CN113398956B - BiOI photocatalyst with visible light response and preparation method and application thereof - Google Patents
BiOI photocatalyst with visible light response and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000004298 light response Effects 0.000 title claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 56
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 38
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011630 iodine Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 52
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 36
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 18
- 238000004729 solvothermal method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000002073 nanorod Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 74
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 239000012922 MOF pore Substances 0.000 abstract description 3
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 description 79
- 230000001699 photocatalysis Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a visible light response BiOI photocatalyst, and a preparation method and application thereof, and belongs to the technical field of catalytic materials. The Bi-MOF is prepared firstly, solvent molecules and reactant molecules in a Bi-MOF framework structure are removed through activation, the influence on subsequent chemical adsorption is prevented, and the specific surface area of the Bi-MOF is increased; iodine simple substance enters a Bi-MOF pore canal of a metal organic framework in a chemical adsorption mode, and is subjected to chemical reaction with O and Bi in the Bi-MOF framework to form BiOI, so that the BiOI agglomeration generated in the chemical adsorption process can be prevented, and the dispersibility of the BiOI can be improved; in addition, as the adsorption reaction is carried out in a closed device, the purity of the BiOI can be improved, and the crystallinity of the BiOI can be improved, so that the prepared BiOI has higher visible light catalytic activity.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a visible light response BiOI photocatalyst and a preparation method thereof.
Background
With the rapid development of economy, environmental pollution and energy exhaustion have caused a number of global problems. Semiconductor photocatalytic technology has been considered as an ideal approach to solve energy and environmental problems because it can convert solar energy into chemical energy for clean fuel synthesis and environmental remediation. In the photocatalytic reaction process, the absorption and utilization rate of light and the carrier separation and transfer efficiency are key factors influencing the exertion of the catalytic activity of the semiconductor photocatalyst. So far, the technology has not been applied on a large scale, and the main reason is that: firstly, the efficiency of directly utilizing sunlight to perform photocatalytic conversion is low; secondly, the separation efficiency of the photo-generated carriers is low, the quantum efficiency is low, and the photo-generated carriers have no catalytic activity especially under the condition of weak light or no light; thirdly, the number of the surface active centers is insufficient, and interface contact is poor, so that surface reaction kinetics is slow. Therefore, the design and preparation of high-efficiency photocatalysts is the core for improving the efficiency of photocatalytic reactions. With respect to limitations of photocatalytic materials, research into visible light responsive catalytic materials has become a trend and a hotspot.
Among the numerous semiconductor photocatalytic materials, bismuth oxyhalide photocatalytic materials have been the focus of research in recent years for photocatalytic technology by virtue of unique electronic and lattice structures. The bismuth oxyiodide (BiOI) has the advantages of wider visible light response range, good physical and chemical stability and the like, and has excellent visible light catalytic performance in the fields of pollutant degradation, photocatalytic water splitting hydrogen production, selective organic matter conversion, carbon dioxide reduction and photocatalytic nitrogen fixation. The conventional preparation method of the bismuth-based photocatalytic material mainly comprises a solid-phase method, a liquid-phase method and a gas-phase method, wherein the hydrothermal reaction method is simple to operate and has low requirements on equipment so as to be widely used. However, the defects are that local concentration is easy to be too high, the obtained product has poor dispersibility, easy agglomeration and uneven particle size, and the exposure of surface active sites is influenced, so that the photocatalytic activity is influenced.
Therefore, there is a need to provide a preparation method of a BiOI photocatalyst with high crystallinity, good dispersibility and high visible light catalytic activity.
Disclosure of Invention
The invention aims to provide a visible light response BiOI photocatalyst, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a visible light response BiOI photocatalyst, which comprises the following steps:
(1) Mixing 1,3, 5-benzene tricarboxylic acid, bismuth nitrate pentahydrate and methanol, and performing solvothermal reaction to obtain Bi-MOF;
(2) And (3) activating the Bi-MOF obtained in the step (1), and then placing the activated Bi-MOF and an iodine simple substance in a closed container for adsorption reaction to obtain the BiOI photocatalyst.
Preferably, the ratio of the amounts of the substances of 1,3, 5-trimellitic acid and bismuth nitrate pentahydrate in the step (1) is (11-13): 1.
Preferably, the ratio of the amount of the 1,3, 5-benzene tricarboxylic acid in the step (1) to the volume of methanol is (3-4) mmol (60-80) mL.
Preferably, the temperature of the solvothermal reaction in the step (1) is 110-125 ℃, and the time of the solvothermal reaction is 18-24 h.
Preferably, the activation temperature in step (2) is 120 to 130 ℃.
Preferably, the activation in step (2) takes 12 to 18 hours.
Preferably, the mass ratio of Bi-MOF to iodine simple substance in the step (2) is (0.5-1.2): 245-255.
Preferably, the temperature of the adsorption reaction in the step (2) is 45-75 ℃, and the time of the adsorption reaction is 20-24 hours.
The invention also provides the BiOI photocatalyst prepared by the preparation method of the technical scheme, and the BiOI photocatalyst is of a lamellar structure.
The invention also provides application of the BiOI photocatalyst in the technical scheme.
The invention provides a preparation method of a visible light response BiOI photocatalyst, which comprises the following steps: mixing 1,3, 5-benzene tricarboxylic acid, bismuth nitrate pentahydrate and methanol, and performing solvothermal reaction to obtain Bi-MOF; and (3) activating the obtained Bi-MOF, and then placing the activated Bi-MOF and an iodine simple substance in a closed container for adsorption reaction to obtain the BiOI photocatalyst. According to the preparation method, the Bi-MOF is prepared firstly, and solvent molecules and reactant molecules in the Bi-MOF framework structure are removed through activation, so that the influence on subsequent chemical adsorption is prevented, and the specific surface area of the Bi-MOF is increased; iodine simple substance enters a Bi-MOF pore canal of a metal organic framework in a chemical adsorption mode to be converted into stable BiOI; the Bi-MOF has larger specific surface area and adsorption sites, so that the I simple substance can be fully adsorbed, so that the I simple substance and O and Bi in the Bi-MOF framework are subjected to chemical reaction to form BiOI, the BiOI agglomeration generated in the chemical adsorption process can be prevented, and the dispersibility of the BiOI can be further improved; in addition, as the adsorption reaction is carried out in a closed device, the purity of the BiOI can be improved, and the crystallinity of the BiOI can be improved, so that the prepared BiOI has higher visible light catalytic activity. The results of the examples show that the BiOI prepared by the invention has visible light and near infrared light responsivity, the light absorption range reaches 800nm, and the BiOI has excellent photocatalytic activity under visible light.
Drawings
FIG. 1 is a photograph of Bi-MOF prepared in example 1 of the present invention;
FIG. 2 is a photograph of a BiOI photocatalyst prepared in example 1 of the present invention;
FIG. 3 is an SEM image of Bi-MOF prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a BiOI photocatalyst prepared in example 1 of the present invention;
FIG. 5 is an XRD pattern of the BiOI photocatalyst prepared in example 1 of the present invention;
FIG. 6 is a graph showing absorbance curves of Bi-MOF and BiOI prepared in example 1 of the present invention;
FIG. 7 is a bar graph showing the adsorption amount of Bi-MOF to iodine in BiOI prepared in example 1 and comparative examples 1 to 3 of the present invention;
FIG. 8 is a bar graph showing the adsorption amount of Bi-MOF to iodine in BiOI prepared in examples 1 and 2 and comparative examples 4 and 5 according to the present invention.
Detailed Description
The invention provides a preparation method of a visible light response BiOI photocatalyst, which comprises the following steps:
(1) Mixing 1,3, 5-benzene tricarboxylic acid, bismuth nitrate pentahydrate and methanol, and performing solvothermal reaction to obtain Bi-MOF;
(2) And (3) activating the Bi-MOF obtained in the step (1), and then placing the activated Bi-MOF and an iodine simple substance in a closed container for adsorption reaction to obtain the BiOI photocatalyst.
The invention mixes 1,3, 5-benzene tricarboxylic acid, bismuth nitrate pentahydrate and methanol, and carries out solvothermal reaction to obtain Bi-MOF. In the invention, the 1,3, 5-benzene tricarboxylic acid is used as an organic ligand, the bismuth nitrate pentahydrate provides metallic bismuth, the methanol is used as a solvent, and the 1,3, 5-benzene tricarboxylic acid, the bismuth nitrate pentahydrate and the methanol form a metallic complex with a hexagonal prism structure under the solvothermal condition.
In the present invention, the ratio of the amounts of the 1,3, 5-trimellitic acid and bismuth nitrate pentahydrate is preferably (11 to 13): 1, more preferably (11 to 12): 1. In the present invention, when the ratio of the amounts of the substances of 1,3, 5-benzenetricarboxylic acid and bismuth nitrate pentahydrate is in the above range, 1,3, 5-benzenetricarboxylic acid and bismuth nitrate pentahydrate can be sufficiently reacted to obtain a metal complex having a uniform structure.
The amount of the methanol to be used in the present invention is not particularly limited, and may be adjusted according to the amount of the 1,3, 5-benzenetricarboxylic acid. In the present invention, the ratio of the amount of the 1,3, 5-benzenetricarboxylic acid substance to the volume of methanol is preferably (3 to 4) mmol (60 to 80) mL, more preferably (3.5 to 3.8) mmol (65 to 70) mL, and most preferably 3.57mmol:60mL. In the present invention, when the ratio of the amount of the 1,3, 5-trimellitic acid substance to the volume of methanol is in the above range, the solvothermal reaction is more favorably carried out sufficiently.
The operation mode of mixing the 1,3, 5-benzene tricarboxylic acid, bismuth nitrate pentahydrate and methanol is not particularly limited, and the above components can be uniformly mixed by adopting a mixing mode well known to those skilled in the art. In the present invention, the mixing of 1,3, 5-benzene tricarboxylic acid, bismuth nitrate pentahydrate and methanol is preferably ultrasonic. The power and time of the ultrasonic wave are not particularly limited in the present invention, and the 1,3, 5-benzene tricarboxylic acid and bismuth nitrate pentahydrate can be completely dissolved in methanol.
In the present invention, the temperature of the solvothermal reaction is preferably 110 to 125 ℃, more preferably 115 to 120 ℃, and most preferably 120 ℃; the time of the solvothermal reaction is preferably 18 to 24 hours, more preferably 22 to 24 hours, and most preferably 24 hours. In the present invention, when the temperature and time of the solvothermal reaction are within the above ranges, 1,3, 5-benzenetricarboxylic acid and bismuth nitrate pentahydrate can be sufficiently reacted.
The apparatus for the solvothermal reaction is not particularly limited in the present invention, and a reaction vessel well known to those skilled in the art may be used. In the invention, the device for solvothermal reaction is preferably a polytetrafluoroethylene reaction kettle.
After the solvothermal reaction is finished, the product obtained by the solvothermal reaction is preferably subjected to centrifugation, washing and drying in sequence to obtain the Bi-MOF. The operation of centrifugation, washing and drying is not particularly limited in the present invention, and the operation of centrifugation, washing and drying, which are well known to those skilled in the art, may be employed. In the present invention, the rotational speed of the centrifugation is preferably 8000 to 10000r/min, more preferably 9000 to 10000r/min; the time for the centrifugation is preferably 5 to 10 minutes, more preferably 6 to 8 minutes. In the present invention, the washing reagent is preferably methanol, and the number of times of washing is not particularly limited, and the unreacted starting material in the Bi-MOF can be sufficiently removed. In the present invention, the drying temperature is preferably 60 to 80 ℃, more preferably 70 to 80 ℃; the drying time is preferably 12 to 24 hours, more preferably 20 to 24 hours; the drying apparatus is not particularly limited, and a drying apparatus known to those skilled in the art may be used. In the present invention, the drying apparatus is preferably a vacuum drying oven.
After Bi-MOF is obtained, the Bi-MOF is activated and then is placed in a closed container together with iodine simple substance to perform adsorption reaction, so as to obtain the BiOI photocatalyst. In the invention, the Bi-MOF has rich adsorption sites and large specific surface area, and can adsorb iodine simple substance, and the iodine simple substance is chemically reacted with O and I in the Bi-MOF to form BiOI.
In the present invention, the activation temperature is preferably 120 to 130 ℃, more preferably 120 to 125 ℃, and most preferably 120 ℃; the activation time is preferably 12 to 18 hours, more preferably 12 to 13 hours, most preferably 12 hours. The activation device of the present invention is not particularly limited, and a heating device known to those skilled in the art may be used to achieve the above temperature range. In the invention, the activation can remove solvent molecules and reactant molecules in the Bi-MOF framework structure, prevent side effects on subsequent adsorption reaction, and can improve the specific surface area of the Bi-MOF.
In the invention, the sealing device can provide a pure iodine adsorption environment and prevent side reactions. The sealing device is not particularly limited, and a sealing space can be formed by using a device known to those skilled in the art. In the present invention, the sealing means is preferably a sealed glass container.
In the invention, the mass ratio of the Bi-MOF to the elemental iodine is preferably (0.5-1.2): 245-255), more preferably (0.9-1.0): 250-255, and most preferably 1:250. In the invention, when the mass ratio of the Bi-MOF to the iodine simple substance is in the above range, the Bi-MOF can fully adsorb the iodine simple substance, and the catalytic activity of the catalyst is further improved.
In the present invention, the temperature of the adsorption reaction is preferably 45 to 75 ℃, more preferably 55 to 75 ℃, and most preferably 75 ℃; the time of the adsorption reaction is preferably 20 to 24 hours, more preferably 24 hours, and most preferably 24 hours. In the present invention, when the temperature and time of the adsorption reaction are in the above ranges, the Bi-MOF can be made to sufficiently adsorb elemental iodine, thereby further improving the catalytic activity of the catalyst.
In the present invention, the adsorption amount of the elemental iodine by the Bi-MOF after the adsorption reaction is preferably calculated from the formula (1).
Q=(m 1 -m 0 )/m 0 (1)
Wherein m is 0 For the mass of Bi-MOF before adsorption, m 1 The mass of the BiOI obtained after the adsorption. In the invention, the formula (1) can determine the adsorption amount of Bi-MOF to iodine simple substance in the obtained BiOI.
The preparation method provided by the invention prepares the Bi-MOF firstly, removes solvent molecules and reactant molecules in the Bi-MOF framework structure through activation, prevents the influence on the subsequent chemical adsorption, and improves the specific surface area of the Bi-MOF; iodine simple substance enters a Bi-MOF pore canal of a metal organic framework in a chemical adsorption mode to be converted into stable BiOI; the Bi-MOF has larger specific surface area and adsorption sites, so that the Bi-MOF can fully adsorb an I simple substance, so that the I simple substance and O and Bi in a Bi-MOF framework are subjected to chemical reaction to form BiOI, and the BiOI agglomeration generated in the chemical adsorption process can be prevented, so that the dispersibility of the BiOI can be improved; in addition, as the adsorption reaction is carried out in a closed device, the purity of the BiOI can be improved, and the crystallinity of the BiOI can be improved, so that the prepared BiOI has higher visible light catalytic activity.
The invention also provides the BiOI photocatalyst prepared by the preparation method of the technical scheme, and the BiOI photocatalyst is of a lamellar structure. In the invention, the BiOI photocatalyst is formed into a lamellar structure by the destruction of the metal-organic framework structure due to the entry of iodine.
According to the BiOI photocatalyst provided by the invention, the iodine simple substance and O and I in the Bi-MOF framework are subjected to chemical reaction to form BiOI, so that the BiOI is uniformly distributed, the BiOI agglomeration can be prevented, and the dispersibility of the BiOI can be further improved; meanwhile, the crystallinity of the BiOI can be improved, so that the BiOI has higher visible light catalytic activity.
The invention also provides application of the BiOI photocatalyst in the technical scheme. The method of the application of the BiOI photocatalyst in the photocatalyst is not particularly limited, and the application method known to those skilled in the art can be adopted.
In the invention, the BiOI has higher dispersivity and crystallinity, so that the BiOI has higher BiOI and can be applied to a photocatalyst.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
Example 1
(1) 1,3, 5-Benzotrimesic acid (3.57 mmol,750 mg) and bismuth nitrate pentahydrate powder (0.31 mmol,150 mg). Put in a 100mL beaker in order, and methanol (molecular weight 32.04, 60 mL) was added. Ultrasonically dispersing the mixed solution for 5min to uniformly mix the solution, then transferring the solution into a 100mL polytetrafluoroethylene reaction kettle, and preserving the heat in a baking oven at 120 ℃ for 24h to perform solvothermal reaction; after the reaction is finished, centrifuging for 5min at 8000r/min, and then washing the solid obtained by centrifugation with methanol for 3 times; the collected white solid was dried in a vacuum oven at 60℃for 12 hours to give Bi-MOF as a white powder. Wherein the ratio of the amounts of 1,3, 5-benzene tricarboxylic acid and bismuth nitrate pentahydrate material is 3.57:0.31.
(2) The Bi-MOF prepared in the step (1) is activated for 12 hours at 120 ℃ in a vacuum drying oven, then two parts of activated Bi-MOF (20 mg) are weighed by a high-precision digital balance and taken as an adsorbent, the adsorbent is placed in a 5mL glass bottle, the glass bottle is moved into a closed glass container, and meanwhile, iodine crystals (5 g) are added to the bottom of the closed glass container. The sealed glass container was then moved into an oven and heated at 75 ℃ for 24 hours to obtain a bisi photocatalyst. The BiOI photocatalyst is weighed, the adsorption quantity of Bi-MOF to iodine is calculated according to the formula (1), and the adsorption quantity of Bi-MOF to iodine in the obtained BiOI is 859.85mg/g.
The photograph of Bi-MOF prepared in this example is shown in FIG. 1; a photograph of the BiOI photocatalyst prepared in this example is shown in FIG. 2. As can be seen from fig. 1 and 2, the Bi-MOF prepared in the present invention is a white powder; the BiOI photocatalyst is orange powder.
The Bi-MOF prepared in this example was tested by a scanning electron microscope, and an SEM image of the obtained Bi-MOF is shown in FIG. 3, and the BiOI prepared in this example was tested by a scanning electron microscope, and an SEM image of the obtained BiOI is shown in FIG. 4. As can be seen from fig. 3 and 4, bi-MOF exhibits a hexagonal prism structure, and the bio-i causes the destruction of the metal-organic framework structure due to the ingress of iodine, forming a nanorod structure.
Commercial BiOI and the BiOI photocatalyst prepared in this example were tested using an X-ray diffractometer to give the XRD patterns of the BiOI photocatalyst shown in FIG. 5. As can be seen from FIG. 5, the characteristic peaks of the BiOI prepared by the preparation method of the present invention are the same as those of the commercial BiOI (JCPLS No. 73-2062), and it is proved that the preparation method of the present invention can obtain the BiOI crystal with higher purity.
The Bi-MOF and BiOI prepared in this example were tested using a solid ultraviolet visible spectrophotometer UV2700, and absorbance graphs are shown in FIG. 6. As can be seen from fig. 6, the BiOI prepared in this example has visible light and near infrared light responsivity, and its light absorption range reaches 800nm. This shows that Bi-MOF adsorbs iodine to form BiOI, which widens the light absorption range, and can absorb visible light in a light response manner, thereby efficiently exerting photocatalytic activity.
Comparative example 1
The difference from example 1 was that the heating time in the step (2) was 12 hours, and the rest was the same as in example 1, and the obtained BiOI had an adsorption amount of Bi-MOF to iodine of 1030.98mg/g.
Comparative example 2
The difference from example 1 was that the heating time in the step (2) was 36 hours, and the rest was the same as in example 1, and the obtained BiOI had an adsorption amount of Bi-MOF to iodine of 1019.98mg/g.
Comparative example 3
The difference from example 1 was that the heating time in step (2) was 1h, and the remaining steps were the same as in example 1, to obtain an adsorption amount of Bi-MOF to iodine of 106.53mg/g.
The adsorption amount histogram of Bi-MOF to iodine in the BiOI prepared in example 1 and comparative examples 1 to 3 is shown in FIG. 7. As can be seen from fig. 7, the Bi-MOF can fully adsorb the elemental iodine within the adsorption time range defined by the present invention for 20 to 24 hours, and the adsorption cannot reach saturation when the adsorption time is short, and the adsorption time is too long, so that the adsorption amount of the elemental iodine cannot be further increased, and the energy consumption is increased.
Example 2
The difference from example 1 was that the temperature of adsorption was 45℃and the rest of the procedure was the same as in example 1, to obtain BiOI in which the amount of iodine adsorbed by Bi-MOF was 871.92mg/g.
Comparative example 4
The difference from example 1 was that the temperature of adsorption was 95℃and the rest of the procedure was the same as in example 1, to obtain BiOI in which the amount of iodine adsorbed by Bi-MOF was 863.57mg/g.
Comparative example 5
The difference from example 1 was that the temperature of adsorption was 25℃and the rest of the procedure was the same as in example 1, to obtain BiOI in which the amount of iodine adsorbed by Bi-MOF was 670.68mg/g.
The adsorption amount bar graph of Bi-MOF to iodine in the BiOI prepared in examples 1 and 2 and comparative examples 4 and 5 is shown in FIG. 8. As can be seen from FIG. 8, in the adsorption temperature range defined by the invention, within 45-75 ℃, bi-MOF can fully adsorb iodine simple substance, when the adsorption temperature is lower, adsorption cannot reach saturation within 24 hours, and when the adsorption temperature is too high, the adsorption amount of iodine simple substance can be reduced, and meanwhile, the energy consumption is increased.
From the comparison example and the embodiment, the BiOI photocatalyst provided by the invention has visible light and near infrared light responsivity, has a light absorption range of 800nm, and has excellent photocatalytic activity under visible light.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A preparation method of a visible light response BiOI photocatalyst comprises the following steps:
(1) Mixing 1,3, 5-benzene tricarboxylic acid, bismuth nitrate pentahydrate and methanol, and performing solvothermal reaction to obtain
Bi-MOF;
(2) Activating the Bi-MOF obtained in the step (1), and then placing the activated Bi-MOF and an iodine simple substance in a closed container for adsorption reaction to obtain a BiOI photocatalyst;
the activation temperature in the step (2) is 120 ℃, the activation time is 12 hours, and the activation is carried out in a vacuum drying oven;
the temperature of the adsorption reaction in the step (2) is 45-75 ℃, and the time of the adsorption reaction is 20-24 hours.
2. The method for preparing a visible light responsive BiOI photocatalyst according to claim 1, wherein the ratio of the amounts of the substances of 1,3, 5-trimellitic acid and bismuth nitrate pentahydrate in the step (1) is (11-13): 1.
3. The method for preparing a visible light responsive BiOI photocatalyst according to claim 1, wherein the ratio of the amount of the 1,3, 5-benzene tricarboxylic acid in the step (1) to the volume of methanol is (3-4) mmol (60-80) mL.
4. The preparation method of the visible light responsive BiOI photocatalyst according to claim 1, wherein the solvothermal reaction temperature in the step (1) is 110-125 ℃, and the solvothermal reaction time is 18-24 hours.
5. The preparation method of the visible light responsive BiOI photocatalyst according to claim 1, wherein the mass ratio of Bi-MOF to iodine simple substance in the step (2) is (0.5-1.2) (245-255).
6. The BiOI photocatalyst prepared by the preparation method according to any one of claims 1-5, wherein the BiOI photocatalyst has a nanorod structure.
7. Use of the BiOI photocatalyst of claim 6 in a photocatalyst.
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