CN112246255B - BiOI-Bi 5 O 7 Preparation method and application of I-Bi three-phase composite material - Google Patents
BiOI-Bi 5 O 7 Preparation method and application of I-Bi three-phase composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 69
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 23
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 8
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 60
- 238000003756 stirring Methods 0.000 description 28
- 238000005303 weighing Methods 0.000 description 26
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000000227 grinding Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 229910052797 bismuth Inorganic materials 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- RULKYXXCCZZKDZ-UHFFFAOYSA-N 2,3,4,5-tetrachlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C(Cl)=C1Cl RULKYXXCCZZKDZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- 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
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- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/16—Reducing
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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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Abstract
The invention belongs to the technical field of photocatalysts, and particularly relates to BiOI-Bi 5 O 7 A preparation method and application of an I-Bi three-phase composite material, aiming at providing a three-phase composite optical substance with higher photocatalytic activity. The invention discloses a preparation method of a three-phase composite material, which comprises the following steps: 1) Dissolving a certain amount of bismuth nitrate in water to obtain a white suspension; then dissolving a certain amount of potassium iodide in the white suspension to obtain a red suspension; adding a certain amount of sodium borohydride into the red suspension, and fully reacting to obtain a reddish brown suspension; 2) Adjusting the reddish brown suspension to pH =6-7 by using sodium hydroxide, and then transferring the suspension to a high-pressure reaction kettle for hydrothermal reaction; 3) And naturally cooling the suspension after the hydrothermal reaction is completed to normal temperature, centrifuging, taking the precipitate, washing and drying to obtain the nano-composite material. The invention also relates to the use of the three-phase compound. The three-phase compound prepared by the method can efficiently degrade organic pollutants.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to BiOI-Bi 5 O 7 A preparation method and application of an I-Bi three-phase composite material.
Background
In recent years, photocatalytic technologies based on semiconductor photocatalytic materials for degrading pollutants in water by utilizing sunlight are rapidly developed. The earliest studied photocatalytic material, tiO 2 The forbidden band width is wide, so that the utilization rate of sunlight is low; and the easy recombination of electrons and holes in the catalytic process of the photocatalyst leads to low photocatalytic efficiency, so that researchers concentrate on developing novel efficient wide-spectral-response photocatalysts.
Among numerous novel photocatalysts, bismuth-based catalysts are favored because of unique crystal structures and high carrier separation efficiency, wherein bismuth oxyhalide (BiOX (X = Cl, br, I) has a lamellar structure with separated positive and negative charges, and the existence of an inter-lamellar electrostatic field can effectively reduce the recombination of photo-generated electrons and holes, so that good catalytic performance is obtained. The energy gap of BiOX is reduced along with the increase of the halogen atomic number, so that the light absorption capacity of the BiOX is correspondingly and gradually enhanced. BiOI has the narrowest bandgap (E) g =1.72-1.92 eV), has strong absorption in the visible light region, and is widely used in the fields of photocatalysis, photoelectrocatalysis, solar energy conversion, and the like. However, in the photocatalytic reaction, the forbidden band of the single-phase BiOI is too narrow, and the recombination rate of the hole-electron pairs is too high, so that the photocatalytic efficiency is greatly reduced. Research shows that BiOI and Bi are mixed 5 O 7 The I forms a p-n heterojunction, can effectively inhibit the recombination of photo-generated electron-hole pairs, and greatly improves the photocatalytic performance. For example, chinese patent CN103316698A discloses a band-adjustable solid solution composite catalyst BiOI-Bi 5 O 7 The composite catalyst shows obviously better than single-phase BiOI or Bi in the degradation process of methyl orange and the preparation method thereof 5 O 7 I catalytic performance. The photocatalytic activity is still very limited, however, because Bi is present 5 O 7 The valence band potential of I is larger, the photogenerated hole oxidation capability is stronger, but the forbidden band width of I causes the light utilization rate of the catalyst to be low.
By using the Surface Plasmon Resonance (SPR) effect of metal, the light absorption and utilization capacity of the semiconductor can be improved, the sunlight conversion can be better realized, and the photocatalytic efficiency can be improved. The bismuth is a typical semimetal, and is a good choice for forming the composite catalyst due to low price, no toxicity, high anisotropy, long average free path of bismuth carriers, low density, small effective mass and higher moving speed. For example, sun et al prepared Bi/BiOI composite catalysts by reducing bismuth oxyiodide with sodium borohydride (Sun M, et al. Synthesis of metallic Bi and defects on BiOI: enhanced photocatalytic NO removal and conversion pathway J chip Journal of Catalysis 2019,40 (6): 826-836.) found that the semimetal Bi can achieve an improvement in photocatalytic performance not only by ultraviolet light but also by migration of surface electrons.
BiOI and Bi have been reported 5 O 7 The composite catalyst of I and Bi consists of two phases, and the two-phase composite material is prepared by a two-step or even three-step method, so that the production process is complex and the production cost is high.
Disclosure of Invention
The invention aims to provide a BiOI-Bi 5 O 7 Method for producing a three-phase I-Bi composite material, and BiOI-Bi produced thereby 5 O 7 The I-Bi three-phase composite material can degrade organic pollutants more efficiently.
BiOI-Bi 5 O 7 The preparation method of the I-Bi three-phase composite material is characterized by comprising the following steps:
1) Dissolving a certain amount of bismuth nitrate in water to obtain a white suspension; then dissolving a certain amount of potassium iodide in the white suspension to obtain a red suspension; adding a certain amount of sodium borohydride into the red suspension, and fully reacting to obtain a reddish brown suspension;
2) Adjusting the pH of the reddish brown suspension to 6-7 by using a sodium hydroxide solution, and then transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction;
3) Naturally cooling the suspension after the hydrothermal reaction is completed to normal temperature, centrifuging, taking the precipitate, washing and drying to obtain the BiOI-Bi 5 O 7 I-Bi three-phase composite material.
The BiOI-Bi is directly obtained by the one-step hydrothermal method 5 O 7 I-Bi IIIThe relative proportion of three phases in the composite material is controlled by controlling the using amount of the reducing agent sodium borohydride, the method is simple, the equipment requirement is low, the time consumption and the energy consumption are low, and the composite material is environment-friendly and energy-saving; simultaneously, the prepared BiOI-Bi 5 O 7 The I-Bi three-phase composite material forms a self-generated heterojunction and shows excellent photocatalytic performance under visible light.
In one embodiment according to the present invention, the molar ratio of bismuth nitrate to potassium iodide is 1:3;
in one embodiment according to the invention, the ratio of bismuth nitrate to water is 1:15.
in one embodiment according to the present invention, the molar ratio of bismuth nitrate to sodium borohydride is 1:0.25-5.5.
In one embodiment according to the invention, the concentration of sodium hydroxide in step 2) is 1-2 mol.L -1 。
In one embodiment according to the present invention, the reaction temperature of the hydrothermal reaction in step 2) is 160 ℃ and the reaction time is 2h.
In one embodiment according to the present invention, the washing in step 3) comprises washing with sequentially deionized water and anhydrous ethanol, and repeating three times.
In one embodiment according to the invention, the drying in step 3) is a drying treatment at a temperature of 60-80 ℃ for 4-10h.
Another aspect of the invention also relates to the BiOI-Bi prepared according to the preparation method of the three-phase composite material 5 O 7 I-Bi triphase complex. The BiOI-Bi 5 O 7 The I-Bi three-phase compound has higher catalytic efficiency when used for photocatalytic degradation of organic pollutants.
The present invention also relates in one aspect to the above-mentioned BiOI-Bi 5 O 7 The application of the I-Bi three-phase compound in degrading organic compounds. The organic compound comprises phenols such as phenol, bisphenol A, tetrachlorophenol and the like, and organic micromolecular dyes such as methyl orange, rhodamine B, methylene blue and the like.
The invention has the beneficial effects that:
1) The preparation method is simple, and the BiOI-Bi is directly obtained by adopting a one-step hydrothermal method 5 O 7 The I-Bi three-phase composite material controls the relative proportion of three phases in the composite material by controlling the using amount of reducing agent sodium borohydride, and has the advantages of simple method, low equipment requirement, low time consumption and energy consumption, environmental protection and energy saving;
2) Prepared BiOI-Bi 5 O 7 The I-Bi three-phase composite material forms a self-generated heterojunction and shows excellent photocatalytic performance under visible light. 50mg BiOI-Bi 5 O 7 The degradation rate of the I-Bi three-phase composite material sample to 200mL 20mg/L bisphenol A after being irradiated for 120min reaches 87.87%, and the degradation rate is 30.97 times that of the Bi/BiOI two-phase composite material in the comparative example 1 and 14.62 times that of the BiOI sample in the comparative example 2.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments made with reference to the following drawings:
FIG. 1 is a TEM photograph of a three-phase composite catalyst prepared in example 1;
FIG. 2 is an XRD contrast pattern of a composite prepared according to example 1, a composite prepared according to example 2, a composite prepared according to example 4, a composite prepared according to comparative example 1, and a material prepared according to comparative example 2;
FIG. 3 is a graph comparing the degradation of bisphenol A by composites prepared according to example 1, example 2, example 4, comparative example 1, and comparative example 2;
FIG. 4 is a graph of the kinetics of bisphenol A degradation for the composite prepared according to example 1, the composite prepared according to example 2, the composite prepared according to example 4, the composite prepared according to comparative example 1, and the material prepared according to comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the related invention are shown in the drawings.
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1: biOI-Bi 5 O 7 Preparation method of I-Bi three-phase composite material
First Bi (NO) 3 ) 3 ·5H 2 Grinding O solid, weighing 0.4850g of KI solid by using an analytical balance, adding the weighed KI solid into 15mL of deionized water, continuously stirring and dissolving to obtain white suspension, weighing 0.4980g of KI solid by using the analytical balance, adding the KI solid into the white suspension, stirring to obtain dark red suspension, accurately weighing 0.0202g of sodium borohydride solid on the analytical balance, adding the sodium borohydride solid into the obtained dark red suspension, and fully reacting to obtain red brown suspension; under the condition of continuous stirring, 1mol/L sodium hydroxide solution is used for adjusting the pH value to 6.7, then the mixture is transferred to a 25mL hydrothermal reaction kettle and put into a blast drying oven, the temperature is kept for 2h at 160 ℃, and the mixture is naturally cooled to the normal temperature after the reaction is finished. The precipitate in the reaction kettle is collected into a centrifuge tube, separated at 10000 rpm, washed with deionized water and absolute ethyl alcohol three times respectively, centrifuged to separate the precipitate and dried at 80 ℃ for 10h.
FIG. 1 is a TEM photograph of the composite material obtained in example 1, and it can be seen that the composite material is a nano-platelet structure.
Example 2: biOI-Bi 5 O 7 Preparation of I-Bi three-phase composite materialPreparation method
Firstly, bi (NO) is added 3 ) 3 ·5H 2 Grinding O solid, weighing 0.4850g of KI solid by using an analytical balance, adding the weighed KI solid into 15mL of deionized water, continuously stirring and dissolving to obtain white suspension, weighing 0.4980g of KI solid by using the analytical balance, adding the KI solid into the white suspension, stirring to obtain dark red suspension, accurately weighing 0.0601g of sodium borohydride solid on the analytical balance, adding the sodium borohydride solid into the obtained dark red suspension, and fully reacting to obtain red brown suspension; under the condition of continuous stirring, 1mol/L sodium hydroxide solution is used for adjusting the pH value to 6.7, then the mixture is transferred to a 25mL hydrothermal reaction kettle and put into a blast drying box, the temperature is kept for 2 hours at 160 ℃, and the mixture is naturally cooled to the normal temperature after the reaction is finished. The precipitate in the reaction kettle is collected into a centrifuge tube, separated at 10000 rpm, washed with deionized water and absolute ethyl alcohol three times respectively, centrifuged to separate the precipitate and dried at 80 ℃ for 10h.
Example 3: biOI-Bi 5 O 7 Preparation method of I-Bi three-phase composite material
First Bi (NO) 3 ) 3 ·5H 2 Grinding O solid, weighing 0.4850g of the ground O solid by using an analytical balance, adding the ground O solid into 15mL of deionized water, continuously stirring and dissolving to obtain white suspension, weighing 0.4980g of KI solid by using the analytical balance, adding the KI solid into the white suspension, stirring to obtain crimson suspension, accurately weighing 0.0801g of sodium borohydride solid on the analytical balance, adding the crimson suspension into the obtained crimson suspension, and fully reacting to obtain reddish brown suspension; under the condition of continuous stirring, 1mol/L sodium hydroxide solution is used for adjusting the pH value to 6.7, then the mixture is transferred to a 25mL hydrothermal reaction kettle and put into a blast drying oven, the temperature is kept for 2h at 160 ℃, and the mixture is naturally cooled to the normal temperature after the reaction is finished. The precipitate in the reaction kettle is collected into a centrifuge tube, separated at 10000 rpm, washed with deionized water and absolute ethyl alcohol three times respectively, centrifuged to separate the precipitate and dried at 80 ℃ for 10h.
Example 4: biOI-Bi 5 O 7 Preparation method of I-Bi three-phase composite material
First Bi (NO) 3 ) 3 ·5H 2 Grinding the O solid, weighing 0.4850g of the O solid by using an analytical balance, adding the weighed 0.4850g of the O solid into 15mL of deionized water, continuously stirring and dissolving to obtain a white suspension, weighing 0.4980g of KI solid by using the analytical balance, adding the KI solid into the white suspension, stirring to obtain a dark red suspension, accurately weighing 0.1000g of sodium borohydride solid on the analytical balance, adding the sodium borohydride solid into the obtained dark red suspension, and fully reacting to obtain a red brown suspension; under the condition of continuous stirring, 1mol/L sodium hydroxide solution is used for adjusting the pH value to 6.7, then the mixture is transferred to a 25mL hydrothermal reaction kettle and put into a blast drying box, the temperature is kept for 2 hours at 160 ℃, and the mixture is naturally cooled to the normal temperature after the reaction is finished. The precipitate in the reaction kettle is collected into a centrifuge tube, separated at 10000 rpm, washed with deionized water and absolute ethyl alcohol three times respectively, centrifuged to separate the precipitate and dried at 80 ℃ for 10h.
Example 5: biOI-Bi 5 O 7 Preparation method of I-Bi three-phase composite material
First Bi (NO) 3 ) 3 ·5H 2 Grinding O solid, weighing 0.4850g of KI solid by using an analytical balance, adding the weighed KI solid into 15mL of deionized water, continuously stirring and dissolving to obtain white suspension, weighing 0.4980g of KI solid by using the analytical balance, adding the KI solid into the white suspension, stirring to obtain dark red suspension, accurately weighing 0.0202g of sodium borohydride solid on the analytical balance, adding the sodium borohydride solid into the obtained dark red suspension, and fully reacting to obtain red brown suspension; under the condition of continuous stirring, 1mol/L sodium hydroxide solution is used for adjusting the pH value to 6.4, then the mixture is transferred to a 25mL hydrothermal reaction kettle and put into a blast drying oven, the temperature is kept for 2h at 160 ℃, and the mixture is naturally cooled to the normal temperature after the reaction is finished. The precipitate in the reaction kettle is collected into a centrifuge tube, separated at 10000 rpm, washed with deionized water and absolute ethyl alcohol three times respectively, centrifuged to separate the precipitate and dried at 80 ℃ for 10h.
Example 6: biOI-Bi 5 O 7 Preparation method of I-Bi three-phase composite material
First Bi (NO) 3 ) 3 ·5H 2 Grinding O solid, weighing 0.4850g of KI solid by using an analytical balance, adding the weighed KI solid into 15mL of deionized water, continuously stirring and dissolving to obtain white suspension, weighing 0.4980g of KI solid by using the analytical balance, adding the KI solid into the white suspension, stirring to obtain dark red suspension, accurately weighing 0.0202g of sodium borohydride solid on the analytical balance, adding the sodium borohydride solid into the obtained dark red suspension, and fully reacting to obtain red brown suspension; under the condition of continuous stirring, 1mol/L sodium hydroxide solution is used for adjusting the pH value to 6.9, then the mixture is transferred to a 25mL hydrothermal reaction kettle and put into a blast drying oven, the temperature is kept for 2h at 160 ℃, and the mixture is naturally cooled to the normal temperature after the reaction is finished. And collecting precipitates in the reaction kettle into a centrifuge tube, separating the precipitates at the rotation speed of 10000 rpm, washing the precipitates respectively with deionized water and absolute ethyl alcohol for three times, centrifuging the precipitates, and drying the precipitates at the temperature of 80 ℃ for 10 hours.
Example 7: biOI-Bi 5 O 7 Preparation method of I-Bi three-phase composite material
First Bi (NO) 3 ) 3 ·5H 2 Grinding O solid, weighing 0.4850g of KI solid by using an analytical balance, adding the weighed KI solid into 15mL of deionized water, continuously stirring and dissolving to obtain white suspension, weighing 0.4980g of KI solid by using the analytical balance, adding the KI solid into the white suspension, stirring to obtain dark red suspension, accurately weighing 0.0202g of sodium borohydride solid on the analytical balance, adding the sodium borohydride solid into the obtained dark red suspension, and fully reacting to obtain red brown suspension; under the condition of continuous stirring, 2mol/L sodium hydroxide solution is used for adjusting the pH value to 6.7, then the mixture is transferred to a 25mL hydrothermal reaction kettle and put into a blast drying oven, the temperature is kept for 2h at 160 ℃, and the mixture is naturally cooled to the normal temperature after the reaction is finished. The precipitate in the reaction kettle is collected into a centrifuge tube, separated at 10000 rpm, washed with deionized water and absolute ethyl alcohol three times respectively, centrifuged to separate the precipitate and dried at 80 ℃ for 10h.
Comparative example 1: preparation method of BiOI-Bi two-phase composite material
First Bi (NO) 3 ) 3 ·5H 2 Grinding O solid, and analyzing with balanceWeighing 0.4850g of solid, adding the solid into 15mL of deionized water, continuously stirring and dissolving to obtain a white suspension, weighing 0.4980g of KI solid by using an analytical balance, adding the solid into the white suspension, stirring to obtain a dark red suspension, accurately weighing 0.2002g of sodium borohydride solid on the analytical balance, adding the solid into the obtained dark red suspension, and fully reacting to obtain a reddish brown suspension; under the condition of continuous stirring, 1mol/L sodium hydroxide solution is used for adjusting the pH value to 6.7, then the mixture is transferred to a 25mL hydrothermal reaction kettle and put into a blast drying oven, the temperature is kept for 2h at 160 ℃, and the mixture is naturally cooled to the normal temperature after the reaction is finished. The precipitate in the reaction kettle is collected into a centrifuge tube, separated at 10000 rpm, washed with deionized water and absolute ethyl alcohol three times respectively, centrifuged to separate the precipitate and dried at 80 ℃ for 10h.
Comparative example 2: preparation method of BiOI single-phase material
First Bi (NO) 3 ) 3 ·5H 2 Grinding the O solid, weighing 0.4850g of KI solid by using an analytical balance, adding the weighed KI solid into 15mL of deionized water, continuously stirring for dissolving to obtain a white suspension, weighing 0.4980g of KI solid by using the analytical balance, adding the KI solid into the white suspension, stirring to obtain a dark red suspension, adjusting the pH value to 6.7 by using 1mol/L sodium hydroxide solution under the condition of continuous stirring, transferring the solution into a 25mL hydrothermal reaction kettle, placing the kettle into a blast type drying box, preserving the heat at 160 ℃ for 2 hours, and naturally cooling to the normal temperature after the reaction is finished. And collecting precipitates in the reaction kettle into a centrifuge tube, separating the precipitates at the rotation speed of 10000 rpm, washing the precipitates respectively with deionized water and absolute ethyl alcohol for three times, centrifuging the precipitates, and drying the precipitates at the temperature of 80 ℃ for 10 hours.
X-ray polycrystalline diffraction analysis was performed on the composite material prepared according to example 1, the composite material prepared according to example 2, the composite material prepared according to example 4, the composite material prepared according to comparative example 1, and the material prepared according to comparative example 2, respectively, and as a result, as shown in FIG. 2, when sodium borohydride was added in an amount of 0.0202g, 0.0601g, 0.1000g, the prepared samples exhibited BiOI, bi 5 O 7 I and Bi. Comparative example 1 is shownBi and bio, comparative example 2 is a mono-phase composition of bio i.
Example 8: biOI-Bi 5 O 7 Photocatalytic performance test of I-Bi three-phase composite material
Preparing 250mL and 20mg/L bisphenol A solution accurately by using a 250mL volumetric flask, transferring 200mL and 20mg/L bisphenol A solution into a photocatalytic reaction kettle accurately by using a transfer pipette, putting 7mL bisphenol A into a centrifuge tube, accurately weighing 50mg of photocatalyst by using an analytical balance, adding the photocatalyst into the reaction kettle, stirring the suspension liquid for 0.5h under a dark condition to achieve adsorption/desorption balance (the process is dark reaction), then turning on a lamp to carry out light reaction, taking samples once every 30min, and taking 6 samples in total. The sample in the centrifuge tube was spun at 10000 r.min -1 Centrifuging for 10min in a desk-top high-speed centrifuge, allowing the photocatalyst to sink to the bottom of the centrifuge tube, and sucking the supernatant with a rubber-tipped dropper to measure the absorbance at 275 nm.
The composite material prepared according to example 1, the composite material prepared according to example 2, the composite material prepared according to example 4, the composite material prepared according to comparative example 1, and the material prepared according to comparative example 2 were respectively tested by the above-described methods, and the results are shown in fig. 3 and fig. 4, respectively. As can be seen from FIG. 3, the composite material of example 1 showed the highest photocatalytic activity, and it was degraded by 87.87% of 20mg/L bisphenol A within 120 min. As can be seen from FIG. 4, bisphenol A (20 mg/L) was degraded within 90min, and the composite material of example 1 had the highest photocatalytic activity, and the degradation rate was 30.97 times that of the Bi/BiOI two-phase composite material of comparative example 1 and 14.62 times that of the BiOI sample of comparative example 2.
So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is apparent to those skilled in the art that the scope of the present invention is not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
Claims (5)
1. BiOI-Bi 5 O 7 The preparation method of the I-Bi three-phase composite material is characterized by comprising the following steps:
1) A certain amount of Bi (NO) 3 ) 3 ·5H 2 Dissolving O in water to obtain white suspension; then dissolving a certain amount of potassium iodide in the white suspension to obtain a red suspension; adding a certain amount of sodium borohydride into the red suspension, and fully reacting to obtain a reddish brown suspension;
2) Adjusting the pH of the reddish brown suspension to 6-7 by using a sodium hydroxide solution, and then transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction;
3) Naturally cooling the suspension after the hydrothermal reaction is completed to normal temperature, centrifuging, taking the precipitate, washing and drying to obtain the BiOI-Bi 5 O 7 I-Bi three-phase composite material;
the Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O to potassium iodide is 1:3;
in mmol: mL, the Bi (NO) 3 ) 3 ·5H 2 The ratio of O to water is 1:15;
the Bi (NO) 3 ) 3 ·5H 2 The mass of O is 0.4850g, and the mass of sodium borohydride is 0.0202g-0.1000g;
the concentration of the sodium hydroxide in the step 2) is 1-2mol -1 ；
The reaction temperature of the hydrothermal reaction in the step 2) is 160 ℃, and the reaction time is 2h.
2. The method of claim 1, wherein the washing in step 3) comprises washing with deionized water and absolute ethanol sequentially and repeating three times.
3. The method for preparing a three-phase composite material according to claim 1, wherein the drying in step 3) is a drying treatment at a temperature of 60 to 80 ℃ for 4 to 10 hours.
4. Method for preparing a three-phase composite material according to any one of claims 1 to 3Preparing the obtained BiOI-Bi 5 O 7 I-Bi triphase complex.
5. The BiOI-Bi of claim 4 5 O 7 The application of the I-Bi three-phase compound in photocatalytic degradation of organic compounds.
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