50mL,10mg L)-1) In the dark, stirring is carried out for 30min to establish adsorption-desorption equilibrium. A300-watt xenon arc lamp equipped with a 420nm cut-off filter was used as the light source, and the reaction was carried out at room temperature (25 ℃ C.). During the reaction, 3mL of suspension was taken out every 10 min. After centrifugation, the solution was examined for the change in absorbance at 540nm using an ultraviolet-visible spectrophotometer (UV-2550, Shimadzu). Silver nitrate (1mmol,8.4mg), methanol (500mmol, 1mL), mannitol (1mmol, 9.1mg), p-benzoquinone (1mmol, 5.4mg) and catalase (1mmol, 8.3mg) as electrons (e), respectively-) Hole (h)+) Hydroxyl radical (OH), superoxide radical (O)2-H) and hydrogen peroxide (H)2O2) To explore the active oxygen species for degrading rhodamine B. The cycling stability experiment was as follows: the photocatalyst used was centrifuged, carefully washed with deionized water, added to a fresh rhodamine B aqueous solution for a second run test, and similarly, 5 cycles of the experiment were performed in total.
(2) Reducing Cr (VI). Bi-MBA (20mg) powder was added to potassium dichromate (40mL,10mg L)-1) In the aqueous solution, the rest process is similar to degradation of rhodamine B. The Cr (VI) content was measured by DPC/acetone method (DPC is an abbreviation for 1, 5-diphenylcarbazide). Every 2h, 2mL of suspension was taken and centrifuged to obtain a clear solution. Then, a sulfuric acid solution (1mL,0.2mol L) was added to the supernatant-1) And DPC/acetone solution (1mL, 0.25% (w/v)). After sufficient color development, the change in absorbance of the solution at 540nm was measured using an ultraviolet-visible spectrophotometer. The cycling stabilization experiment was similar to that described above, with a total of 5 cr (vi) reductions.
(3) Reduction of CO2。CO2The photocatalytic reduction of (a) was carried out in a quartz reactor (as shown in FIG. 7). Bi-MBA (100mg) powder was uniformly covered in a circular ceramic lid having a diameter of about 6.5 cm. The lid was transferred to a quartz reactor and deionized water (1mL) was injected outside the circumference of the lid. The reactor volume was 50mL min-1Of high purity CO2The gas was bubbled for 20min and then completely sealed. Then the reaction system is placed in the dark for 1h, the adsorption-desorption balance is established, and then the reaction system is exposed under a 300-watt xenon arc lamp for illumination. Every 2h, 0.8mL of CO gas was withdrawn by syringe and the yield of CO gas was measured by gas chromatography (GC-7920). In addition, the photocatalytic CO is also carried out by the Bi-MBA loaded with Pd2And (4) reducing. The supported Pd adopts a photo-deposition method: to 100mL of deionized water were added Bi-MBA (100mg) powder and chloropalladite (940. mu.L, 0.01mol L)-1) The mixture was then irradiated with light for 1h with stirring. Then filtered and dried in an oven at 60 ℃ for 24h to give Bi-MBA doped with 1 wt% Pd.
In this example, firstly, rhodamine B was used as a probe molecule to study Bi-MBA in O2Photocatalytic reduction ability in activation. Bi-MBA shows high-efficiency RhB degradation, and about 95% of rhodamine B is degraded within 30min under visible light (as shown in (a) in figure 8). Five cycles of experiments confirmed the stability of the catalyst (as shown in fig. 8 (b)). Catalase, AgNO3Addition of mannitol and methanol had no effect on the degradation rate, indicating that H2O2、e-OH, and h+Is not the predominant reactive oxygen species. And p-benzoquinone as O2-The addition of a scavenger significantly suppresses the reaction rate, i.e. O2-Is a main active oxygen species that degrades rhodamine B (as shown in fig. 8 (c)). This result indicates that the photo-generated electrons are able to reduce O2。
Secondly, the reduction of Cr (VI) is studied, and the photocatalytic reduction capability of Bi-MBA is further revealed. Under the irradiation of visible light, Cr (VI) is effectively reduced within 6h, and under the irradiation of Bi-MBA for 420nm, the degradation rate is 86%. Control experiments without light and without catalyst showed that cr (vi) was not reduced (as shown in fig. 8 (d)). Likewise, five cycle experiments demonstrated the stability of the catalyst (as shown in fig. 8 (e)). The reduction experiment of Cr (VI) further proves that the photoproduction electrons of the Bi-MBA easily participate in the photocatalytic reaction and have strong reduction capability.
Finally, the photocatalytic reduction of CO by Bi-MBA was investigated2And (4) activity. CO was detected as the major reduction product, with the amount observed over 10h being 0.85. mu. mol for pure Bi-MBA. The deposition of Pd on Bi-MBA increases the activity, approximately 2.4 times that of pure Bi-MBA (as shown in FIG. 8 (f)).
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the bismuth-based metal organic framework material is characterized by comprising the steps of taking triphenyl bismuth as a Bi source and 4-mercaptobenzoic acid as an organic ligand, and obtaining the bismuth-based metal organic framework material by adopting a one-step condensation method.
2. The process of claim 1, wherein benzoic acid is added as a modifier.
3. The method of claim 1, comprising: adding triphenyl bismuth and 4-mercaptobenzoic acid into an organic solvent, simultaneously adding benzoic acid, uniformly mixing, and heating and refluxing to obtain the bismuth tungstate.
4. The method of claim 3, wherein the organic solvent comprises xylene, toluene, and carbon tetrachloride; preferably xylene;
the molar ratio of the triphenyl bismuth to the 4-mercaptobenzoic acid to the benzoic acid is 1: 1-5; preferably 1:2.18: 2.18;
the specific conditions of heating reflux are as follows: reacting at 50-70 ℃ for 20-28h, preferably at 60 ℃ for 24 h.
5. The preparation method according to claim 3, wherein the reaction product is purified to obtain the bismuth-based metal organic framework material;
preferably, the purification comprises the following specific steps: washing and drying the reaction product to obtain the catalyst;
wherein the washing step comprises washing with methanol and acetone for 2-3 times respectively;
the drying method comprises the following steps: drying at 100-120 ℃ for 20-28 h; preferably at 120 ℃ for 24 h.
6. A bismuth-based metal-organic framework material obtained by the production method according to any one of claims 1 to 5; the bismuth-based metal organic framework material is characterized in that the bismuth-based metal organic framework material is a single crystal, and Bi which is one-dimensional along a crystallographic a axis2S4The crystal structure characteristic of the long chain is that the crystal is crystallized in an orthogonal space group Cmcm; each Bi (III) coordinates with one benzene ring of triphenyl bismuth as a Bi source and four sulfur atoms in four ligand molecules, and Bi is penta-coordinated in Bi-MBA; along [011 ]]Direction, two adjacent Bi2S4The carboxyl (-COOH) functional groups on the chain are connected by hydrogen bonds;
(010) and (011) crystal plane corresponds to two distinct peaks at 6.2 and 11.5 degrees, which are microscopically rod-like and flake-like.
7. Use of the bismuth-based metal organic framework material of claim 6 in photocatalytic reduction.
8. A photocatalyst comprising the bismuth-based metal organic framework material according to any one of claims 1 to 5.
9. A method for carrying out photocatalytic reduction, characterized in that the method comprises adding the bismuth-based metal-organic framework material according to claim 6 and/or the photocatalyst according to claim 8 to a reaction;
preferably, the substance to be reduced comprises O2Cr (VI) and CO2；
Preferably, when reducing CO2When the photocatalyst is a compound of the bismuth-based metal organic framework material and Pd.
10. Use of the bismuth-based metal-organic framework material of claim 6, the photocatalyst of claim 8 and/or the method for performing photocatalytic reduction of claim 9 in environmental pollution remediation;
preferably, the environmental pollution remediation comprises degrading organic pollutants and/or reducing heavy metal toxicity.
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