WO2022051898A1 - Magnetic composite light catalyst and production method therefor, and application in antibiotic wastewater treatment - Google Patents

Magnetic composite light catalyst and production method therefor, and application in antibiotic wastewater treatment Download PDF

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Publication number
WO2022051898A1
WO2022051898A1 PCT/CN2020/113995 CN2020113995W WO2022051898A1 WO 2022051898 A1 WO2022051898 A1 WO 2022051898A1 CN 2020113995 W CN2020113995 W CN 2020113995W WO 2022051898 A1 WO2022051898 A1 WO 2022051898A1
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magnetic composite
composite photocatalyst
solution
magnetic
antibiotic
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PCT/CN2020/113995
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French (fr)
Chinese (zh)
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罗鸿斌
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东莞理工学院
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Priority to PCT/CN2020/113995 priority Critical patent/WO2022051898A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • 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

Definitions

  • the invention relates to the field of antibiotic wastewater treatment, in particular to a magnetic composite photocatalyst, a preparation method thereof, and an application in antibiotic wastewater treatment.
  • antibiotics have been widely used not only in the treatment of human diseases, but also in animal husbandry and aquaculture.
  • these antibiotics are difficult to be completely metabolized, and even excreted in the original state.
  • Residual antibiotics in the environment can induce the growth of drug-resistant bacteria and endanger human health, and at higher concentrations, can lead to mutation and variation of human chromosomes. Therefore, how to quickly and efficiently degrade antibiotics has become an urgent problem to be solved.
  • Photocatalyst technology has the advantages of mild reaction conditions, no secondary pollution, low energy consumption and high efficiency, and has attracted much attention in the field of antibiotic wastewater treatment.
  • the photocatalytic materials have the defects of unsatisfactory responsiveness in the visible light region, poor electron and hole transfer and separation ability, low specific surface area of the material itself, low recovery rate, and high cost, which make the photocatalytic material unable to The ideal photocatalytic effect is obtained, which limits its further application.
  • the invention patent with the application number CN201910716666.X discloses a magnetically separable catalyst for photocatalytic degradation of antibiotics, and a preparation method and application thereof.
  • the catalyst uses magnetic zinc ferrite as a carrier, and the magnetic zinc ferrite is decorated with nitrogen-doped carbon quantum dots and silver carbonate; the mass fraction of the nitrogen-doped carbon quantum dots is 0.15-0.20%; the The mass fraction of silver carbonate is 20-30%.
  • the invention patent with the application number CN201610238572.2 discloses a magnetic composite photocatalyst and a preparation method and application thereof.
  • the magnetic composite photocatalyst takes Fe 3 O 4 nanoparticles as the core, the surface of the Fe 3 O 4 nanoparticles is covered with a SiO 2 inert layer, the surface of the SiO 2 inert layer is enriched with Ag 3 PO 4 , and the surface of the Ag 3 PO 4 is modified with AgCl.
  • the invention patent with the application number of CN201811178680.0 discloses a magnetic bismuth vanadate/bismuth titanate/iron tetroxide photocatalyst and a preparation method and application thereof.
  • the photocatalyst uses flower-like bismuth vanadate as a matrix, and the surface of flower-like bismuth vanadate particles is simultaneously modified with bismuth titanate and ferric oxide nanoparticles, and finally forms a bismuth vanadate/bismuth titanate/ferric oxide composite photocatalyst .
  • the invention patent with the application number CN201711261410.1 discloses a gC 3 N 4 -Fe 3 O 4 heterojunction photocatalyst and a preparation method thereof.
  • the preparation method includes the following steps: calcining melamine at high temperature to obtain gC 3 N 4 ; mixing the obtained gC 3 N 4 with Fe 3 O 4 precursor, and preparing gC 3 N 4 /Fe 3 O 4 by sol-hydrothermal method Photocatalyst; react the obtained gC 3 N 4 /Fe 3 O 4 under the action of a shrinking agent to obtain a gC 3 N 4 -Fe 3 O 4 heterojunction photocatalyst.
  • the purpose of the present invention is to provide a magnetic composite photocatalyst and its preparation method and application in the treatment of antibiotic wastewater.
  • the present invention provides a method for preparing a magnetic composite photocatalyst.
  • the Bi 2 WO 6 -Fe 3 O 4 composite magnetic microspheres are synthesized by a hydrothermal method;
  • a gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalytic system was constructed by hydrothermal composite method to prepare a magnetic composite photocatalyst;
  • melamine is calcined at a high temperature of 500-600 ° C under the protection of an inert atmosphere for 3-5 hours, cooled and ground to obtain a calcined product, and then the calcined product is placed in a solution of glacial acetic acid, and magnetically stirred for 1-3 hours , ultrasonically pulverized for 8-15 hours, centrifugally precipitated and washed to neutrality, then dried and ground to obtain gC 3 N 4 ;
  • step S3 adding the Bi 2 WO 6 -Fe 3 O 4 prepared in step S1 and the gC 3 N 4 prepared in step S2 into deionized water in a predetermined proportion, and magnetically stirring for 1-2 hours to fully mix to obtain a mixed solution , adding the mixed solution into a hydrothermal kettle, reacting at 150-180 ° C for 4-6 h, cooling, centrifuging and precipitation to obtain gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite material, as the magnetic composite photocatalyst.
  • the present invention also provides the magnetic composite photocatalyst prepared by the above preparation method.
  • the magnetic composite photocatalyst is a composite material composed of Bi 2 WO 6 , Fe 3 O 4 and gC 3 N 4 and has magnetic and semiconductor photocatalytic properties and adsorption properties.
  • the present invention also provides the application of the magnetic composite photocatalyst in the treatment of antibiotic wastewater.
  • the mixed solution is stirred under dark conditions, and after reaching the adsorption-desorption equilibrium, the mixed solution is subjected to a photocatalytic reaction under visible light irradiation to complete the degradation treatment of antibiotics in wastewater.
  • the preparation method of the magnetic composite photocatalyst provided by the present invention has the advantages of high photo-induced electron-hole separation and transfer efficiency, excellent photocatalytic activity, high photocatalytic degradation efficiency of antibiotics, and can effectively recycle and reuse gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalytic system, the mechanism of which is:
  • Three -dimensional flower-like Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres were synthesized by hydrothermal method .
  • the porous structure has uniform morphology and uniform particle size, and has fast magnetic response performance under an external magnetic field.
  • the three-dimensional flower-shaped Bi 2 WO 6 is composed of upper and lower layers of (Bi 2 O 2 ) 2+ and (WO 4 ) 2- of the middle layer alternately, and has a regular layered structure.
  • the unique layered structure makes it have Excellent adsorption properties.
  • Bi 2 WO 6 and gC 3 N 4 have staggered band gaps and matching energy band structures. After the two are recombined, electrons on the conduction band of gC 3 N 4 can be rapidly transferred to Bi 2 WO 6 -Fe 3 O 4 On the conduction band of Bi 2 WO 6 in the composite microspheres, the holes on the valence band of Bi 2 WO 6 are transported to the valence band of gC 3 N 4 , thereby realizing the efficient separation and transfer of light-induced electrons and holes, effectively The defects of low photocatalytic efficiency of Bi 2 WO 6 and gC 3 N 4 monomers as photocatalysts are improved, and the catalytic activity of composite photocatalysts is significantly improved.
  • the nanosheets of Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres appeared dispersed, and were embedded and supported on the surface of gC 3 N 4 , so that the specific surface area of the composite photocatalyst was significantly increased, and the catalyst The contact area with antibiotic molecules increases, the reactive sites increase, and the photocatalytic activity is enhanced.
  • the combination of Bi 2 WO 6 and gC 3 N 4 produces a synergistic effect, which broadens the response range of the composite photocatalyst to visible light.
  • the interaction between Fe3O4 and gC3N4 in the ternary composite system stabilizes the structure of the composite photocatalyst, enhances the separation efficiency of photogenerated electron - hole pairs of the composite photocatalyst, and leads to More photogenerated electron-hole pairs are generated, and the energy required for the transition to occur is reduced, thereby enhancing the photocatalytic activity.
  • Bi 2 WO 6 , Fe 3 O 4 and gC 3 N 4 cooperate with each other, so that the composite
  • the ternary heterojunction structure is formed in the photocatalyst, which is conducive to the separation of photogenerated carriers, can effectively inhibit the recombination of photogenerated electrons and holes in the photocatalytic reaction, and enhance the separation of photogenerated electron-hole pairs of the composite photocatalyst.
  • the efficiency of photocurrent response was significantly improved, and the ternary compounding jointly improved the photocatalytic activity of the composite photocatalyst, and significantly improved the efficiency of photocatalytic degradation of antibiotics.
  • the magnetic composite photocatalyst provided by the present invention has excellent photocatalytic activity, high efficiency of photocatalytic degradation of antibiotics, and can be effectively recycled and reused, and has a huge application prospect in the field of photocatalytic degradation of antibiotic pollution.
  • the invention provides a preparation method of a magnetic composite photocatalyst, comprising the following steps:
  • melamine is calcined at a high temperature of 500-600 ° C under the protection of an inert atmosphere for 3-5 hours, cooled and ground to obtain a calcined product, and then the calcined product is placed in a solution of glacial acetic acid, and magnetically stirred for 1-3 hours , ultrasonically pulverized for 8-15 hours, centrifugally precipitated and washed to neutrality, then dried and ground to obtain gC 3 N 4 ;
  • step S3 adding the Bi 2 WO 6 -Fe 3 O 4 prepared in step S1 and the gC 3 N 4 prepared in step S2 into deionized water in a predetermined proportion, and magnetically stirring for 1-2 hours to fully mix to obtain a mixed solution , adding the mixed solution into a hydrothermal kettle, reacting at 150-180°C for 4-6 hours, cooling, centrifuging and precipitation to obtain gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalysis system as the magnetic composite photocatalyst.
  • step S1 the molar ratio of the Bi(NO 3 ) 3 ⁇ 5H 2 O to the Na 2 WO 4 ⁇ 2H 2 O is (2-4):1; the Bi(NO 3 ) 3 ⁇ 5H The molar ratio of 2 O to the nano Fe 3 O 4 powder is (4-6):1; the volume ratio of the deionized water and the concentrated nitric acid is (45-65):1.
  • step S2 the concentration of the glacial acetic acid solution is 1.5 ⁇ 2.5mol/L;
  • step S3 the mass fraction ratio of the Bi 2 WO 6 -Fe 3 O 4 to the gC 3 N 4 is 50-60%: 40-50%.
  • the present invention also provides the application of the magnetic composite photocatalyst in the treatment of antibiotic wastewater.
  • the specific application process is as follows: according to a predetermined dosage ratio, the magnetic composite photocatalyst is mixed with the antibiotic wastewater to obtain a mixed solution, and the mixture is prepared in the dark. Stirring treatment is carried out under the conditions, and after reaching the adsorption-desorption equilibrium, the mixed solution is subjected to photocatalytic reaction under the irradiation of visible light, so as to complete the degradation treatment of the antibiotics in the waste water body.
  • the stirring treatment time is 30-60 min; the photocatalytic reaction treatment time is 60-180 min; the pH value of the antibiotic wastewater is 6-8; the initial concentration of the antibiotic in the antibiotic wastewater is 5-180 min 20mg/L, the addition amount of the magnetic composite photocatalyst is 0.5-3.0g/L.
  • a preparation method of a magnetic composite photocatalyst comprising the following steps:
  • step S3 adding the Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres prepared in step S1 and the gC 3 N 4 prepared in step S2 into deionized water at a mass fraction ratio of 55%: 45%, Magnetic stirring for 2 hours until fully mixed to obtain a mixed solution, which was added to a hydrothermal kettle, reacted at 180 °C for 4 hours, cooled, centrifuged and precipitated, and dried at 60 °C to obtain gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalyst system as the magnetic composite photocatalyst.
  • Example 1 The difference from Example 1 is that the photocatalyst of Comparative Example 1 is Bi 2 WO 6 monomer.
  • Example 2 The difference from Example 1 is that the photocatalyst of Comparative Example 2 is gC 3 N 4 monomer.
  • Example 3 The difference from Example 1 is that the photocatalyst of Comparative Example 3 is Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres.
  • Example 1 The difference from Example 1 is that the photocatalyst of Comparative Example 4 is a gC 3 N 4 /Bi 2 WO 6 composite catalyst, that is, no nano Fe 3 O 4 powder is added in step S1.
  • the photocatalyst of Comparative Example 4 is a gC 3 N 4 /Bi 2 WO 6 composite catalyst, that is, no nano Fe 3 O 4 powder is added in step S1.
  • Example 1 The difference from Example 1 is that the photocatalyst of Comparative Example 5 is the gC 3 N 4 -Fe 3 O 4 composite catalyst prepared in the prior art.
  • the photocatalyst is mixed with ciprofloxacin antibiotic wastewater with an initial concentration of 10 mg/L according to the addition amount of 1.0 g/L to obtain a mixed solution, and is stirred for 30 min under dark conditions, and after reaching the adsorption-desorption equilibrium, The mixed solution was irradiated with visible light (36W UV-LED light source) for photocatalytic reaction for 90 min respectively, and the degradation rate of ciprofloxacin was tested.
  • Table 1 shows the degradation performance of the photocatalysts prepared in Example 1 and Comparative Examples 1-5
  • Example Ciprofloxacin degradation rate Cefixime degradation rate Example 1 90.2% 94.8% Comparative Example 1 41.2% 43.3% Comparative Example 2 36.4% 37.6% Comparative Example 3 45.4% 48.0% Comparative Example 4 88.6% 91.8% Comparative Example 5 63.7% 64.9%
  • the synergistic effect of Fe 3 O 4 and gC 3 N 4 can improve the separation efficiency of photogenerated electron-hole pairs of the composite photocatalyst, significantly improve the photocurrent response performance, and make it exhibit excellent photocatalytic activity.
  • the efficiency of photocatalytic degradation of antibiotics was significantly improved.
  • Example 1 The difference from Example 1 is that the Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres and gC 3 N 4 are set differently according to the mass fraction ratio.
  • Table 2 is the parameter setting of the photocatalyst prepared by Example 1-3
  • gC 3 N 4 has a thin layered structure after ultrasonic treatment .
  • the layered mesoporous nanosheets of the microspheres appear dispersed, and are supported on the surface of gC 3 N 4 by doping and polymerization for bonding, which significantly increases the specific surface area of the composite photocatalyst and the photocatalytic activity.
  • Example 1 The difference from Example 1 is that the molar ratio of Bi(NO 3 ) 3 ⁇ 5H 2 O and nano Fe 3 O 4 powder is set differently.
  • Table 3 is the parameter setting of the photocatalyst prepared in Example 1 and Example 4-5
  • Example Molar ratio of Bi(NO 3 ) 3 ⁇ 5H 2 O to Fe 3 O 4 Example 1 5:1
  • the invention adopts a hydrothermal method to synthesize three -dimensional flower - shaped Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres .
  • the mesoporous structure significantly increases the specific surface area of the composite photocatalyst.
  • the introduction of Fe 3 O 4 into the photocatalyst makes the composite photocatalyst present a superparamagnetic state, which can quickly achieve magnetic separation without causing secondary pollution and can be recycled.
  • the interaction between Fe 3 O 4 and gC 3 N 4 also occurs, resulting in the generation of more photogenerated electron-hole pairs, thereby enhancing the photocatalytic activity.
  • the dosage of photocatalyst and the photocatalytic reaction time can be adjusted according to the type and initial concentration of antibiotics and light conditions. Penicillins, tetracyclines, ⁇ -lactams and the like can be used.
  • the present invention provides a magnetic composite photocatalyst, a preparation method thereof, and an application in the treatment of antibiotic wastewater.
  • Bi 2 WO 6 -Fe 3 O 4 composite magnetic microspheres were synthesized by hydrothermal method; then, graphitic carbon nitride (gC 3 N 4 ) was prepared by melamine high temperature calcination polymerization method; finally, it was constructed by hydrothermal composite method
  • the gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalyst system was used to prepare a magnetic composite photocatalyst.
  • the ternary complex of the magnetic composite photocatalyst cooperates with each other to make the photoinduced electron-hole separation and transfer efficiency high, has excellent photocatalytic activity, high photocatalytic degradation efficiency of antibiotics, and can be effectively recycled and reused. Catalytic degradation of antibiotic pollution has great application prospects.

Abstract

The present invention provides a magnetic composite light catalyst and a production method therefor, and an application in antibiotic wastewater treatment. First, Bi2WO6-Fe3O4 composite magnetic microspheres can be synthesized by using a hydrothermal method; then graphite phase carbon nitride (g-C3N4) is produced by using a melamine high-temperature calcination polymerization method; finally, a g-C3N4/Bi2WO6-Fe3O4 ternary composite light catalyst system is constructed by using a hydrothermal composite method, so that a magnetic composite light catalyst is produced. Ternary complexes of the magnetic composite light catalyst exhibit a synergetic effect with each other to achieve high light-induced electron-hole separation and transport efficiency, and the magnetic composite light catalyst has excellent light catalytic activity and high light catalytic antibiotic degradation efficiency, supports effective recycling and reuse, and has a broad application prospect in the field of light catalytic antibiotic degradation pollution.

Description

磁性复合光催化剂及其制备方法和在抗生素废水处理中的应用Magnetic composite photocatalyst and preparation method thereof and application in antibiotic wastewater treatment 技术领域technical field
本发明涉及抗生素废水处理领域，尤其涉及一种磁性复合光催化剂及其制备方法和在抗生素废水处理中的应用。The invention relates to the field of antibiotic wastewater treatment, in particular to a magnetic composite photocatalyst, a preparation method thereof, and an application in antibiotic wastewater treatment.
背景技术Background technique
近几十年，抗生素不仅广泛应用于人类疾病的治疗，也广泛应用在畜牧业及水产养殖业。但是，这些抗生素药物很难完全代谢，甚至以原态排除体外。环境中残留的抗生素会诱导耐药性细菌的生长和危害人类的健康，在较高浓度时，可导致人体染色体的突变和变异。因此如何快速高效绿色降解抗生素成为目前亟待解决的问题。In recent decades, antibiotics have been widely used not only in the treatment of human diseases, but also in animal husbandry and aquaculture. However, these antibiotics are difficult to be completely metabolized, and even excreted in the original state. Residual antibiotics in the environment can induce the growth of drug-resistant bacteria and endanger human health, and at higher concentrations, can lead to mutation and variation of human chromosomes. Therefore, how to quickly and efficiently degrade antibiotics has become an urgent problem to be solved.
半导体光催化剂技术具有反应条件温和、没有二次污染、能耗低效率高等优点而在抗生素废水处理领域备受关注。然而，在现有研究中，光催化材料存在在可见光区域的响应性不够理想、电子及空穴传递和分离能力差、材料本身比表面积低、回收率低、成本高等缺陷，使得光催化材料无法取得理想的光催化效果，限制了其进一步应用。Semiconductor photocatalyst technology has the advantages of mild reaction conditions, no secondary pollution, low energy consumption and high efficiency, and has attracted much attention in the field of antibiotic wastewater treatment. However, in the existing research, the photocatalytic materials have the defects of unsatisfactory responsiveness in the visible light region, poor electron and hole transfer and separation ability, low specific surface area of the material itself, low recovery rate, and high cost, which make the photocatalytic material unable to The ideal photocatalytic effect is obtained, which limits its further application.
申请号为CN201910716666.X的发明专利公开了一种用于光催化降解抗生素的可磁分离的催化剂及其制备方法和应用。所述催化剂以磁性铁酸锌为载体，并且所述磁性铁酸锌上修饰有氮掺杂碳量子点和碳酸银；所述氮掺杂碳量子点的质量分数为0.15～0.20％；所述碳酸银的质量分数为20～30％。The invention patent with the application number CN201910716666.X discloses a magnetically separable catalyst for photocatalytic degradation of antibiotics, and a preparation method and application thereof. The catalyst uses magnetic zinc ferrite as a carrier, and the magnetic zinc ferrite is decorated with nitrogen-doped carbon quantum dots and silver carbonate; the mass fraction of the nitrogen-doped carbon quantum dots is 0.15-0.20%; the The mass fraction of silver carbonate is 20-30%.
申请号为CN201610238572.2的发明专利公开了一种磁性复合光催化剂及其制备方法和应用。该磁性复合光催化剂以Fe 3O 4纳米颗粒为核，Fe 3O 4纳米颗粒表面包覆有SiO 2惰性层，SiO 2惰性层表面富集有Ag 3PO 4，Ag 3PO 4表面修饰有AgCl。 The invention patent with the application number CN201610238572.2 discloses a magnetic composite photocatalyst and a preparation method and application thereof. The magnetic composite photocatalyst takes Fe 3 O 4 nanoparticles as the core, the surface of the Fe 3 O 4 nanoparticles is covered with a SiO 2 inert layer, the surface of the SiO 2 inert layer is enriched with Ag 3 PO 4 , and the surface of the Ag 3 PO 4 is modified with AgCl.
申请号为CN201811178680.0的发明专利公开了一种磁性钒酸铋/钛酸铋/四氧化三铁光催化剂及其制备方法与应用。该光催化剂以鲜花状钒酸铋为基 体，鲜花状钒酸铋颗粒表面同时修饰有钛酸铋和四氧化三铁纳米颗粒，最终形成钒酸铋/钛酸铋/四氧化三铁复合光催化剂。The invention patent with the application number of CN201811178680.0 discloses a magnetic bismuth vanadate/bismuth titanate/iron tetroxide photocatalyst and a preparation method and application thereof. The photocatalyst uses flower-like bismuth vanadate as a matrix, and the surface of flower-like bismuth vanadate particles is simultaneously modified with bismuth titanate and ferric oxide nanoparticles, and finally forms a bismuth vanadate/bismuth titanate/ferric oxide composite photocatalyst .
申请号为CN201711261410.1的发明专利公开了一种g-C 3N 4–Fe 3O 4异质结光催化剂及其制备方法。该制备方法包括如下步骤：将三聚氰胺高温煅烧，得到g-C 3N 4；将所得g-C 3N 4与Fe 3O 4前驱物混合，通过溶胶-热液法制备得到g-C 3N 4/Fe 3O 4光催化剂；将所得g-C 3N 4/Fe 3O 4在缩水剂作用下反应，得到g-C 3N 4–Fe 3O 4异质结光催化剂。 The invention patent with the application number CN201711261410.1 discloses a gC 3 N 4 -Fe 3 O 4 heterojunction photocatalyst and a preparation method thereof. The preparation method includes the following steps: calcining melamine at high temperature to obtain gC 3 N 4 ; mixing the obtained gC 3 N 4 with Fe 3 O 4 precursor, and preparing gC 3 N 4 /Fe 3 O 4 by sol-hydrothermal method Photocatalyst; react the obtained gC 3 N 4 /Fe 3 O 4 under the action of a shrinking agent to obtain a gC 3 N 4 -Fe 3 O 4 heterojunction photocatalyst.
但是，上述光催化剂的电子及空穴传递和分离能力、光催化活性以及光催化降解抗生素的效率并没有得到很大程度上的提升。因此，研发并提供一种光生电子-空穴分离和转移效率高、光吸收效率高、光催化活性高且可回收再利用的复合光催化剂，对于高效降解废水中抗生素具有重要的意义和实用价值。However, the electron and hole transport and separation capabilities, photocatalytic activity, and photocatalytic degradation efficiency of antibiotics of the above-mentioned photocatalysts have not been greatly improved. Therefore, developing and providing a composite photocatalyst with high photo-generated electron-hole separation and transfer efficiency, high light absorption efficiency, high photocatalytic activity and recyclable reusability is of great significance and practical value for the efficient degradation of antibiotics in wastewater. .
发明内容SUMMARY OF THE INVENTION
针对上述现有技术的不足，本发明的目的是提供一种磁性复合光催化剂及其制备方法和在抗生素废水处理中的应用。In view of the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a magnetic composite photocatalyst and its preparation method and application in the treatment of antibiotic wastewater.
为了实现上述发明目的，本发明提供了一种磁性复合光催化剂的制备方法，首先采用水热法合成Bi 2WO 6-Fe 3O 4复合磁性微球；然后，采用三聚氰胺高温煅烧聚合法制备得到石墨相氮化碳(g-C 3N 4)；最后，通过水热复合法构建g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系，制备得到磁性复合光催化剂； In order to achieve the above purpose of the invention, the present invention provides a method for preparing a magnetic composite photocatalyst. First, the Bi 2 WO 6 -Fe 3 O 4 composite magnetic microspheres are synthesized by a hydrothermal method; Graphitic carbon nitride (gC 3 N 4 ); finally, a gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalytic system was constructed by hydrothermal composite method to prepare a magnetic composite photocatalyst;
具体包括如下步骤：Specifically include the following steps:
S1，按预定比例，将Bi(NO 3) 3·5H 2O分散于去离子水中，然后逐渐滴入浓硝酸，磁力搅拌20～40min至溶液澄清，再加入纳米Fe 3O 4粉末继续搅拌20～40min使溶液混合均匀，制备得到第一溶液；将Na 2WO 4·2H 2O分散在去离子水中，磁力搅拌20～40min至完全溶解，制备得到第二溶液；将所述第二溶液缓慢加入所述第一溶液中,连续搅拌30～60min后,调节pH至3～7，转入 反应釜中,在180～200℃反应6～20h，反应结束后,自然冷却至室温，洗涤烘干处理，制备得到Bi 2WO 6-Fe 3O 4； S1: Disperse Bi(NO 3 ) 3 ·5H 2 O in deionized water according to a predetermined proportion, then gradually drop concentrated nitric acid, stir magnetically for 20-40 min until the solution is clear, then add nano Fe 3 O 4 powder and continue stirring for 20 minutes Mix the solution uniformly for ~40min to prepare the first solution; disperse Na 2 WO 4 ·2H 2 O in deionized water, stir magnetically for 20-40 min to completely dissolve, and prepare the second solution; slowly disperse the second solution Add into the first solution, after continuous stirring for 30-60min, adjust the pH to 3-7, transfer to the reaction kettle, react at 180-200 ℃ for 6-20h, after the reaction is completed, naturally cool to room temperature, wash and dry treatment to prepare Bi 2 WO 6 -Fe 3 O 4 ;
S2，按预定比例，将三聚氰胺于500～600℃、惰性气氛保护下，高温煅烧3～5h，冷却研磨处理得到煅烧产物，然后将所述煅烧产物置于冰醋酸溶液中，磁力搅拌1～3h，超声粉碎8～15h，离心沉淀并洗涤至中性，然后烘干研磨处理，得到g-C 3N 4； S2, according to a predetermined proportion, melamine is calcined at a high temperature of 500-600 ° C under the protection of an inert atmosphere for 3-5 hours, cooled and ground to obtain a calcined product, and then the calcined product is placed in a solution of glacial acetic acid, and magnetically stirred for 1-3 hours , ultrasonically pulverized for 8-15 hours, centrifugally precipitated and washed to neutrality, then dried and ground to obtain gC 3 N 4 ;
S3，将步骤S1制备的所述Bi 2WO 6-Fe 3O 4和步骤S2制备的所述g-C 3N 4按预定比例加入到去离子水中，磁力搅拌1～2h至充分混合，得到混合溶液，将所述混合溶液加入水热釜中，150～180℃下反应4～6h，冷却、离心及沉淀处理后，得到g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合材料，作为所述磁性复合光催化剂。 S3, adding the Bi 2 WO 6 -Fe 3 O 4 prepared in step S1 and the gC 3 N 4 prepared in step S2 into deionized water in a predetermined proportion, and magnetically stirring for 1-2 hours to fully mix to obtain a mixed solution , adding the mixed solution into a hydrothermal kettle, reacting at 150-180 ° C for 4-6 h, cooling, centrifuging and precipitation to obtain gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite material, as the magnetic composite photocatalyst.
为了实现上述发明目的，本发明还提供了上述制备方法制备得到的磁性复合光催化剂。所述磁性复合光催化剂是由Bi 2WO 6、Fe 3O 4和g-C 3N 4三者复合而成的具备磁性和半导体光催化性能以及吸附性能的复合材料。 In order to achieve the above purpose of the invention, the present invention also provides the magnetic composite photocatalyst prepared by the above preparation method. The magnetic composite photocatalyst is a composite material composed of Bi 2 WO 6 , Fe 3 O 4 and gC 3 N 4 and has magnetic and semiconductor photocatalytic properties and adsorption properties.
为了实现上述发明目的，本发明还提供了上述磁性复合光催化剂在抗生素废水处理中的应用，具体应用过程为：按预定投加比例，将所述磁性复合光催化剂与所述抗生素废水混合，得到混合液，并在黑暗条件下进行搅拌处理，达到吸附-解吸平衡后，将所述混合液在可见光照射下进行光催化反应，完成对废水水体中抗生素的降解处理。In order to achieve the above purpose of the invention, the present invention also provides the application of the magnetic composite photocatalyst in the treatment of antibiotic wastewater. The mixed solution is stirred under dark conditions, and after reaching the adsorption-desorption equilibrium, the mixed solution is subjected to a photocatalytic reaction under visible light irradiation to complete the degradation treatment of antibiotics in wastewater.
1、本发明提供的磁性复合光催化剂的制备方法，构建出光诱导电子-空穴分离和转移效率高，光催化活性优异，光催化降解抗生素效率高，并且可有效回收循环再利用的g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系，其机理在于： 1. The preparation method of the magnetic composite photocatalyst provided by the present invention has the advantages of high photo-induced electron-hole separation and transfer efficiency, excellent photocatalytic activity, high photocatalytic degradation efficiency of antibiotics, and can effectively recycle and reuse gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalytic system, the mechanism of which is:
1)用水热法合成了三维花朵状Bi 2WO 6-Fe 3O 4磁性微球，由三维花朵状Bi 2WO 6微球镶嵌分散的纳米Fe 3O 4微球颗粒组成，具有明显的介孔结构，其形貌均匀，粒径均一，在外加磁场下具有快速的磁响应性能。其中，三维花朵状Bi 2WO 6由上下两层的(Bi 2O 2) 2+和中间层的(WO 4) 2-交替构成，具有规则的层状结构，独特的层状结构使得其具备优异的吸附性能。该介孔结构和规则 的层状结构，以及Fe 3O 4微球颗粒的纳米尺度效应，使得复合光催化剂具备优异的吸附能力，大的比表面积，显著增大了催化剂与抗生素分子的接触面积，使得光敏位点显著增多，有利于光催化反应的进行，从而加快了光降解速率，同时其规则有序的结构有利于电子和空穴的分离，使其具备优异的光催化活性。 1) Three -dimensional flower-like Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres were synthesized by hydrothermal method . The porous structure has uniform morphology and uniform particle size, and has fast magnetic response performance under an external magnetic field. Among them, the three-dimensional flower-shaped Bi 2 WO 6 is composed of upper and lower layers of (Bi 2 O 2 ) 2+ and (WO 4 ) 2- of the middle layer alternately, and has a regular layered structure. The unique layered structure makes it have Excellent adsorption properties. The mesoporous structure and regular layered structure, as well as the nanoscale effect of Fe 3 O 4 microsphere particles, make the composite photocatalyst have excellent adsorption capacity, large specific surface area, and significantly increase the contact area between the catalyst and antibiotic molecules , resulting in a significant increase in photosensitive sites, which is conducive to the photocatalytic reaction, thereby accelerating the photodegradation rate, and its regular and ordered structure is conducive to the separation of electrons and holes, making it have excellent photocatalytic activity.
2)Bi 2WO 6和g-C 3N 4具有交错的带隙和匹配的能带结构，两者复合后，可以使g-C 3N 4导带上的电子迅速传输到Bi 2WO 6-Fe 3O 4复合微球中Bi 2WO 6的导带上，Bi 2WO 6价带上的空穴传输到g-C 3N 4的价带上，从而实现光诱导电子和空穴的高效分离和转移，有效改善了Bi 2WO 6和g-C 3N 4单体作为光催化剂时光催化效率低的缺陷，显著提升了复合光催化剂的催化活性。两者通过水热法复合后，Bi 2WO 6-Fe 3O 4磁性微球的纳米片出现分散现象，并镶嵌负载在g-C 3N 4表面，使得复合光催化剂的比表面积显著增大，催化剂与抗生素分子的接触面积增大，反应活性位点增多，光催化活性增强。且Bi 2WO 6和g-C 3N 4两者复合后产生协同效应，拓宽了复合光催化剂对可见光的响应范围。 2) Bi 2 WO 6 and gC 3 N 4 have staggered band gaps and matching energy band structures. After the two are recombined, electrons on the conduction band of gC 3 N 4 can be rapidly transferred to Bi 2 WO 6 -Fe 3 O 4 On the conduction band of Bi 2 WO 6 in the composite microspheres, the holes on the valence band of Bi 2 WO 6 are transported to the valence band of gC 3 N 4 , thereby realizing the efficient separation and transfer of light-induced electrons and holes, effectively The defects of low photocatalytic efficiency of Bi 2 WO 6 and gC 3 N 4 monomers as photocatalysts are improved, and the catalytic activity of composite photocatalysts is significantly improved. After the two were composited by hydrothermal method, the nanosheets of Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres appeared dispersed, and were embedded and supported on the surface of gC 3 N 4 , so that the specific surface area of the composite photocatalyst was significantly increased, and the catalyst The contact area with antibiotic molecules increases, the reactive sites increase, and the photocatalytic activity is enhanced. Moreover, the combination of Bi 2 WO 6 and gC 3 N 4 produces a synergistic effect, which broadens the response range of the composite photocatalyst to visible light.
3)将Fe 3O 4引入光催化剂中，构造出g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系，催化性能稳定，并且使得复合光催化剂呈现超顺磁状态，使其在外加磁场的作用下能快速实现固液分离，不会造成二次污染且能循环再利用。同时，三元复合体系中，Fe 3O 4和g-C 3N 4之间会发生相互作用，使得复合光催化剂的结构稳定，增强了复合光催化剂的光生电子-空穴对的分离效率，并且导致生成更多的光生电子-空穴对，发生跃迁所需的能量减少，从而增强了光催化活性。 3) Introducing Fe 3 O 4 into the photocatalyst to construct a gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalytic system, which has stable catalytic performance and makes the composite photocatalyst exhibit a superparamagnetic state, It can quickly achieve solid-liquid separation under the action of an external magnetic field, without causing secondary pollution and can be recycled and reused. At the same time, the interaction between Fe3O4 and gC3N4 in the ternary composite system stabilizes the structure of the composite photocatalyst, enhances the separation efficiency of photogenerated electron - hole pairs of the composite photocatalyst, and leads to More photogenerated electron-hole pairs are generated, and the energy required for the transition to occur is reduced, thereby enhancing the photocatalytic activity.
由此，本发明构建的g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系中，Bi 2WO 6、Fe 3O 4和g-C 3N 4三者相互协同，使得复合光催化剂中形成了三元异质结结构，有利于光生载流子的分离，能有效抑制光催化反应时光生电子和空穴的复合，增强了复合光催化剂的光生电子-空穴对的分离效率，显著提升了光电流响应性能，三元复合共同提高了复合光催化剂的光催化活性，并且 显著提升了光催化降解抗生素的效率。 Therefore, in the gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalytic system constructed by the present invention, Bi 2 WO 6 , Fe 3 O 4 and gC 3 N 4 cooperate with each other, so that the composite The ternary heterojunction structure is formed in the photocatalyst, which is conducive to the separation of photogenerated carriers, can effectively inhibit the recombination of photogenerated electrons and holes in the photocatalytic reaction, and enhance the separation of photogenerated electron-hole pairs of the composite photocatalyst. The efficiency of photocurrent response was significantly improved, and the ternary compounding jointly improved the photocatalytic activity of the composite photocatalyst, and significantly improved the efficiency of photocatalytic degradation of antibiotics.
2、本发明提供的磁性复合光催化剂，光催化活性优异，光催化降解抗生素效率高，并且可有效回收循环再利用，在光催化降解抗生素污染领域具有巨大的应用前景。2. The magnetic composite photocatalyst provided by the present invention has excellent photocatalytic activity, high efficiency of photocatalytic degradation of antibiotics, and can be effectively recycled and reused, and has a huge application prospect in the field of photocatalytic degradation of antibiotic pollution.
具体实施方式detailed description
以下对本发明各实施例的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施例，都属于本发明所保护的范围。The technical solutions of the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.
本发明提供了一种磁性复合光催化剂的制备方法，包括如下步骤：The invention provides a preparation method of a magnetic composite photocatalyst, comprising the following steps:
S1，按预定比例，将Bi(NO 3) 3·5H 2O分散于去离子水中，然后逐渐滴入浓硝酸，磁力搅拌20～40min至溶液澄清，再加入纳米Fe 3O 4粉末继续搅拌20～40min使溶液混合均匀，制备得到第一溶液；将Na 2WO 4·2H 2O分散在去离子水中，磁力搅拌20～40min至完全溶解，制备得到第二溶液；将所述第二溶液缓慢加入所述第一溶液中，连续搅拌30～60min后,调节pH至3～7，转入反应釜中，在180～200℃反应6～20h，反应结束后，自然冷却至室温，洗涤烘干处理，制备得到Bi 2WO 6-Fe 3O 4； S1: Disperse Bi(NO 3 ) 3 ·5H 2 O in deionized water according to a predetermined proportion, then gradually drop concentrated nitric acid, stir magnetically for 20-40 min until the solution is clear, then add nano Fe 3 O 4 powder and continue stirring for 20 minutes Mix the solution uniformly for ~40min to prepare the first solution; disperse Na 2 WO 4 ·2H 2 O in deionized water, stir magnetically for 20-40 min to completely dissolve, and prepare the second solution; slowly disperse the second solution Add into the first solution, after continuous stirring for 30-60min, adjust the pH to 3-7, transfer to the reaction kettle, react at 180-200 ℃ for 6-20h, after the reaction is completed, naturally cool to room temperature, wash and dry treatment to prepare Bi 2 WO 6 -Fe 3 O 4 ;
S2，按预定比例，将三聚氰胺于500～600℃、惰性气氛保护下，高温煅烧3～5h，冷却研磨处理得到煅烧产物，然后将所述煅烧产物置于冰醋酸溶液中，磁力搅拌1～3h，超声粉碎8～15h，离心沉淀并洗涤至中性，然后烘干研磨处理，得到g-C 3N 4； S2, according to a predetermined proportion, melamine is calcined at a high temperature of 500-600 ° C under the protection of an inert atmosphere for 3-5 hours, cooled and ground to obtain a calcined product, and then the calcined product is placed in a solution of glacial acetic acid, and magnetically stirred for 1-3 hours , ultrasonically pulverized for 8-15 hours, centrifugally precipitated and washed to neutrality, then dried and ground to obtain gC 3 N 4 ;
S3，将步骤S1制备的所述Bi 2WO 6-Fe 3O 4和步骤S2制备的所述g-C 3N 4按预定比例加入到去离子水中，磁力搅拌1～2h至充分混合，得到混合溶液，将所述混合溶液加入水热釜中，150～180℃下反应4～6h，冷却、离心及沉淀处理后，得到g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系，作为所述磁性复合光 催化剂。 S3, adding the Bi 2 WO 6 -Fe 3 O 4 prepared in step S1 and the gC 3 N 4 prepared in step S2 into deionized water in a predetermined proportion, and magnetically stirring for 1-2 hours to fully mix to obtain a mixed solution , adding the mixed solution into a hydrothermal kettle, reacting at 150-180°C for 4-6 hours, cooling, centrifuging and precipitation to obtain gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalysis system as the magnetic composite photocatalyst.
在步骤S1中，所述Bi(NO 3) 3·5H 2O与所述Na 2WO 4·2H 2O的摩尔比为(2～4)：1；所述Bi(NO 3) 3·5H 2O与所述纳米Fe 3O 4粉末的摩尔比为(4～6)：1；所述去离子水和所述浓硝酸的体积比为(45～65)：1。 In step S1, the molar ratio of the Bi(NO 3 ) 3 ·5H 2 O to the Na 2 WO 4 ·2H 2 O is (2-4):1; the Bi(NO 3 ) 3 ·5H The molar ratio of 2 O to the nano Fe 3 O 4 powder is (4-6):1; the volume ratio of the deionized water and the concentrated nitric acid is (45-65):1.
在步骤S2中，所述冰醋酸溶液的浓度为1.5～2.5mol/L；In step S2, the concentration of the glacial acetic acid solution is 1.5～2.5mol/L;
在步骤S3中，所述Bi 2WO 6-Fe 3O 4和所述g-C 3N 4的质量分数比为50～60％：40～50％。 In step S3, the mass fraction ratio of the Bi 2 WO 6 -Fe 3 O 4 to the gC 3 N 4 is 50-60%: 40-50%.
本发明还提供了上述磁性复合光催化剂在抗生素废水处理中的应用，具体应用过程为：按预定投加比例，将所述磁性复合光催化剂与所述抗生素废水混合，得到混合液，并在黑暗条件下进行搅拌处理，达到吸附-解吸平衡后，将所述混合液在可见光照射下进行光催化反应，完成对废水水体中抗生素的降解处理。The present invention also provides the application of the magnetic composite photocatalyst in the treatment of antibiotic wastewater. The specific application process is as follows: according to a predetermined dosage ratio, the magnetic composite photocatalyst is mixed with the antibiotic wastewater to obtain a mixed solution, and the mixture is prepared in the dark. Stirring treatment is carried out under the conditions, and after reaching the adsorption-desorption equilibrium, the mixed solution is subjected to photocatalytic reaction under the irradiation of visible light, so as to complete the degradation treatment of the antibiotics in the waste water body.
其中，所述搅拌处理的时间为30～60min；所述光催化反应处理的时间为60～180min；所述抗生素废水的pH值为6～8；所述抗生素废水中抗生素的初始浓度为5～20mg/L，所述磁性复合光催化剂的添加量为0.5～3.0g/L。Wherein, the stirring treatment time is 30-60 min; the photocatalytic reaction treatment time is 60-180 min; the pH value of the antibiotic wastewater is 6-8; the initial concentration of the antibiotic in the antibiotic wastewater is 5-180 min 20mg/L, the addition amount of the magnetic composite photocatalyst is 0.5-3.0g/L.
下面通过具体的实施例对本发明提供的磁性复合光催化剂及其在抗生素废水处理中的应用做进一步的详细描述。The magnetic composite photocatalyst provided by the present invention and its application in the treatment of antibiotic wastewater are further described in detail below through specific examples.
实施例1Example 1
一种磁性复合光催化剂的制备方法，包括如下步骤：A preparation method of a magnetic composite photocatalyst, comprising the following steps:
S1，将6mmoLBi(NO 3) 3·5H 2O分散于去100mL离子水中，然后逐渐滴入4mL浓硝酸，磁力搅拌30min至溶液澄清，再加入1.2mmoL纳米Fe 3O 4粉末继续搅拌30min使溶液混合均匀，制备得到第一溶液；将2mmoL Na 2WO 4·2H 2O分散在去40mL离子水中，磁力搅拌30min至完全溶解，制备得到第二溶液；将所述第二溶液缓慢加入所述第一溶液中，连续搅拌40min后，调节pH至5，转入聚四氟乙烯反应釜中，在185℃反应10h，反应结束后，冷却至室温，再用去离子水和无水乙醇磁分离分别洗涤3次，最后在真 空干燥箱120℃温度下烘干，制备得到Bi 2WO 6-Fe 3O 4磁性微球； S1, disperse 6 mmoLBi(NO 3 ) 3 ·5H 2 O in 100 mL of deionized water, then gradually drop in 4 mL of concentrated nitric acid, stir magnetically for 30 min until the solution is clear, then add 1.2 mmoL of nano Fe 3 O 4 powder and continue stirring for 30 min to make the solution Mix evenly to prepare a first solution; disperse 2 mmoL Na 2 WO 4 ·2H 2 O in 40 mL of deionized water, stir magnetically for 30 min to completely dissolve, and prepare a second solution; slowly add the second solution to the second solution In a solution, after continuous stirring for 40min, adjust the pH to 5, transfer to a polytetrafluoroethylene reaction kettle, and react at 185°C for 10h. Washed 3 times, and finally dried at 120°C in a vacuum drying oven to prepare Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres;
S2，将三聚氰胺于550℃、氦气惰性气氛保护下，高温煅烧4h，冷却研磨处理得到煅烧产物，然后将所述煅烧产物置于2.0mol/L冰醋酸溶液中，磁力搅拌3h，超声粉碎12h，离心沉淀并洗涤至中性，然后烘干研磨处理，得到粉末状g-C 3N 4； S2, calcining melamine at 550°C under the protection of an inert helium atmosphere at high temperature for 4 hours, cooling and grinding to obtain a calcined product, and then placing the calcined product in a 2.0 mol/L glacial acetic acid solution, magnetically stirring for 3 hours, and ultrasonically pulverizing for 12 hours , centrifugal precipitation and washing to neutrality, then drying and grinding to obtain powdery gC 3 N 4 ;
S3，将步骤S1制备的所述Bi 2WO 6-Fe 3O 4磁性微球和步骤S2制备的所述g-C 3N 4按质量分数比为55％：45％的比例加入到去离子水中，磁力搅拌2h至充分混合，得到混合溶液，将所述混合溶液加入水热釜中，180℃下反应4h，冷却、离心及沉淀处理后，60℃烘干得到g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系，作为所述磁性复合光催化剂。 S3, adding the Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres prepared in step S1 and the gC 3 N 4 prepared in step S2 into deionized water at a mass fraction ratio of 55%: 45%, Magnetic stirring for 2 hours until fully mixed to obtain a mixed solution, which was added to a hydrothermal kettle, reacted at 180 °C for 4 hours, cooled, centrifuged and precipitated, and dried at 60 °C to obtain gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalyst system as the magnetic composite photocatalyst.
对比例1Comparative Example 1
与实施例1的不同之处在于：对比例1的光催化剂为Bi 2WO 6单体。 The difference from Example 1 is that the photocatalyst of Comparative Example 1 is Bi 2 WO 6 monomer.
对比例2Comparative Example 2
与实施例1的不同之处在于：对比例2的光催化剂为g-C 3N 4单体。 The difference from Example 1 is that the photocatalyst of Comparative Example 2 is gC 3 N 4 monomer.
对比例3Comparative Example 3
与实施例1的不同之处在于：对比例3的光催化剂为Bi 2WO 6-Fe 3O 4磁性微球。 The difference from Example 1 is that the photocatalyst of Comparative Example 3 is Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres.
对比例4Comparative Example 4
与实施例1的不同之处在于：对比例4的光催化剂为g-C 3N 4/Bi 2WO 6复合催化剂，即，步骤S1中不添加纳米Fe 3O 4粉末。 The difference from Example 1 is that the photocatalyst of Comparative Example 4 is a gC 3 N 4 /Bi 2 WO 6 composite catalyst, that is, no nano Fe 3 O 4 powder is added in step S1.
对比例5Comparative Example 5
与实施例1的不同之处在于：对比例5的光催化剂为现有技术中制备出的g-C 3N 4–Fe 3O 4复合催化剂。 The difference from Example 1 is that the photocatalyst of Comparative Example 5 is the gC 3 N 4 -Fe 3 O 4 composite catalyst prepared in the prior art.
实施例1及对比例1-5制备的光催化剂在两种不同的抗生素废水处理中的应用，具体实验过程为：The application of the photocatalyst prepared in Example 1 and Comparative Examples 1-5 in the treatment of two different antibiotic wastewater, the specific experimental process is:
1)将光催化剂按添加量为1.0g/L与初始浓度为10mg/L的环丙沙星抗生 素废水混合，得到混合液，并在黑暗条件下进行搅拌处理30min，达到吸附-解吸平衡后，将所述混合液在可见光(36W的UV-LED光源)照射下分别进行光催化反应90min，测试环丙沙星降解率。1) The photocatalyst is mixed with ciprofloxacin antibiotic wastewater with an initial concentration of 10 mg/L according to the addition amount of 1.0 g/L to obtain a mixed solution, and is stirred for 30 min under dark conditions, and after reaching the adsorption-desorption equilibrium, The mixed solution was irradiated with visible light (36W UV-LED light source) for photocatalytic reaction for 90 min respectively, and the degradation rate of ciprofloxacin was tested.
2)将光催化剂按添加量为1.0g/L与初始浓度为10mg/L的头孢克肟抗生素废水混合，得到混合液，并在黑暗条件下进行搅拌处理30min，达到吸附-解吸平衡后，将所述混合液在可见光(36W的UV-LED光源)照射下进行光催化反应90min，检测头孢克肟降解率。2) Mix the photocatalyst with cefixime antibiotic wastewater with an initial concentration of 10 mg/L according to the addition amount of 1.0 g/L to obtain a mixed solution, and perform stirring treatment under dark conditions for 30 min to reach the adsorption-desorption equilibrium. The mixed solution was irradiated with visible light (36W UV-LED light source) for photocatalytic reaction for 90 min, and the degradation rate of cefixime was detected.
表1为实施例1及对比例1-5制备的光催化剂的降解性能Table 1 shows the degradation performance of the photocatalysts prepared in Example 1 and Comparative Examples 1-5
实施例Example 环丙沙星降解率Ciprofloxacin degradation rate 头孢克肟降解率Cefixime degradation rate
实施例1Example 1 90.2％90.2% 94.8％94.8%
对比例1Comparative Example 1 41.2％41.2% 43.3％43.3%
对比例2Comparative Example 2 36.4％36.4% 37.6％37.6%
对比例3Comparative Example 3 45.4％45.4% 48.0％48.0%
对比例4Comparative Example 4 88.6％88.6% 91.8％91.8%
对比例5Comparative Example 5 63.7％63.7% 64.9％64.9%
由表1可以看出，实施例1制备的g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化剂对环丙沙星和头孢克肟的降解性能分别达到90.2％和94.8％，均高于对比例1-5中的光催化剂的降解效率，表明本发明实施例1构建的g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系中，Bi 2WO 6、Fe 3O 4和g-C 3N 4三者的协同作用可以提高复合光催化剂的光生电子-空穴对的分离效率，显著提升了光电流响应性能，使其表现出优异的光催化活性，显著提升了光催化降解抗生素的效率。 It can be seen from Table 1 that the degradation performance of gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalyst prepared in Example 1 on ciprofloxacin and cefixime reached 90.2% and 94.8%, respectively. , all higher than the degradation efficiencies of the photocatalysts in Comparative Examples 1-5, indicating that in the gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalytic system constructed in Example 1 of the present invention, Bi 2 WO 6. The synergistic effect of Fe 3 O 4 and gC 3 N 4 can improve the separation efficiency of photogenerated electron-hole pairs of the composite photocatalyst, significantly improve the photocurrent response performance, and make it exhibit excellent photocatalytic activity. The efficiency of photocatalytic degradation of antibiotics was significantly improved.
实施例2-3Example 2-3
与实施例1的不同之处在于：Bi 2WO 6-Fe 3O 4磁性微球和g-C 3N 4按质量分数比设置不同。 The difference from Example 1 is that the Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres and gC 3 N 4 are set differently according to the mass fraction ratio.
表2为实施例1-3制备的光催化剂的参数设置Table 2 is the parameter setting of the photocatalyst prepared by Example 1-3
Figure PCTCN2020113995-appb-000001
Figure PCTCN2020113995-appb-000001
Figure PCTCN2020113995-appb-000002
Figure PCTCN2020113995-appb-000002
本发明中，g-C 3N 4经过超声处理，拥有较薄的层状结构，与三维花朵状Bi 2WO 6-Fe 3O 4磁性微球进行复合后，Bi 2WO 6-Fe 3O 4磁性微球的层状介孔纳米片出现分散现象，通过掺杂和聚合方式负载在g-C 3N 4表面进行结合，使得复合光催化剂的比表面积显著增大，光催化活性显著提升。但随着Bi 2WO 6-Fe 3O 4质量分数的继续增大，Bi 2WO 6-Fe 3O 4磁性微球的纳米片有序排列结构被破坏，在水热复合过程中与g-C 3N 4紧密结合，复合光催化剂出现块状不规则结构，比表面积受到一定的影响，同时也影响异质结的形成，致使光催化剂的催化活性受到一定的影响，降解抗生素的效率呈现下降趋势。 In the present invention, gC 3 N 4 has a thin layered structure after ultrasonic treatment . After being compounded with three -dimensional flower - shaped Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres The layered mesoporous nanosheets of the microspheres appear dispersed, and are supported on the surface of gC 3 N 4 by doping and polymerization for bonding, which significantly increases the specific surface area of the composite photocatalyst and the photocatalytic activity. However, as the mass fraction of Bi 2 WO 6 -Fe 3 O 4 continued to increase, the ordered structure of the nanosheets of Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres was destroyed, and in the process of hydrothermal recombination with gC 3 N 4 is closely combined, and the composite photocatalyst has a block-like irregular structure, and the specific surface area is affected to a certain extent. At the same time, it also affects the formation of heterojunction, resulting in a certain impact on the catalytic activity of the photocatalyst, and the efficiency of degrading antibiotics shows a downward trend.
实施例4-5Example 4-5
与实施例1的不同之处在于：Bi(NO 3) 3·5H 2O与纳米Fe 3O 4粉末的摩尔比设置不同。 The difference from Example 1 is that the molar ratio of Bi(NO 3 ) 3 ·5H 2 O and nano Fe 3 O 4 powder is set differently.
表3为实施例1及实施例4-5制备的光催化剂的参数设置Table 3 is the parameter setting of the photocatalyst prepared in Example 1 and Example 4-5
实施例Example Bi(NO 3) 3·5H 2O与Fe 3O 4的摩尔比 Molar ratio of Bi(NO 3 ) 3 ·5H 2 O to Fe 3 O 4
实施例1Example 1 5∶15:1
实施例4Example 4 4∶14:1
实施例5Example 5 6∶16:1
本发明采用水热法合成了三维花朵状Bi 2WO 6-Fe 3O 4磁性微球，由三维花朵状Bi 2WO 6微球镶嵌分散的纳米Fe 3O 4微球颗粒组成，具有明显的介孔结构，使得复合光催化剂的比表面积显著提升。将Fe 3O 4引入光催化剂中，使得复合光催化剂呈现超顺磁状态，能快速实现磁分离，不会造成二次污染且能循环再利用。在三元复合体系中，Fe 3O 4和g-C 3N 4之间还会发生相互作用，导致生成更多的光生电子-空穴对，从而增强了光催化活性。但是，随着Fe 3O 4比例的增大，纳米Fe 3O 4在与Bi 2WO 6复合的过程会出现团聚现象，影响介孔结构，导致比表面积呈现一定的下降趋势，进而不利于复合光催化剂的光催化活性。 The invention adopts a hydrothermal method to synthesize three -dimensional flower - shaped Bi 2 WO 6 -Fe 3 O 4 magnetic microspheres . The mesoporous structure significantly increases the specific surface area of the composite photocatalyst. The introduction of Fe 3 O 4 into the photocatalyst makes the composite photocatalyst present a superparamagnetic state, which can quickly achieve magnetic separation without causing secondary pollution and can be recycled. In the ternary composite system, the interaction between Fe 3 O 4 and gC 3 N 4 also occurs, resulting in the generation of more photogenerated electron-hole pairs, thereby enhancing the photocatalytic activity. However, as the proportion of Fe 3 O 4 increases, the nano-Fe 3 O 4 will agglomerate in the process of compounding with Bi 2 WO 6 , which will affect the mesoporous structure and cause the specific surface area to show a certain downward trend, which is not conducive to compounding. Photocatalytic activity of photocatalysts.
需要注意的是，本领域技术人员应当理解，在抗生素废水处理实际应用 过程中，光催化剂的投加量和光催化反应时间可以根据抗生素的种类和初始浓度以及光照条件进行相应的调整，抗生素种类还可以为青霉素类、四环素类、β-内酰胺类等。It should be noted that those skilled in the art should understand that in the actual application process of antibiotic wastewater treatment, the dosage of photocatalyst and the photocatalytic reaction time can be adjusted according to the type and initial concentration of antibiotics and light conditions. Penicillins, tetracyclines, β-lactams and the like can be used.
综上所述，本发明提供了一种磁性复合光催化剂及其制备方法和在抗生素废水处理中的应用。首先采用水热法合成Bi 2WO 6-Fe 3O 4复合磁性微球；然后，采用三聚氰胺高温煅烧聚合法制备得到石墨相氮化碳(g-C 3N 4)；最后，通过水热复合法构建g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系，制备得到磁性复合光催化剂。该磁性复合光催化剂的三元复合物相互协同以使光诱导电子-空穴分离和转移效率高，具有优异的光催化活性，光催化降解抗生素效率高，并且可有效回收循环再利用，在光催化降解抗生素污染领域具有巨大的应用前景。 In summary, the present invention provides a magnetic composite photocatalyst, a preparation method thereof, and an application in the treatment of antibiotic wastewater. Firstly, Bi 2 WO 6 -Fe 3 O 4 composite magnetic microspheres were synthesized by hydrothermal method; then, graphitic carbon nitride (gC 3 N 4 ) was prepared by melamine high temperature calcination polymerization method; finally, it was constructed by hydrothermal composite method The gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalyst system was used to prepare a magnetic composite photocatalyst. The ternary complex of the magnetic composite photocatalyst cooperates with each other to make the photoinduced electron-hole separation and transfer efficiency high, has excellent photocatalytic activity, high photocatalytic degradation efficiency of antibiotics, and can be effectively recycled and reused. Catalytic degradation of antibiotic pollution has great application prospects.
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明实施例技术方案。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be Modifications are made to the technical solutions described in the foregoing embodiments, or some or all of the technical features thereof are equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention.

Claims (10)

  1. 一种磁性复合光催化剂的制备方法，其特征在于：包括如下步骤：A preparation method of a magnetic composite photocatalyst is characterized in that: comprises the following steps:
    S1，按预定比例，将Bi(NO 3) 3·5H 2O分散于去离子水中，然后逐渐滴入浓硝酸，磁力搅拌20～40min至溶液澄清，再加入纳米Fe 3O 4粉末继续搅拌20～40min使溶液混合均匀，制备得到第一溶液；将Na 2WO 4·2H 2O分散在去离子水中，磁力搅拌20～40min至完全溶解，制备得到第二溶液；将所述第二溶液缓慢加入所述第一溶液中，连续搅拌30～60min后，调节pH至3～7，转入反应釜中，在180～200℃反应6～20h，反应结束后自然冷却至室温，洗涤烘干处理，制备得到Bi 2WO 6-Fe 3O 4； S1: Disperse Bi(NO 3 ) 3 ·5H 2 O in deionized water according to a predetermined proportion, then gradually drop concentrated nitric acid, stir magnetically for 20-40 min until the solution is clear, then add nano Fe 3 O 4 powder and continue stirring for 20 minutes Mix the solution uniformly for ~40min to prepare the first solution; disperse Na 2 WO 4 ·2H 2 O in deionized water, stir magnetically for 20-40 min to completely dissolve, and prepare the second solution; slowly disperse the second solution Add into the first solution, after continuous stirring for 30-60min, adjust the pH to 3-7, transfer to the reaction kettle, react at 180-200 ℃ for 6-20h, after the reaction is finished, cool to room temperature naturally, wash and dry , to prepare Bi 2 WO 6 -Fe 3 O 4 ;
    S2，按预定比例，将三聚氰胺于500～600℃、惰性气氛保护下，高温煅烧3～5h，冷却研磨处理得到煅烧产物，然后将所述煅烧产物置于冰醋酸溶液中，磁力搅拌1～3h，超声粉碎8～15h，离心沉淀并洗涤至中性，然后烘干研磨处理，得到g-C 3N 4； S2, according to a predetermined proportion, melamine is calcined at a high temperature of 500-600 ° C under the protection of an inert atmosphere for 3-5 hours, cooled and ground to obtain a calcined product, and then the calcined product is placed in a solution of glacial acetic acid, and magnetically stirred for 1-3 hours , ultrasonically pulverized for 8-15 hours, centrifugally precipitated and washed to neutrality, then dried and ground to obtain gC 3 N 4 ;
    S3，将步骤S1制备的所述Bi 2WO 6-Fe 3O 4和步骤S2制备的所述g-C 3N 4按预定比例加入到去离子水中，磁力搅拌1～2h至充分混合，得到混合溶液，将所述混合溶液加入水热釜中，150～180℃下反应4～6h，冷却、离心及沉淀处理后，得到g-C 3N 4/Bi 2WO 6-Fe 3O 4三元复合光催化体系，作为所述磁性复合光催化剂。 S3, adding the Bi 2 WO 6 -Fe 3 O 4 prepared in step S1 and the gC 3 N 4 prepared in step S2 into deionized water in a predetermined proportion, and magnetically stirring for 1-2 hours to fully mix to obtain a mixed solution , adding the mixed solution into a hydrothermal kettle, reacting at 150-180°C for 4-6 hours, cooling, centrifuging and precipitation to obtain gC 3 N 4 /Bi 2 WO 6 -Fe 3 O 4 ternary composite photocatalysis system as the magnetic composite photocatalyst.
  2. 根据权利要求1所述的磁性复合光催化剂的制备方法，其特征在于：在步骤S1中，所述Bi(NO 3) 3·5H 2O与所述Na 2WO 4·2H 2O的摩尔比为(2～4)：1。 The method for preparing a magnetic composite photocatalyst according to claim 1, wherein in step S1, the molar ratio of the Bi(NO 3 ) 3 ·5H 2 O to the Na 2 WO 4 ·2H 2 O (2 to 4): 1.
  3. 根据权利要求1所述的磁性复合光催化剂的制备方法，其特征在于：在步骤S1中，所述Bi(NO 3) 3·5H 2O与所述纳米Fe 3O 4粉末的摩尔比为(4～6)：1。 The method for preparing a magnetic composite photocatalyst according to claim 1, wherein in step S1, the molar ratio of the Bi(NO 3 ) 3 .5H 2 O to the nano Fe 3 O 4 powder is ( 4 to 6): 1.
  4. 根据权利要求1所述的磁性复合光催化剂的制备方法，其特征在于：在步骤S1中，所述去离子水和所述浓硝酸的体积比为(45～65)：1。The method for preparing a magnetic composite photocatalyst according to claim 1, wherein in step S1, the volume ratio of the deionized water and the concentrated nitric acid is (45-65):1.
  5. 根据权利要求1所述的磁性复合光催化剂的制备方法，其特征在于： 在步骤S2中，所述冰醋酸溶液的浓度为1.5～2.5mol/L。The method for preparing a magnetic composite photocatalyst according to claim 1, characterized in that: in step S2, the concentration of the glacial acetic acid solution is 1.5-2.5 mol/L.
  6. 根据权利要求1所述的磁性复合光催化剂的制备方法，其特征在于：在步骤S3中，所述Bi 2WO 6-Fe 3O 4和所述g-C 3N 4的质量分数比为50～60％：40～50％。 The method for preparing a magnetic composite photocatalyst according to claim 1, wherein in step S3, the mass fraction ratio of the Bi 2 WO 6 -Fe 3 O 4 to the gC 3 N 4 is 50-60 %: 40 to 50%.
  7. 一种由权利要求1至6中任一项权利要求所述的磁性复合光催化剂的制备方法制备得到的磁性复合光催化剂，其特征在于：所述磁性复合光催化剂是由Bi 2WO 6、Fe 3O 4和g-C 3N 4三者复合而成的具备磁响应性能和半导体光催化性能以及吸附性能的复合材料。 A magnetic composite photocatalyst prepared by the method for preparing a magnetic composite photocatalyst according to any one of claims 1 to 6, wherein the magnetic composite photocatalyst is composed of Bi 2 WO 6 , Fe 3 O 4 and gC 3 N 4 are composite materials with magnetic response properties, semiconductor photocatalytic properties and adsorption properties.
  8. 磁性复合光催化剂在抗生素废水处理中的应用，其特征在于：采用权利要求1至6所述的磁性复合光催化剂的制备方法制备得到的磁性复合光催化剂或权利要求7所述的磁性复合光催化剂，具体应用过程为：按预定投加比例，将所述磁性复合光催化剂与所述抗生素废水混合，得到混合液，并在黑暗条件下进行搅拌处理，达到吸附-解吸平衡后，将所述混合液在可见光照射下进行光催化反应，完成对废水水体中抗生素的降解处理。The application of magnetic composite photocatalyst in antibiotic wastewater treatment is characterized in that: the magnetic composite photocatalyst prepared by the preparation method of magnetic composite photocatalyst according to claims 1 to 6 or the magnetic composite photocatalyst according to claim 7 The specific application process is as follows: according to a predetermined dosage ratio, the magnetic composite photocatalyst is mixed with the antibiotic wastewater to obtain a mixed solution, and the mixed solution is stirred under dark conditions, and after reaching the adsorption-desorption equilibrium, the mixed solution is mixed. The liquid undergoes a photocatalytic reaction under the irradiation of visible light to complete the degradation treatment of antibiotics in the wastewater.
  9. 根据权利要求8所述的磁性复合光催化剂在抗生素废水处理中的应用，其特征在于：所述搅拌处理的时间为30～60min；所述光催化反应处理的时间为60～180min；所述抗生素废水的pH值为6～8。The application of the magnetic composite photocatalyst in antibiotic wastewater treatment according to claim 8, characterized in that: the stirring treatment time is 30-60 min; the photocatalytic reaction treatment time is 60-180 min; the antibiotic treatment time is 60-180 min; The pH of the wastewater is 6-8.
  10. 根据权利要求8所述的磁性复合光催化剂在抗生素废水处理中的应用，其特征在于：所述抗生素废水中抗生素的初始浓度为5～20mg/L，所述磁性复合光催化剂的添加量为0.5～3.0g/L。The application of the magnetic composite photocatalyst in antibiotic wastewater treatment according to claim 8, wherein the initial concentration of antibiotics in the antibiotic wastewater is 5-20 mg/L, and the addition amount of the magnetic composite photocatalyst is 0.5 mg/L. ~3.0g/L.
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