CN113019392A - Z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3And uses thereof - Google Patents
Z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3And uses thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 229910002367 SrTiO Inorganic materials 0.000 title claims abstract description 37
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 30
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- 239000000956 alloy Substances 0.000 claims abstract description 29
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
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- 238000001354 calcination Methods 0.000 claims abstract description 12
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- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 20
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- 239000000203 mixture Substances 0.000 claims description 8
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- 238000005406 washing Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 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 claims 1
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
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- 229910017053 inorganic salt Inorganic materials 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
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- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8973—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony or bismuth
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/23—
-
- B01J35/39—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- 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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- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a Z-type photocatalyst CuPd/SrTiO with double promoters3‑CuPd‑Bi2O3And applications thereof. Adopting a chemical reduction and high-temperature calcination method: mixing CuPd/SrTiO3CuPd and Bi2O3Dispersing in deionized water, performing ultrasonic treatment, centrifuging, drying the obtained precipitate, grinding, transferring into a muffle furnace, calcining at 500 deg.C for 3.0h to obtain Z-type CuPd/SrTiO3‑CuPd‑Bi2O3A photocatalyst. In the invention, the CuPd alloy as the cocatalyst not only can provide high-activity reaction sites, but also can promote the synergistic conversion effect between Cu and Pd, so that the synthesized Z-type CuPd/SrTiO3‑CuPd‑Bi2O3The composite photocatalyst is applied to the treatment of organic dye wastewater containing N and S elements, and has high photocatalytic degradation and conversion activity.
Description
Technical Field
The invention belongs to the field of photocatalysis, and relates to a novel photocatalyst CuPd/SrTiO3-CuPd-Bi2O3The preparation, the photocatalytic degradation and the conversion of organic dyes containing N and S elements into main raw materials (NH) of fertilizers4)2SO4The use of (1).
Background
In recent years, the phenomenon of water pollution is increasingly serious, and the safe water sources available for drinking are sharply reduced. The presence of contaminants in water poses a serious hazard to the ecosystem. These contaminants often contain large amounts of organic dyes. Some organic dyes such as methylene blue, malachite green, bromophenol blue, etc. are commonly used in the paint, printing, leather, cosmetic, and textile industries. About 10% of these organic dyes are typically wasted during production and use and are discharged with the waste water into the body of water. The design and operational management of wastewater treatment processes are rendered difficult by the complex structure, non-biodegradability and high temperature resistance of these materials, coupled with the intermittent nature of wastewater discharge and the large variation of water quality and quantity over time. The removal of organic dyes from wastewater is very challenging. The current industrial dye wastewater treatment methods commonly used at home and abroad include biological treatment, chemical treatment, adsorption and the like. However, these methods have the disadvantages of high cost, high consumption, long time, incomplete treatment, etc. Therefore, it is crucial to find a clean, inexpensive and efficient way to process organic dyes.
In recent years, the photocatalytic technology is widely applied as a high-efficiency, pollution-free, energy-saving and environment-friendly technology. Generally, organic dyes are treated with photocatalytic techniques to degrade the dye by mineralizing it primarily into water, carbon dioxide and some inorganic salt anions. For dyes containing N and S elements (e.g. methylene blue), NO is formed after mineralization2 -、NO3 -、SO3 2-And SO4 2-. Some inorganic salt ions also cause serious environmental pollution, such as NO3 -And NO2 -. Excessive NO intake by human body2 -It can react with blood to form methemoglobin, so that the blood loses oxygen carrying function and the human body is poisoned by oxygen deficiency. So a novel photocatalyst is designed to firstly degrade the dye and then convert harmful ions into nontoxic or useful substances (such as N)2And NH4 +) Is very necessary.
Disclosure of Invention
In order to solve the problem of environmental and ecological pollution caused by organic dye containing N and S elements, the invention designs a novel Z-type CuPd/SrTiO3-CuPd-Bi2O3The photocatalyst has strong oxidation and reduction capability, and can realize the purposes of degrading dye and converting inorganic ions.
The technical scheme adopted by the invention is as follows: z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3In terms of particle ratio, SrTiO3:Bi2O3＝1:1。
Furthermore, the Z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3Cu and Pd as promoters deposited in the form of an alloy on SrTiO3In mol percent, Cu and Pd are both SrTiO 31% of the total.
Z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3The preparation method comprises the following steps: CuPd/SrTiO3Dispersing CuPd in deionized water, adding Bi2O3Stirring the powder for 4.0h, centrifuging, drying the obtained precipitate at 60 ℃ for 12h, grinding, calcining in a muffle furnace at 500 ℃ for 3.0h, and grinding again to obtain the Z-type photocatalyst CuPd/SrTiO3-CuPd-Bi2O3。
Further, the preparation method is CuPd/SrTiO3The preparation method of the/CuPd comprises the following steps: SrTiO3Dispersing the solid in deionized waterPerforming ultrasonic dispersion for 30min to obtain SrTiO3Adding Cu (NO) into the suspension3)2And Pd (NO)3)2Continuing to stir for 3.0min, adding NaBH4Reacting in ice water bath for 1.0-2.0 h, centrifuging to obtain solid, washing with deionized water, drying at 60 ℃, and grinding to obtain CuPd/SrTiO3CuPd powder.
Further, the above preparation method, SrTiO3The preparation method comprises the following steps: taking Sr (NO)3)2Dispersing citric acid in deionized water, and adjusting the pH to 8 to form a solution A; a mixture of Ti (OBu)4Dispersing in anhydrous ethanol to form solution B, mixing solution A and solution B under stirring, heating at 70 deg.C to gel, drying at 80 deg.C for 12 hr, grinding, and calcining at 700 deg.C for 4.0 hr to obtain SrTiO3Nanoparticles.
Further, the above-mentioned preparation method, the Bi2O3The preparation method comprises the following steps: bi (NO)3)3·5H2Dissolving O in deionized water completely, adjusting pH to 11-12, stirring for 50min, transferring into a reaction kettle, reacting in an oven at 180 deg.C for 24 hr, centrifuging, washing with deionized water, drying at 60 deg.C for 12 hr, grinding, and calcining at 600 deg.C for 2.0 hr to obtain Bi2O3Nanoparticles.
The invention provides a Z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3In the conversion of organic dyes to (NH)4)2SO4The use of (1).
Further, the organic dye is an organic dye containing N and S elements.
Further, the organic dye containing N and S elements is methylene blue.
Further, the method is as follows: adding a Z-type photocatalyst CuPd/SrTiO with double promoters into the wastewater of organic dye containing N and S elements3-CuPd-Bi2O3Conversion of organic dyes to (NH) under solar irradiation4)2SO4。
The invention has the beneficial effects that:
1. the invention designs a novel photocatalyst CuPd/SrTiO by adopting a chemical reduction and high-temperature calcination method3-CuPd-Bi2O3. Two semiconductors SrTiO in the catalyst3And Bi2O3Has relatively matched conduction band and valence band potential values, and can form a Z-type photocatalytic system. In addition, due to the introduction of the promoter CuPd alloy, not only is a high-activity reaction site provided, but also NO can be selectively reduced2 -And NO3 -Is NH4 +. Moreover, the CuPd alloy is also introduced into the photocatalytic system during the preparation process to serve as a conductive channel to accelerate electron transfer. The results show that the conversion of the dye and the SO are increased due to the formation of the Z-type system and the introduction of the cocatalyst and the conductive channel4 2-、NH4 +The generation rate of (c).
2. The CuPd alloy is used as a double-promoter to convert organic dye containing N and S elements into main raw material (NH) of fertilizer4)2SO4. This is because the CuPd alloy is synergistic and selective, Pd vs. NO2 -Has strong adsorption capacity and can adsorb NO2 -Reduction to N2Cu can convert NO2 -Reduction to NH4 +But with the disadvantages of Cu to NO2 -Is weak in adsorption capacity. Therefore, NO can be converted only when Cu and Pd coexist2 -Reduction to NH4 +And can convert organic dye containing N into main raw material (NH) of fertilizer4)2SO4. In addition, Cu and Pd can not only provide more active sites, but also accelerate electron transfer. Synthesized Z-type photocatalyst CuPd/SrTiO3-CuPd-Bi2O3The photocatalyst can show high photocatalytic activity when being applied to the treatment of organic dye wastewater containing N and S elements.
3. The photocatalyst has the characteristics of high degradation efficiency, stable property, simple synthesis method and the like, and can be widely applied to the fields of water environment purification, industrial wastewater treatment, polluted water body remediation and the like.
Drawings
FIG. 1a is SrTiO3X-ray powder diffraction (XRD) pattern of (a).
FIG. 1b is Bi2O3X-ray powder diffraction (XRD) pattern of (a).
FIG. 1c is CuPd/SrTiO3-CuPd-Bi2O3X-ray powder diffraction (XRD) pattern of (a).
FIG. 2 is CuPd/SrTiO3-CuPd-Bi2O3Scanning Electron Microscope (SEM) images of (a).
FIG. 3a is CuPd/SrTiO3-CuPd-Bi2O3A Transmission Electron Microscope (TEM) test pattern of (a).
FIG. 3b is CuPd/SrTiO3-CuPd-Bi2O3High power transmission electron microscopy (HRTEM) test pattern.
FIG. 4a is CuPd/SrTiO loaded CuPd alloy prepared with different reductants3-CuPd-Bi2O3The effect of the photocatalyst on the degradation of methylene blue.
FIG. 4b is CuPd/SrTiO3-CuPd-Bi2O3Photocatalyst for NO3 -,NO2 -And SO3 2-The conversion of (a).
FIG. 4c is CuPd/SrTiO3-CuPd-Bi2O3(1) Photocatalyst for NO3 -,NO2 -And SO3 2-The conversion of (a).
FIG. 4d is CuPd/SrTiO3-CuPd-Bi2O3(2) Photocatalyst for NO3 -,NO2 -And SO3 2-The conversion of (a).
FIG. 5 is CuPd/SrTiO3-CuPd-Bi2O3The number of times the photocatalyst is used.
FIG. 6 is CuPd/SrTiO3-CuPd-Bi2O3A mechanism diagram of organic dye containing N and S elements.
Detailed Description
Example 1
(one) Z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3
The preparation method comprises the following steps:
(1)SrTiO3preparation of nanoparticles
8.44g Sr(NO3)2And 8.41g citric acid (C)6H8O7) Dispersed in 80mL deionized water using NH3·H2O the pH of the suspension was adjusted to 8.0 to form solution A. 13.60g Ti (OBu)4Dispersed in 25mL of absolute ethanol to form solution B. Solution B was slowly added to solution a with constant stirring. The resulting mixture was heated at 70 ℃ until a sol was obtained and aging continued at room temperature for 30min to form a gel. Drying at 80 deg.C for 12h, grinding, and calcining at 700 deg.C for 4.0h to obtain SrTiO3Nanoparticles.
(2)Bi2O3Preparation of nanoparticles
9.70g Bi(NO3)3·5H2Dissolving O powder in 30mL deionized water, adding appropriate amount of NH3·H2Adjusting the pH value to 11 by O, and continuing stirring for 50 min. The resulting mixture was transferred to an autoclave and heated at 180 ℃ for 24 h. After cooling to room temperature, it was centrifuged and washed 3 times with deionized water. Drying the obtained solid at 60 deg.C for 12h, grinding, and calcining at 600 deg.C for 2.0h to obtain Bi2O3Nanoparticles.
(3) With NaBH4Preparation of CuPd/SrTiO for reducing agent3/CuPd
1.50g of SrTiO3The powder was dispersed in a beaker containing 20mL of deionized water. 0.05g of Cu (NO)3)2And 0.04g Pd (NO)3)2The powders were dissolved in 10mL of deionized water to form Cu (NO)3)2Solution and Pd (NO)3)2And (3) solution. Then, Cu (NO)3)2Solution and Pd (NO)3)2The solution was added dropwise to SrTiO3The suspension was stirred for another 30min, and then 5mL of 0.1M NaBH was added4Adding the solution to the mixture in iceThe reaction was stirred in a water bath for 1.0 h. Subsequently, the solid was separated using a centrifuge and washed 3 times with deionized water. Then drying at 60 ℃ for 12h, grinding to obtain CuPd/SrTiO3CuPd, marked as CuPd/SrTiO3/CuPd(I)。
(4)CuPd/SrTiO3-CuPd-Bi2O3And (4) preparing.
1.0g of Bi2O3And 0.70g of CuPd/SrTiO3/CuPd (I) was mixed and dispersed in 50mL deionized water, sonicated for 4.0h, centrifuged, and washed 3 times with deionized water and ethanol. Separating, drying the solid at 60 deg.C for 12h, grinding, calcining at 500 deg.C in muffle furnace for 3.0h, and grinding again to obtain CuPd/SrTiO3-CuPd-Bi2O3Marked as CuPd/SrTiO3-CuPd-Bi2O3(I)。
(II) comparative example
Comparative example 1: with C6H8O6Preparation of CuPd/SrTiO for reducing agent3-CuPd-Bi2O3
1.50g of SrTiO3The powder was dispersed in a beaker containing 20mL of deionized water. 0.05g of Cu (NO)3)2And 0.04g Pd (NO)3)2The powders were dissolved in 10mL of deionized water to form Cu (NO)3)2Solution and Pd (NO)3)2And (3) solution. Then, Cu (NO)3)2And Pd (NO)3)2The solution was added dropwise to SrTiO3The suspension was further stirred for 30 min. Then 5mL of fresh 0.1M C6H8O6The solution was added to the resulting mixture and the reaction stirred in an ice-water bath for 1.0 h. Subsequently, the solid was separated using a centrifuge and washed three times with deionized water. Then drying at 60 ℃ for 12h, grinding to obtain CuPd/SrTiO3CuPd sample, labeled CuPd/SrTiO3/CuPd(Ⅱ)。
0.70g of CuPd/SrTiO3CuPd (II) with 1.0g Bi2O3Mixing and dispersing in 50mL of deionized water, performing ultrasonic treatment for 2.0h, centrifuging to obtain solid, and washing with deionized water and ethanol for 3 times. Is divided intoSeparating the solid, drying at 60 deg.C for 12h, grinding, and calcining at 500 deg.C in a muffle furnace for 3.0h to obtain CuPd/SrTiO3-CuPd-Bi2O3Marked as CuPd/SrTiO3-CuPd-Bi2O3(Ⅱ)。
Comparative example 2: with N2H4·H2Preparation of CuPd/SrTiO by using O as reducing agent3-CuPd-Bi2O3
1.50g of SrTiO3The powder was dispersed in a beaker containing 20mL of deionized water. 0.05g of Cu (NO)3)2And 0.04g Pd (NO)3)2The powders were dissolved in 10mL of deionized water to form Cu (NO)3)2Solution and Pd (NO)3)2And (3) solution. Then, Cu (NO)3)2And Pd (NO)3)2The solution was added dropwise to SrTiO3The suspension of (4) was stirred for 30 min. Then, 500. mu.L of N with a mass percentage concentration of 80%2H4·H2O solution was added to the resulting mixture, and the reaction was stirred in an ice water bath for 1.0 h. Subsequently, the solid was separated using a centrifuge and washed three times with deionized water. Then drying at 60 ℃ for 12h, grinding to obtain CuPd/SrTiO3/CuPd(Ⅲ)。
0.70g of CuPd/SrTiO3CuPd (III) with 1.0g Bi2O3Mixing and dispersing in 50mL deionized water, performing ultrasonic treatment for 2.0h, centrifuging to obtain solid, and washing with deionized water and ethanol for 3 times. Separating to obtain solid, drying at 60 deg.C for 12 hr, grinding, and calcining at 500 deg.C in muffle furnace for 3.0 hr to obtain CuPd/SrTiO3-CuPd-Bi2O3Marked as CuPd/SrTiO3-CuPd-Bi2O3(Ⅲ)。
(III) detection
1. FIG. 1a to FIG. 1c are SrTiO3，Bi2O3，CuPd/SrTiO3-CuPd-Bi2X-ray powder diffraction (XRD) pattern of O (I).
In FIG. 1a, SrTiO TiO in the peak and cubic phase at 32.43 ° (110), 39.97 ° (111), 46.44 ° (200) and 57.74 ° (211) is shown3(JCPDS:35-0734) crystal planes correspond.Also, no extra diffraction peak was observed, indicating that the synthesized SrTiO3The sample is of high purity.
In FIG. 1b, the main diffraction peaks of the sample are associated with monoclinic Bi at 27.50 ° (120), 28.17 ° (012), 33.36 ° (202), 46.47 ° (223) and 52.53 ° (322)2O3The crystal faces of (JCPDS:41-1449) correspond. Shows that Bi2O3Was successfully prepared.
In FIG. 1c, it can be seen that some of the major diffraction peaks are attributed to SrTiO3And Bi2O3The characteristic diffraction peak of the CuPd alloy can be observed at 42.76 ° 2 θ, which indicates that NaBH is used4CuPd/SrTiO prepared by using CuPd/SrTiO as reducing agent3-CuPd-Bi2O3(I) Samples were successfully prepared.
2. FIG. 2 is CuPd/SrTiO3-CuPd-Bi2O3(I) Scanning Electron Microscope (SEM) images of (a).
Scanning Electron Microscopy (SEM) was used to observe the prepared CuPd/SrTiO3-CuPd-Bi2O3(I) The morphology of the sample, the results of the test are shown in figure 2. As can be seen from FIG. 2, SrTiO3Particles and BiVO4The particles are connected by CuPd alloy particles. And in SrTiO3Some CuPd alloy particles can also be found on the surface of (a). These results illustrate the Z-form CuPd/SrTiO3-CuPd-Bi2O3Photocatalysts have been successfully prepared.
3. FIG. 3a and FIG. 3b are CuPd/SrTiO, respectively3-CuPd-Bi2O3(I) A Transmission Electron Microscope (TEM) image and a high power transmission electron microscope (HRTEM) image of (a).
In FIG. 3a it can be seen that the larger size particles are SrTiO3Sample, the smaller size particles being Bi2O3And (3) sampling. In SrTiO3And Bi2O3There is an elliptic particle of about 20nm between them, which is CuPd alloy as a conductive channel. In SrTiO3There are also some 20nm elliptical particles on the surface, which are CuPd alloy as a promoter. These results are one in SEMThus, the Z-type CuPd/SrTiO is further explained3-CuPd-Bi2O3Photocatalysts have been successfully prepared.
In fig. 3b, an image obtained with a high magnification electron microscope (HRTEM) is shown, and lattice fringes are calculated to divide the composition of the composite sample. As shown, the lattice spacings measured were 0.398nm, 0.332nm, 0.210nm, which correspond to SrTiO, respectively3(200) Crystal face, Bi2O3(201) Crystal face and CuPd (110) crystal face. Moreover, the positional relationship of the respective components is in agreement with the expectation. These results show that the Z-type photocatalyst CuPd/SrTiO3-CuPd-Bi2O3Have been successfully prepared.
Example 2Z-type photocatalyst CuPd/SrTiO with Dual promoters3-CuPd-Bi2O3Conversion of NO while degrading methylene blue3 -、NO2 -And SO3 2-Is (NH)4)2SO4Application of
(one) CuPd alloy prepared by different reducing agents for Z-type photocatalyst CuPd/SrTiO3-CuPd-Bi2O3Photocatalytic degradation of methylene blue with simultaneous conversion of NO3 -、NO2 -And SO3 2-Is (NH)4)2SO4Influence of (2)
The experimental method comprises the following steps: A300W xenon lamp was used as the light source. The photocatalytic degradation and simultaneous conversion experiments were carried out in specially made quartz tubes at 25 ℃ and 101325 Pa. 100mL of methylene blue aqueous solution with the concentration of 10mg/L are respectively added into 3 special quartz tubes, and the CuPd/SrTiO prepared in the example 1 is respectively added under the condition of continuous stirring3-CuPd-Bi2O3(I)、CuPd/SrTiO3-CuPd-Bi2O3(II) and CuPd/SrTiO3-CuPd-Bi2O3(III) a photocatalyst. The reaction was carried out for 4.0h under continuous irradiation with a 300W xenon lamp. 5mL of the suspension was taken every 1.0 h. And (4) taking the supernatant, measuring the ultraviolet spectrum of the supernatant at 200-800nm, and calculating the degradation rate by using the absorbance value at 660 nm. Simultaneously, an ion chromatograph is used for taking a proper amount of supernatant to carry out NO treatment3 -、NO2 -、SO3 2-、SO4 2-And NH4 +And (4) detecting the concentration, and calculating the conversion rate and the generation rate of corresponding ions.
Comparing CuPd/SrTiO3-CuPd-Bi2O3(I)、CuPd/SrTiO3-CuPd-Bi2O3(II) and CuPd/SrTiO3-CuPd-Bi2O3(III) degrading Effect on methylene blue and on NO3 -、NO2 -And SO3 2-The results are shown in FIGS. 4a to 4 d.
FIG. 4a shows CuPd/SrTiO3-CuPd-Bi2O3(I)、CuPd/SrTiO3-CuPd-Bi2O3(II) and CuPd/SrTiO3-CuPd-Bi2O3(III) results of the degradation of methylene blue. As can be seen from FIG. 4a, the load is represented by NaBH4CuPd/SrTiO CuPd alloy prepared as reducing agent3-CuPd-Bi2O3(I) The photocatalyst shows good photocatalytic activity in the process of degrading methylene blue. The degradation rate reaches 93.87 percent. This is because NaBH4Is moderate, so that NaBH is used4The CuPd alloy prepared by using the CuPd alloy as a reducing agent has high alloy yield and uniform particle size, and the particles are in SrTiO3The surface is uniformly distributed. So that the CuPd alloy can well promote SrTiO3/Bi2O3The photocatalytic system has high separation efficiency of electrons and holes, and thus, the activity of the photocatalyst is improved.
FIG. 4b, FIG. 4c and FIG. 4d show CuPd/SrTiO, respectively3-CuPd-Bi2O3(I)、CuPd/SrTiO3-CuPd-Bi2O3(II) and CuPd/SrTiO3-CuPd-Bi2O3(III) conversion of NO3 -、NO2 -And SO3 2-Is (NH)4)2SO4And (6) obtaining the result. By comparison, it can be seen that the SO in FIG. 4b3 2-And NH4 +The highest production rate. Indicating CuPd/SrTiO3-CuPd-Bi2O3(I) For conversion of NO3 -、NO2 -And SO3 2-Is (NH)4)2SO4Has the highest photocatalytic activity. This is because NaBH4Is moderate, so that NaBH is used4The CuPd alloy prepared by using the CuPd alloy as a reducing agent has high alloy yield and uniform particle size, and the particles are in SrTiO3The surface distribution is uniform. On one hand, the CuPd alloy can well help promote SrTiO3/Bi2O3The photocatalysis system separates electrons and holes, can efficiently degrade methylene blue and can quickly oxidize SO generated by degradation3 2-Is SO4 2-. On the other hand, the CuPd alloy can fully react with NO generated in the degradation process3 -And NO2 -Ionic contact, thereby increasing the conversion efficiency, i.e. promoting NH4 +And (4) generating.
(II) CuPd/SrTiO3-CuPd-Bi2O3Investigation of the number of times of use of photocatalyst
The experimental method comprises the following steps: 100mL of methylene blue aqueous solution with the concentration of 10mg/L is measured and put into a special quartz tube, and CuPd/SrTiO is added3-CuPd-Bi2O3(I) The photocatalyst is irradiated for 4.0h under simulated sunlight, 5mL of suspension is taken out, and the ultraviolet spectrum of the supernatant is measured at 200-800nm by taking the supernatant. The absorbance at 660nm was taken to calculate the degradation rate of methylene blue. Simultaneously, an ion chromatograph is used for taking a proper amount of supernatant to carry out NO treatment3 -、NO2 -、SO3 2-、SO4 2-And NH4 +And (4) detecting the concentration, and calculating the conversion rate and the generation rate of corresponding ions. After 4.0h, the photocatalyst in the solution was dried and re-subjected to the photocatalytic degradation experiment, and the same procedure was repeated four times, with the results shown in fig. 5.
By degradation of methylene blue and by NO3 -、NO2 -And SO3 2-The conversion of ions, CuPd/SrTiO3-CuPd-Bi2O3(I) The stability of the photocatalyst over four cycles is shown in figure 5. It was found that the degradation rate of methylene blue in the fourth cycle was 87.94%, which was slightly decreased compared to the first cycle. SO of the fourth period4 2-And NH4 +The production rate can still reach 89.56% and 66.52% respectively. Also, in four cycles, NH4 +All are products with the highest production rate in the N-containing substances. Thus, these results indicate that the Z-form CuPd/SrTiO3-CuPd-Bi2O3Degradation of methylene blue and NO by photocatalyst3 -、NO2 -And SO3 2-The conversion of ions has high photocatalytic activity and is also sensitive to NH4 +The formation of ions has good selectivity. Thus, the Z-type photocatalyst CuPd/SrTiO can be seen3-CuPd-Bi2O3Has considerable application prospect in treating organic dye containing N and S elements in wastewater.
Based on the above results, Z-type CuPd/SrTiO is proposed3-CuPd-Bi2O3Photocatalyst degradation and conversion of organic dye containing N and S elements to form (NH)4)2SO4Possible mechanisms of (2). As shown in fig. 6. In Z type photocatalyst CuPd/SrTiO3-CuPd-Bi2O3When SrTiO3(ΔEbg＝3.40eV，ECB1.26eV and EVB= 2.14eV) and Bi2O3(ΔEbg＝2.80eV，ECBNot more than +0.33eV and EVB+3.13eV) is simultaneously excited by sunlight, photogenerated electrons (e) are generated on the respective Conduction Band (CB) and Valence Band (VB)-) And a cavity (h)+). Since Bi2O3CB potential (+0.33eV) of (A) and SrTiO3Is relatively close to VB potential (+2.14eV), Bi is therefore2O3Can be rapidly transferred to SrTiO3Then recombines with the holes to form a Z-type electron transport path. On one hand, the Z-type SrTiO is well promoted by the special electron transfer mode3/Bi2O3Separation of photogenerated carriers in a photocatalytic system. On the other hand, reserve SrTiO3Relatively negative conduction band (E)CB1.15eV) and Bi2O3Relative positive valence band (E)VB+3.15eV) to have strong reducing and oxidizing abilities. Moreover, in order to improve the conversion efficiency of inorganic ions and control the final product, CuPd alloy nano-particles are adopted as a cocatalyst to react with Z-type SrTiO3/Bi2O3The photocatalytic system is modified. In addition, during the preparation of the photocatalyst, the CuPd alloy nanoparticles are first deposited on SrTiO3Surface of then with Bi2O3Combine to form CuPd/SrTiO3-CuPd-Bi2O3. Shows that the CuPd alloy nano-particles are in a Z-type photocatalyst CuPd/SrTiO3-CuPd-Bi2O3The conductive channel plays a role in accelerating electron transfer on a Z-shaped path.
Organic dye containing N and S elements in Bi2O3Is oxidized and mineralized into CO2、H2O、NO2 -、NO3 -And SO3 2-. Among them, harmful NO2 -、NO3 -And SO3 2-Further converted into (NH) which can be used as fertilizer4)2SO4。NO2 -、NO3 -And SO3 2-Is different. NO2 -And NO3 -Conversion to NH4 +Is a series of reduction reactions which occur during the deposition on SrTiO3The surface of the CuPd alloy nano-particles is used as a cocatalyst. Cu to NO3 -Has strong adsorption capacity through SrTiO3Cu can adsorb NO relative to electrons captured by a negative conduction band3 -Reduction to NO2 -. And NO produced by the above reduction reaction and the dye mineralization process2 -Can be adsorbed by Pd. Further, Pd can be derived from SrTiO3Electrons trapped in the conduction band and a small amount of NO2 -Reduction to N2Large amount of NO remaining2 -Transformation will be imminentThe near Cu surface is reduced to NH4 +. During the adsorption conversion process, because the distance between Cu and Pd in the alloy is very small, a strong synergistic effect is formed between Cu and Pd, and the strong synergistic effect greatly promotes NO2 -And NO3 -To NH4 +The transformation of (3). For SO3 2-Conversion of Bi2O3Oxidation reaction of the valence band of (3), SO3 2-Can be oxidized directly to SO by the cavity4 2-. SO formed subsequently4 2-And NH4 +Combined to finally form (NH)4)2SO4Can be used as fertilizer for agricultural production.
Claims (10)
1. Z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3Characterized in that, in terms of particle ratio, SrTiO3:Bi2O3＝1:1。
2. The CuPd/SrTiO dual-promoter Z-type photocatalyst of claim 13-CuPd-Bi2O3The method is characterized in that: cu and Pd as promoters are deposited on SrTiO in the form of alloy3In mol percent, Cu and Pd are both SrTiO31% of the total.
3. Z-type photocatalyst CuPd/SrTiO with double promoters3-CuPd-Bi2O3The preparation method is characterized by comprising the following steps: CuPd/SrTiO3Dispersing CuPd in deionized water, adding Bi2O3Stirring the powder for 4.0h, centrifuging, drying the obtained precipitate at 60 ℃ for 12h, grinding, calcining in a muffle furnace at 500 ℃ for 3.0h, and grinding again to obtain the Z-type photocatalyst CuPd/SrTiO3-CuPd-Bi2O3。
4. The method according to claim 3, wherein the CuPd/SrTiO is3Preparation method of/CuPdThe method comprises the following steps: SrTiO3Dispersing the solid in deionized water, and ultrasonically dispersing for 30min to obtain SrTiO3Adding Cu (NO) into the suspension3)2And Pd (NO)3)2Stirring for 30min, adding NaBH4Reacting in ice water bath for 1.0-2.0 h, centrifuging to obtain solid, washing with deionized water, drying at 60 ℃, and grinding to obtain CuPd/SrTiO3CuPd powder.
5. The method according to claim 4, wherein the SrTiO is3The preparation method comprises the following steps: taking Sr (NO)3)2Dispersing citric acid in deionized water, and adjusting the pH to 8 to form a solution A; a mixture of Ti (OBu)4Dispersing in anhydrous ethanol to form solution B, mixing solution A and solution B under stirring, heating at 70 deg.C to gel, drying at 80 deg.C for 12 hr, grinding, and calcining at 700 deg.C for 4.0 hr to obtain SrTiO3Nanoparticles.
6. The method according to claim 3, wherein said Bi2O3The preparation method comprises the following steps: bi (NO)3)3·5H2Dissolving O in deionized water, adjusting pH to 11-12, stirring for 50min, transferring to a reaction kettle, reacting in an oven at 180 deg.C for 24h, centrifuging, washing with deionized water, drying at 60 deg.C for 12h, grinding, and calcining at 600 deg.C for 2.0h to obtain Bi2O3Nanoparticles.
7. The dual-cocatalyst Z-type photocatalyst CuPd/SrTiO of claim 1 or 23-CuPd-Bi2O3In the conversion of organic dyes to (NH)4)2SO4The use of (1).
8. Use according to claim 7, wherein the organic dye is an organic dye containing N and S elements.
9. Use according to claim 8, wherein the organic dye containing the elements N and S is methylene blue.
10. Use according to claim 9, characterized in that the method is as follows: adding the Z-type photocatalyst CuPd/SrTiO with double promoters according to claim 1 or 2 into the wastewater of organic dye containing N and S elements3-CuPd-Bi2O3Conversion of organic dyes to (NH) under solar irradiation4)2SO4。
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| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN106563431A (en) * | 2016-11-07 | 2017-04-19 | 杭州同净环境科技有限公司 | Composite photocatalyst, preparation method and application thereof |
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| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN106563431A (en) * | 2016-11-07 | 2017-04-19 | 杭州同净环境科技有限公司 | Composite photocatalyst, preparation method and application thereof |
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| 张萌: ""几种助催剂修饰的Z型光催化剂转化有机染料生成(NH4)2SO4的研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 * |
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