CN111729677A - Ag/BiOCl/AgIO3Heterojunction photocatalyst and preparation method and application thereof - Google Patents

Ag/BiOCl/AgIO3Heterojunction photocatalyst and preparation method and application thereof Download PDF

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CN111729677A
CN111729677A CN202010604855.0A CN202010604855A CN111729677A CN 111729677 A CN111729677 A CN 111729677A CN 202010604855 A CN202010604855 A CN 202010604855A CN 111729677 A CN111729677 A CN 111729677A
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biocl
agio
powder
heterojunction photocatalyst
heterojunction
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CN111729677B (en
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谈国强
张碧鑫
张丹
王敏
党明月
王勇
任慧君
夏傲
刘文龙
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Shaanxi University of Science and Technology
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract

The invention provides Ag/BiOCl/AgIO3The preparation method comprises the following steps of 1, preparing a suspension from BiOCl powder with an exposed (001) crystal face by using deionized water, and adding AgNO3Powder and NaIO3Uniformly mixing the powder to obtain a mixed system; step 2, carrying out illumination reaction on the mixed system under a light source to obtain a reaction solution; step 3, separating the product in the reaction liquid and dryingTo obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst. The electrons of Ag can be transferred to BiOCl to raise the Fermi level of BiOCl, and BiOCl and AgIO with I-type energy band structure3The structure is converted into a direct Z-shaped (staggered) heterojunction structure, so that the reduction capability of photoproduction electrons and the oxidation capability of photoproduction holes are improved, the dissociation of excitons at a heterojunction interface is accelerated, and the heterojunction photocatalyst can effectively degrade organic pollutants.

Description

Ag/BiOCl/AgIO3Heterojunction photocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of semiconductor photocatalytic functional materials, and particularly relates to Ag/BiOCl/AgIO3A heterojunction photocatalyst, a preparation method and application thereof.
Background
In recent years, semiconductor photocatalysis technology has a wide application prospect in the aspect of controlling environmental pollution, and is receiving attention of researchers.
BiOCl is a layered structure consisting of a bismuth oxide layer and a chlorine atomic layer, and photo-generated electrons and holes are easy to have strong interaction in the limited layered structure to generate new photo-generated species-excitons, so that the carriers in the BiOCl are not obviously separated, and the photocatalysis performance is not ideal. To facilitate exciton dissociation, a suitable heterojunction structure can be constructed that allows efficient dissociation of excitons into free electrons and holes at the heterojunction interface. In addition, BiOCl is a wide bandgap semiconductor that responds only to ultraviolet light. Aiming at the defects of weak visible light absorption, unobvious separation of photon-generated carriers and the like of BiOCl, noble metal can be loaded on the surface and a heterojunction can be constructed to modify the surface. Among the numerous noble metals, Ag is the most economical and noble metal having a strong Surface Plasmon Resonance (SPR) effect, which enhances the absorption of semiconductors in the visible region. In recent years, Z-type heterojunctions have been widely studied because they can not only retain the strong reduction and oxidation potentials of semiconductors, but also accelerate exciton dissociation at the heterojunction interface.
In conclusion, under the action of the SPR effect of Ag and the Z-type heterojunction, the visible light absorption of BiOCl can be enhanced, the dissociation of excitons can be accelerated, and the effective separation of photo-generated charges can be realized. Therefore, it is necessary to prepare a heterojunction photocatalyst based on BiOCl and Ag, but there is no report on the preparation.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides Ag/BiOCl/AgIO3The heterojunction photocatalyst, the preparation method and the application thereof have the advantages of low cost and simple operation, and can be used for degrading organic pollutants.
The invention is realized by the following technical scheme:
Ag/BiOCl/AgIO3The preparation method of the heterojunction photocatalyst comprises the following steps,
step 1, preparing a suspension of BiOCl powder with exposed (001) crystal face by using deionized water, and then adding AgNO3Powder and NaIO3Uniformly mixing the powder to obtain a mixed system;
step 2, carrying out illumination reaction on the mixed system under a light source to obtain a reaction solution;
step 3, separating and drying the product in the reaction solution to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Preferably, in the step 1, deionized water is added into the BiOCl powder with the (001) crystal face exposed, and the mixture is stirred at room temperature for 30-40 min to obtain a suspension.
Preferably, BiOCl powder and AgNO in step 13Powder and NaIO3The mass ratio of the powder is 0.3: (0.01-0.05): (0.05-0.3).
Preferably, BiOCl powder and AgNO in step 13Powder and NaIO3The concentration of the powder in the mixed system is recorded in g/mL, and the proportion is (5.00-7.50): (0.17-1.25): (0.83-7.50).
Preferably, the illumination reaction time in the step 2 is 2-3 h.
Preferably, in step 2, the mixed system is reacted in a photochemical reactor.
Ag/BiOCl/AgIO of any one of the above3Ag/BiOCl/AgIO obtained by preparation method of heterojunction photocatalyst3A heterojunction photocatalyst.
Further, the Ag/BiOCl/AgIO3The heterojunction photocatalyst is direct Z-type heterojunction photocatalyst, wherein Ag and AgIO3Are deposited on the (001) crystal plane of BiOCl.
Ag/BiOCl/AgIO3Application of the heterojunction photocatalyst in degrading rhodamine B under sunlight and near infrared light.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to Ag/BiOCl/AgIO3The preparation method of the heterojunction photocatalyst comprises the steps of preparing a suspension from BiOCl powder with an exposed (001) crystal face, and adding AgNO3Powder and NaIO3The powder is subjected to illumination reaction, and the product is separated and dried to obtain Ag/BiOCl/AgIO3Heterojunction photocatalyst, Ag/BiOCl/AgIO3The material belongs to a Z-type heterojunction, and the layered structure of BiOCl endows the material with a strong exciton effect, namely, most of photo-generated electrons and holes can be combined to form a large number of primary excitons under illumination due to coulomb action force, and only few photo-generated electrons can be transferred to a (001) crystal face of the BiOCl; the SPR effect of Ag can enhance the light absorption of the semiconductor; the Z-type heterojunction can keep the strong oxidation potential and the strong reduction potential of a semiconductor on one hand, and on the other hand, the Z-type heterojunction can accelerate excitons to be dissociated into free electrons and holes at the heterojunction interface, so that the establishment of the Z-type heterojunction is beneficial to exciton separation. Under illumination, only few photo-generated electrons migrate to the (001) crystal face of BiOCl, so that reduction of Ag is insufficient+Thus Ag+And IO3 -Will react preferentially to form AgIO3。AgIO3The nucleus further attracts Ag+Forming an adsorption layer to form AgIO3·Ag+Colloidal particles, AgIO3·Ag+Colloidal particles adsorbing NO in solution3 -Finally generate AgIO3·Ag+·NO3 -And (4) micelle. According to DLVO theory, AgIO3·Ag+Attracted to the (001) crystal plane of BiOCl, which has few electrons, by van der waals forces. AgIO3Self-assembled into irregular sheets to be adsorbed on the (001) crystal face of BiOCl to form two-dimensional AgIO3And two-dimensional BiOCl interface. And Ag+Attracted by a small amount of electrons on the face of BiOCl (001) and reduced to Ag. Finally, AgIO3And Ag are deposited on the (001) crystal face of BiOCl to prepare Ag/BiOCl/AgIO3A heterojunction photocatalyst. Although BiOCl and AgIO3Is in I-type (embedded) energy band structure, but because the work function of Ag is less than that of BiOCl, the electrons of Ag can be transferred to BiOCl to raise the Fermi level of BiOCl, and the BiOCl and AgIO of I-type energy band structure3The structure is converted into a direct Z-shaped (staggered) heterojunction structure, so that the reduction capability of photoproduction electrons and the oxidation capability of photoproduction holes are improved, the dissociation of excitons at a heterojunction interface is accelerated, and the heterojunction photocatalyst can effectively degrade organic pollutants.
Under the irradiation of light, free electrons in Ag compete for holes in primary excitons in BiOCl to form secondary excitons and release electrons in the primary excitons. Electrons released by the primary exciton reach a BiOCl conduction band to participate in reduction reaction, and a BiOCl valence band hole and AgIO3Conduction band electron recombination, retention of BiOCl conduction band electron with strong reduction capability and AgIO with strong oxidation capability3The valence band hole not only accelerates the dissociation of excitons in the BiOCl, but also improves the redox capability of the material.
The invention proves that the heterojunction photocatalyst has high degradation rate on rhodamine B under sunlight through simulated sunlight, can effectively degrade the rhodamine B under near infrared light, and has good application prospect.
Drawings
FIG. 1 is XRD patterns of products prepared in comparative examples 1 to 2 and examples 1 to 6 of the present invention.
Fig. 2 is an enlarged view of fig. 1 at 2 θ of 10 to 15 °.
Fig. 3 is an enlarged view of fig. 1 at 22-28 °.
FIG. 4 is a Raman diagram of products prepared in comparative examples 1 to 2 and examples 1 to 6 of the present invention.
FIG. 5 is a graph showing UV-visDRS of products prepared in comparative examples 1 to 2 and examples 1 to 6 according to the present invention.
FIG. 6 is an XPS plot of a product prepared in example 4 of the present invention.
Fig. 7 is an SEM image of the product prepared in comparative example 1 of the present invention.
FIG. 8 is an HRTEM image of the product prepared in comparative example 1 of the present invention.
FIG. 9 is an SEM photograph of a product prepared in comparative example 2 of the present invention.
FIG. 10 is an SEM photograph of a product prepared in example 4 of the present invention.
FIG. 11 shows Ag/BiOCl/AgIO prepared by the present invention3A mechanism diagram of the formation of the heterojunction photocatalyst.
FIG. 12 is a PL diagram of products prepared in comparative examples 1 to 2 and examples 1 to 6 of the present invention.
FIG. 13 is a graph showing photocurrents i-t of products prepared in comparative examples 1 to 2 and examples 1 to 6 of the present invention.
FIG. 14 is EIS charts of electrochemical impedance spectra of products prepared in comparative examples 1 to 2 and examples 1 to 6 of the present invention.
FIG. 15 is a graph showing the removal rate of rhodamine B and the capture of active species in simulated sunlight (500W) for the products prepared in comparative examples 1 to 2 and examples 1 to 6 of the present invention.
FIG. 16 is a graph showing the removal rate of rhodamine B from the product prepared in example 4 of the present invention under irradiation of near infrared monochromatic light (850nm, 940nm, and 1100 nm).
FIG. 17 is a graph of the work function of Ag calculated by DFT theory.
Fig. 18 is a graph of the work function of BiOCl calculated by DFT theory.
FIG. 19 is a graph of the work function of Ag (001)/BiOCl (001) calculated by DFT theory.
FIG. 20 is a schematic diagram of electron transfer after interface formation between Ag and BiOCl.
FIG. 21 shows Ag/BiOCl/AgIO prepared by the present invention3A photocatalytic mechanism diagram of a heterojunction photocatalyst.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention uses Bi (NO)3)3·5H2Preparing BiOCl with an exposed (001) crystal face by a hydrothermal method, wherein O is a Bi source, NaCl is a Cl source; with AgNO3As a source of Ag, NaIO3Is IO3 -The source is prepared into Ag/BiOCl/AgIO by adopting a light reduction method3A heterojunction photocatalyst.
The Ag/BiOCl/AgIO of the invention3The preparation method of the heterojunction photocatalyst concretely comprises the following steps:
step 1, Bi (NO) is added according to the molar ratio of 1:13)3·5H2Dissolving O and NaCl in deionized water, taking 48mL of the deionized water, and stirring for 2h to obtain a reaction precursor solution; reacting the precursor solution at 160 ℃ for 18h, cooling the temperature to room temperature after the reaction is finished, taking out the reaction kettle, standing to remove supernatant, washing precipitates respectively with deionized water and absolute ethyl alcohol for 3 times, drying at 70 ℃, and grinding to obtain BiOCl powder with the crystal face (001) exposed;
step 2, adding 40-60 ml of deionized water into the BiOCl powder with the exposed (001) crystal face obtained in the step 1, stirring at room temperature for 30-40 min to obtain a suspension A, and adding AgNO3And NaIO3Adding into the suspension A to obtain a mixed system B, wherein the mixed system B is BiOCl powder with an exposed (001) crystal face, AgNO3And NaIO3Is 0.3: (0.01-0.05): (0.05-0.3) and the corresponding concentration in g/mL is (5.00-7.50): (0.17-1.25): (0.83-7.50), placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 2-3 hours to obtain reaction liquid, and adopting a light source with illumination as a xenon lamp as simulated sunlight;
under illumination, Ag+And IO3 -Will react preferentially to form AgIO3。AgIO3The nucleus further attracts Ag+Forming an adsorption layer to form AgIO3·Ag+Colloidal particles, AgIO3·Ag+Colloidal particle suckerNO in the side solution3 -Finally generate AgIO3·Ag+·NO3 -And (4) micelle. According to DLVO theory, AgIO3·Ag+Attracted to the (001) crystal plane of BiOCl, which has few electrons, by van der waals forces. AgIO3Self-assembled into irregular sheets to be adsorbed on the (001) crystal face of BiOCl to form two-dimensional AgIO3And two-dimensional BiOCl interface. And Ag+Attracted by a small amount of electrons on the face of BiOCl (001) and reduced to Ag. Finally, AgIO3And Ag are deposited on the (001) crystal face of BiOCl to prepare Ag/BiOCl/AgIO3A heterojunction photocatalyst. Although BiOCl and AgIO3Is of I-type (embedded) energy band structure, but because the work function of Ag is less than that of BiOCl, the electrons of Ag can be transferred to BiOCl to raise the Fermi level of BiOCl, and the BiOCl and AgIO of I-type (embedded) energy band structure3And the structure is converted into a direct Z-type (staggered) heterojunction structure.
Under the irradiation of light, free electrons in Ag compete for holes in the primary exciton in the BiOCl to form a secondary exciton, and electrons in the primary exciton are released. Electrons released by the primary exciton reach a BiOCl conduction band to participate in reduction reaction, and a BiOCl valence band hole and AgIO3Conduction band electron recombination, retention of BiOCl conduction band electron with strong reduction capability and AgIO with strong oxidation capability3The valence band hole not only accelerates the dissociation of excitons in the BiOCl, but also improves the redox capability of the material.
Then filtering the reaction solution, washing the obtained precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
The composite photocatalyst can be used for degrading organic pollutants.
The Ag/BiOCl/AgIO of the invention3The preparation of the heterojunction photocatalyst was carried out as follows:
example 1:
step 1: adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL deionized water, stirring at room temperature for 2h to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reactionReacting in a kettle at 160 ℃ for 18h, cooling the temperature to room temperature after the reaction is finished, taking out the reaction kettle, standing to remove supernatant, respectively washing precipitates with deionized water and absolute ethyl alcohol for 3 times, drying at 70 ℃ and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl suspension A, and adding 0.03g of AgNO3And 0.05g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 2.5h to obtain a reaction solution, filtering the reaction solution, washing the precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 2:
step 1: adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove a supernatant, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl suspension A, and adding 0.03g of AgNO3And 0.10g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 2.5h to obtain a reaction solution, filtering the reaction solution, washing the precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 3:
step 1: adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL deionized water, stirring at room temperature for 2h to obtain reaction precursor solution, and mixingTransferring the precursor solution into a hydrothermal reaction kettle, reacting at 160 ℃ for 18h, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, respectively washing precipitates for 3 times by using deionized water and absolute ethyl alcohol, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl suspension A, and adding 0.03g of AgNO3And 0.15g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 2.5h to obtain a reaction solution, filtering the reaction solution, washing the precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 4:
step 1: adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove a supernatant, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl suspension A, and adding 0.03g of AgNO3And 0.20g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 2.5h to obtain a reaction solution, filtering the reaction solution, washing the precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 5:
step 1: adding 8mmol of Bi (NO)3)3·5H2O, 8mmol NaCl in 48mL deionized water, stirring at room temperatureObtaining reaction precursor liquid after 2 hours, transferring the precursor liquid into a hydrothermal reaction kettle, reacting for 18 hours at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 70 ℃ to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 60mL of water, stirring at room temperature for 40min to obtain (001) crystal face BiOCl suspension A, and adding 0.03g of AgNO3And 0.25g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 2.5h to obtain a reaction solution, filtering the reaction solution, washing the precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 6:
step 1: adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove a supernatant, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 60mL of water, stirring at room temperature for 40min to obtain (001) crystal face BiOCl suspension A, and adding 0.03g of AgNO3And 0.30g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 2.5h to obtain a reaction solution, filtering the reaction solution, washing the precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 7:
step 1: adding 8mmol of Bi (NO)3)3·5H2O, 8mmol NaCl dissolved in 48mLStirring in ionized water at room temperature for 2 hours to obtain reaction precursor liquid, transferring the precursor liquid to a hydrothermal reaction kettle, reacting at 160 ℃ for 18 hours, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3 times by using the ionized water and absolute ethyl alcohol respectively, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 40mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl suspension A, and adding 0.03g of AgNO3And 0.20g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for 2h of illumination reduction reaction to obtain a reaction solution, filtering the reaction solution, respectively cleaning precipitates with deionized water and absolute ethyl alcohol for 3 times, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 8:
step 1: adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove a supernatant, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 50mL of water, stirring at room temperature for 35min to obtain (001) crystal face BiOCl suspension A, and adding 0.03g of AgNO3And 0.20g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 2.5h to obtain a reaction solution, filtering the reaction solution, washing the precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 9:
step 1: adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove a supernatant, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 60mL of water, stirring at room temperature for 35min to obtain (001) crystal face BiOCl suspension A, and adding 0.01g of AgNO3And 0.20g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for illumination reduction reaction for 3h to obtain a reaction solution, filtering the reaction solution, respectively cleaning precipitates with deionized water and absolute ethyl alcohol for 3 times, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Example 10:
step 1: adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove a supernatant, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
step 2:
dissolving 0.3g of exposed (001) crystal face BiOCl powder in 60mL of water, stirring at room temperature for 40min to obtain (001) crystal face BiOCl suspension A, and adding 0.05g of AgNO3And 0.20g NaIO3Adding into the suspension A to obtain a mixed system B, placing the mixed system B in an XPA-3 photochemical reactor for 2h of illumination reduction reaction to obtain a reaction solution, filtering the reaction solution, respectively cleaning precipitates with deionized water and absolute ethyl alcohol for 3 times, and drying at 70 ℃ to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
Comparative example 1
Adding 8mmol of Bi (NO)3)3·5H2Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove a supernatant, washing precipitates for 3 times by using the deionized water and absolute ethyl alcohol respectively, drying at 70 ℃, and grinding to obtain exposed (001) crystal face BiOCl powder;
comparative example 2
0.2g of NaIO3And 0.03g AgNO3Dissolving in 60mL deionized water, stirring at room temperature for 3h, standing to remove supernatant, washing precipitate with deionized water and anhydrous ethanol for 3 times, drying at 70 deg.C, and grinding to obtain AgIO3Powder;
the above conclusions and mechanisms are specifically explained below.
FIG. 1 shows Ag/BiOCl/AgIO prepared by the present invention3XRD pattern of the heterojunction photocatalyst. Wherein a and b are BiOCl and AgIO synthesized according to comparative example 1 and comparative example 2, respectively3And c, d, e, f, g and h are photocatalysts synthesized according to example 1, example 2, example 3, example 4, example 5 and example 6, respectively. FIG. 1, AgIO3And diffraction peaks of BiOCl respectively correspond to the orthogonal phase AgIO3And tetragonal BiOCl, which shows strong and sharp diffraction peaks, shows that the crystal planes (001), (002) and (003) have high crystallinity, and the diffraction peaks of the other crystal planes are obviously higher than those of the rest crystal planes, which indicates that the BiOCl exposes the (001) crystal plane. All Ag/BiOCl/AgIO3All the photocatalysts contain AgIO3And the characteristic diffraction peak of BiOCl proves that Ag/BiOCl/AgIO3In the presence of AgIO3And BiOCl. From a partial enlarged view (fig. 2, 2 θ 10-15 ° and fig. 3, 2 θ 22-28 °), Ag/BiOCl/AgIO was observed3The diffraction peak of (A) is significantly shifted compared with that of BiOCl, which indicates that AgIO3And BiOCl. Compared with BiOCl, Ag/BiOCl/AgIO3The decrease in the diffraction peak intensity of the (001), (002) and (003) planes of (A) and (B) is due to the deposition of Ag and AgIO on the BiOCl (001) plane3The shielding effect of (1).
FIG. 4 shows Ag/BiOCl/AgIO prepared by the present invention3Raman spectra of heterojunction photocatalysts, wherein a and b are BiOCl and AgIO synthesized according to comparative example 1 and comparative example 2, respectively3And c, d, e, f, g, h are the Ranman spectra of the photocatalysts synthesized according to example 1, example 2, example 3, example 4, example 5 and example 6, respectively. BiOCl at 145cm-1And 199cm-1The Raman peaks correspond to A1gBi-Cl stretching vibration mode of (A) and (B)gThe Bi-Cl stretching vibration mode of (1). AgIO3At-143 cm-1The peak at (A) is due to Ag and IO3 -700-800 cm in length-1Raman peak at is derived from IO3 -。Ag/BiOCl/AgIO3Simultaneous presence of BiOCl and AgIO in photocatalyst3The Raman characteristic peaks of (A) indicate BiOCl and AgIO3Coexisting, consistent with XRD results. In addition, Ag/BiOCl/AgIO3At 145cm-1And 199cm-1The intensity of the Raman peak is obviously lower than that of BiOCl, which is caused by simultaneously depositing Ag and AgIO on the surface of BiOCl3And the result is that.
In the light absorption curves of FIG. 5, a and b are BiOCl and AgIO synthesized according to comparative example 1 and comparative example 2, respectively3And c, d, e, f, g and h are photocatalysts synthesized according to examples 1, 2, 3, 4, 5 and 6, respectively, it being noted that BiOCl is only comparable to AgIO3The lower point is slightly lower, the two almost coincide when drawing, but the trends of the whole of the embodiments 1, 2, 3, 4, 5 and 6 are the same, the lines also almost coincide, but the marks are made in the subsequent enlarged insets, and the position after 800nm is almost unchanged. The light absorption curves are only for calculation of the band gaps of comparative examples 1 and 2 and illustrate that there is an SPR peak for Ag and that the light absorption of the heterojunction is higher than in comparative examples 1 and 2. BiOCl and AgIO3Are respectively positioned near 372nm and 363nm, and the band gap values (BiOCl: 3.33eV, AgIO)3: 3.41eV) was obtained by the formula (1), and further the conduction band position and the valence band position of BiOCl were obtained as 0.475eV, 3.805eV, AgIO, respectively, according to the formulas (2) and (3)3The conduction band and valence band positions of (a) are 0.435eV and 3.845eV, respectively. Pure phase BiOCl and AgIO3In the visible and near redThe light absorption in the outer light area is very weak, however, Ag/BiOCl/AgIO3The light absorption in the visible and even near infrared region is significantly enhanced. A localized surface plasmon resonance peak (LSPR) of Ag was also found at about 535nm, further demonstrating Ag/BiOCl/AgIO3Presence of Ag in the photocatalyst. The LSPR effect of noble metals can enhance the light absorption capability of the material, thus Ag/BiOCl/AgIO3The enhancement of the light absorption capacity is attributed to the LSPR effect of Ag. The LSPR peak position is closely related to the size, number and shape of the noble metal. NaIO3As an electron acceptor, it will react with Ag+Contend for photoelectrons generated by BiOCl. Thus, NaIO3The amount of Ag added directly affects the amount of Ag on the surface of BiOCl. Thus, different Ag/BiOCl/AgIO3The LSPR peak positions of the photocatalysts are also different, as shown in the inset.
Figure BDA0002560629360000151
In the formula:
λ -the threshold of light absorption of the photocatalyst.
EVB＝χ-Ee+0.5Eg(2)
ECB＝EVB-Eg(3)
In the formula:
EVB-a value of a semiconductor valence band potential;
ECB-a value of the semiconductor conduction band potential;
χ -absolute electronegativity of the semiconductor;
Ee-energy level of free electrons with respect to the standard hydrogen electrode (4.5 eV);
Eg-the bandgap value of the semiconductor.
FIG. 6 shows Ag/BiOCl/AgIO prepared according to example 4 of the present invention3XPS spectra of the heterojunction photocatalyst. The peaks at 366eV and 372eV in the figure originate from Ag+The peaks at 367eV and 373eV are from Ag, and the results of combining the graphs of figures 1 to 6 prove that the prepared Ag/BiOCl/AgIO3BiOCl, AgIO in heterojunction photocatalyst3Coexisting with Ag。
FIG. 7, FIG. 8, FIG. 9 and FIG. 10 show Ag/BiOCl/AgIO prepared by the present invention3Microstructure and morphology of the heterojunction photocatalyst. FIG. 7 shows that BiOCl is a disk-like structure (length: 1.5-6 μm, width: 1.5-3 μm, thickness: 0.3-0.6 μm), and the corresponding HRTEM image (FIG. 8) shows a clear fringe spacing of 0.276nm, indicating that the BiOCl prepared exposes the (001) crystal plane. FIG. 9 shows AgIO3Is an irregular lamellar structure (length: 1-6 μm, thickness: 50 nm). Ag/BiOCl/AgIO of FIG. 103In a heterojunction photocatalyst, AgIO3Deposited on the (001) crystal face of BiOCl and closely contacted with BiOCl to form a heterojunction. In addition, the (001) crystal face of BiOCl has many small points, and the small points are Ag as can be seen by combining XPS and an ultraviolet-visible diffuse reflection curve.
FIG. 11 shows Ag/BiOCl/AgIO prepared by the present invention3A mechanism diagram of the formation of the heterojunction photocatalyst. Due to the strong exciton effect of BiOCl, only few electrons and few holes migrate to the (001) and (110) crystal planes of BiOCl, respectively, while a large number of excitons (e) exist--h+) And (4) generating. When AgNO3And NaIO3After adding into the BiOCl suspension, because the (001) crystal face of BiOCl has few electrons, the few electrons are not enough to attract Ag by electrostatic action+，Ag+Will communicate with IO3 -Preferential generation of ions to AgIO3As shown in formula (5). AgIO3The nucleus will further attract Ag+Forming an adsorption layer to form AgIO3·Ag+Colloidal particles (as described in formula (6)), AgIO3·Ag+Will adsorb NO in solution3 -Forming a diffusion layer to finally generate AgIO3·Ag+·NO3 +(as described in formula (7)). According to DLVO theory, AgIO is acted on by van der Waals force3·Ag+The colloidal particles are attracted to the (001) crystal plane by a small amount of electrons of the BiOCl (001) crystal plane. AgIO3Self-assembling to form an irregular lamellar and adsorbing the irregular lamellar on the (001) crystal face of BiOCl to form 2D AgIO3And a 2D BiOCl binding interface; ag+Is reduced into Ag by a small amount of electrons of a (001) crystal face and is dispersed in the (001) crystal face of BiOCl. Finally, Ag and AgIO3Simultaneously depositing on the (001) crystal face of BiOCl to form Ag/BiOCl/AgIO3The photocatalyst is shown as a formula (8).
BiOCl+hυ→e- few(001)BiOCl+h+ few(110)BiOCl+(e--h+) (4)
Ag++IO3 -→AgIO3(5)
AgIO3+Ag+→AgIO3·Ag+(6)
AgIO3·Ag++NO3 -→AgIO3·Ag+·NO3 -(7)
AgIO3·Ag++e-(001)BiOCl→Ag·AgIO3(001)BiOCl (8)
FIG. 12 shows Ag/BiOCl/AgIO prepared by the present invention3PL profile of the heterojunction photocatalyst. Wherein a is BiOCl synthesized according to comparative example 1 and c, d, e, f, g and h are photocatalysts synthesized according to examples 1, 2, 3, 4, 5 and 6, respectively. Ag/BiOCl/AgIO3The PL peak intensity of (A) is significantly lower than that of BiOCl, which indicates that Ag/BiOCl/AgIO3The separation rate of the medium charges is higher than that of BiOCl. In all Ag/BiOCl/AgIO3In the photocatalyst, Ag/BiOCl/AgIO3PL Peak intensity of-4 is weakest, indicating when NaIO3When the amount of (2) is 0.2g, the separation rate of photogenerated carriers is maximized.
FIGS. 13 and 14 are schematic views of Ag/BiOCl/AgIO prepared according to the present invention3I-t curves and EIS spectra of the heterojunction photocatalyst. Wherein a and b are BiOCl and AgIO synthesized according to comparative example 1 and comparative example 2, respectively3And c, d, e, f, g and h are photocatalysts synthesized according to example 1, example 2, example 3, example 4, example 5 and example 6, respectively, and fig. 13 shows that all samples have photocurrent responses under simulated sunlight, which indicates that they can generate photo-generated charges under illumination and photo-generated electrons can be directionally transferred. Apparently, pure phase BiOCl and AgIO3The photocurrent of (2) is extremely weak, since they are all wide band gap semiconductors, only to the ultraviolet light of around 6% of the sunlightAnd (4) responding to light. Compared with a pure phase sample, Ag/BiOCl/AgIO3The photocurrent of the photocatalyst is obviously enhanced, Ag/BiOCl/AgIO3The photocurrent of-4 was 0.25 μ A, which indicates that its photocurrent separation rate and mobility were the greatest. In FIG. 14, Ag/BiOCl/AgIO3Circular arc radius ratio BiOCl and AgIO of photocatalyst3Is small. Further by impedance fitting, an equivalent circuit diagram (inset in fig. 11) and a corresponding charge transfer resistance value (R) were obtainedctAs shown in table 1). Ag/BiOCl/AgIO3R of-4ctMinimum value (1.86 × 10)4Ω)，RctSmaller values indicate faster interfacial charge transfer and higher carrier separation rates. Therefore, according to the radius of the arc and RctThe value is known as Ag/BiOCl/AgIO3The photocatalyst is more beneficial to carrier separation, and Ag/BiOCl/AgIO3-4 has the greatest carrier separation ratio.
Table 1 equivalent circuit fitting results
Figure BDA0002560629360000181
FIG. 15 is a graph showing that the products prepared in comparative examples 1 to 2 and 1 to 6 of the present invention degrade 10mg/L of rhodamine B (RhB) solution, FIG. 16 is a graph showing that the products prepared in example 4 degrade 5mg/L of rhodamine B (RhB) solution, wherein a and b are BiOCl and AgIO synthesized in comparative examples 1 and 2, respectively3And c, d, e, f, g and h are photocatalysts synthesized according to example 1, example 2, example 3, example 4, example 5 and example 6, respectively. In FIG. 15, after the illumination for 2h, BiOCl and AgIO3The degradation rates for RhB were 32% and 20%, respectively, however, Ag/BiOCl/AgIO3The degradation rate of RhB can reach 91%. Due to Ag/BiOCl/AgIO3The light absorption in the near infrared region is obviously higher than that of BiOCl and AgIO3The same degradation experiment was also performed under near infrared light waves. As shown in FIG. 16, Ag/BiOCl/AgIO3The RhB can be degraded under 850nm, 940nm and 1100nm, the degradation rates are 86%, 84% and 82% respectively, which shows that Ag/BiOCl/AgIO3Solar energy can be utilized more efficiently.
In the active species trapping experiment of FIG. 15, p-benzoquinone (pBQ), disodium ethylenediaminetetraacetate (EDTA-2Na) and t-butanol (tBuOH) were introduced as. O2 -，h+And OH trapping agent plays a role in inhibiting photodegradation reaction to different degrees. From the capture result,. O2 -And h+Is the primary active species, while. OH is the secondary active species. BiOCl and AgIO previously calculated from light absorption curves3Has a conduction potential of 0.475V and 0.435V, respectively, which is lower than O2/·O2 -Potential (-0.046V). In this case, it is impossible to generate O2 -This contradicts experimental facts. Therefore, there must be another mechanism to raise the conduction band potential of the semiconductor, resulting in the generation of O2 -. Next, BiOCl and AgIO were calculated3Work function (W) ofF). The work functions of Ag and BiOCl were 4.23eV and 7.37eV, respectively (see fig. 17 and 18). As can be seen from the work function definition, the larger the work function is, the Fermi level (E) is shownF) The lower. When Ag and BiOCl are contacted, an interface is formed, and in order to balance the fermi level, electrons flow from the end with a high fermi level to the end with a low fermi level, that is, electrons in Ag flow to BiOCl (this process is shown by an arrow in fig. 20). The work function of Ag-BiOCl was 4.86eV (as in fig. 19) lower than that of BiOCl (7.37eV), indicating that Ag can raise the fermi level of BiOCl. This is due to the fact that the electron concentration itself in Ag is high, the electron flow has little effect on its fermi level, but is mainly a rise in the BiOCl fermi level (see fig. 20). Finally, the photodegradation stage can generate O2 -。
FIG. 21 shows Ag/BiOCl/AgIO prepared by the present invention3A photocatalytic mechanism diagram of a heterojunction photocatalyst. Based on the above theoretical calculation results, the fermi level of BiOCl is raised by 2.51eV, and the new fermi level is shown as the thick dashed line on the right side of the figure. In this case, the conduction band potential and the valence band potential of BiOCl were-2.035V and 1.295V, respectively, and BiOCl and AgIO3Has an embedded structure. Under illumination, BiOCl and AgIO3The valence band electrons are excited into the conduction band leaving a corresponding hole in the valence band. If AgIO3The valence band hole migrates to the valence band of BiOCl, which then does not correspond to the active species result (in which case OH is the predominant active species). Thus, BiOCl and AgIO3A direct Z-shaped heterojunction is inevitably formed between the two layers, and direct Z-shaped Ag/BiOCl/AgIO is generated3A photocatalyst. AgIO3Electrons of the conduction band recombine with holes of the BiOCl valence band, leaving electrons of the BiOCl conduction band and AgIO3The holes of the valence band participate in the redox reaction. Due to the strong exciton effect of BiOCl, only few electrons are generated, and a large number of primary excitons are generated (as shown in the lower right ellipse of the figure). Under illumination, high-energy electrons generated by Ag contribute to near-infrared degradation, however, free electrons in Ag do high-speed motion around a nucleus, and the energy of the free electrons is higher than that of electrons in primary excitons. Therefore, the free electrons in Ag compete for the holes in the primary excitons to generate secondary excitons (the process is shown by the lower left arrow), while the electrons in the primary excitons are released into the conduction band of BiOCl to participate in the reduction reaction (the process is shown by the upper right arrow). Under the action of Ag and direct Z-type heterojunction, exciton dissociation and carrier separation are accelerated, and Ag/BiOCl/AgIO is endowed3High photocatalytic activity. Simulating Ag/BiOCl/AgIO in sunlight3The degradation rates of RhB are BiOCl and AgIO respectively32.8 and 6.4 times of that of the compound and can effectively degrade RhB under near infrared light.
The above description is only one embodiment of the present invention, and not all or only one embodiment, and any equivalent alterations to the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.

Claims (9)

1. Ag/BiOCl/AgIO3A method for preparing a heterojunction photocatalyst is characterized by comprising the following steps,
step 1, preparing a suspension of BiOCl powder with exposed (001) crystal face by using deionized water, and then adding AgNO3Powder and NaIO3Uniformly mixing the powder to obtain a mixed system;
step 2, carrying out illumination reaction on the mixed system under a light source to obtain a reaction solution;
step 3, separating and drying the product in the reaction solution to obtain Ag/BiOCl/AgIO3A heterojunction photocatalyst.
2. Ag/BiOCl/AgIO according to claim 13The preparation method of the heterojunction photocatalyst is characterized in that in the step 1, deionized water is added into BiOCl powder with an exposed (001) crystal face, and the mixture is stirred at room temperature for 30-40 min to obtain a suspension.
3. Ag/BiOCl/AgIO according to claim 13The preparation method of the heterojunction photocatalyst is characterized in that BiOCl powder and AgNO in the step 13Powder and NaIO3The mass ratio of the powder is 0.3: (0.01-0.05): (0.05-0.3).
4. Ag/BiOCl/AgIO according to claim 13The preparation method of the heterojunction photocatalyst is characterized in that BiOCl powder and AgNO in the step 13Powder and NaIO3The concentration of the powder in the mixed system is recorded in g/mL, and the proportion is (5.00-7.50): (0.17-1.25): (0.83-7.50).
5. Ag/BiOCl/AgIO according to claim 13The preparation method of the heterojunction photocatalyst is characterized in that the illumination reaction time in the step 2 is 2-3 h.
6. Ag/BiOCl/AgIO according to claim 13The preparation method of the heterojunction photocatalyst is characterized in that in the step 2, the mixed system reacts in a photochemical reactor.
7. A Ag/BiOCl/AgIO material according to any one of claims 1 to 63Ag/BiOCl/AgIO obtained by preparation method of heterojunction photocatalyst3A heterojunction photocatalyst.
8. Ag/BiOCl/AgIO according to claim 73The heterojunction photocatalyst is characterized in that the Ag/BiOCl/AgIO3The heterojunction photocatalyst is direct Z-type heterojunction photocatalyst, wherein Ag and AgIO3Are deposited on the (001) crystal plane of BiOCl.
9. An Ag/BiOCl/AgIO as claimed in any one of claims 7 to 83Application of the heterojunction photocatalyst in degrading rhodamine B under sunlight and near infrared light.
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