CN112058276A - Iron ion modified photocatalyst composite material and preparation method thereof - Google Patents

Iron ion modified photocatalyst composite material and preparation method thereof Download PDF

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CN112058276A
CN112058276A CN202010864811.1A CN202010864811A CN112058276A CN 112058276 A CN112058276 A CN 112058276A CN 202010864811 A CN202010864811 A CN 202010864811A CN 112058276 A CN112058276 A CN 112058276A
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iron
parts
doped nano
weight
titanium dioxide
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喻金星
徐晓翔
汪永彬
李红元
查杨
刘记林
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Changzhou Enqi New Materials Co ltd
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Changzhou Enqi New Materials Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89Catalysts 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
    • B01J23/8933Catalysts 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
    • B01J23/8953Catalysts 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 zinc, cadmium or mercury
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/002Catalysts characterised by their physical properties
    • B01J35/004Photocatalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/031Precipitation
    • B01J37/035Precipitation on carriers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/036Precipitation; Co-precipitation to form a gel or a cogel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/06Polluted air

Abstract

An iron ion modified photocatalyst composite material is characterized in that: the photocatalyst composite material comprises the following components in parts by weight: 5-20 parts of iron-doped nano zinc oxide: 1-10 parts of nano silver:1-8 parts of nano platinum: 0.025-0.2 parts of graphene: 0.1-5 parts of penetrant: 0.1-2 parts of dispersant: 0.5-3 parts of deionized water: 200 portions of 450 portions, wherein the chemical structural formula of the iron-doped nano titanium dioxide is Fe-TiO with the concentration of x mol percent2(x is more than or equal to 0.05 and less than or equal to 2), the chemical structural formula of the iron-doped nano zinc oxide is ymol% Fe-ZnO (y is more than or equal to 0.05 and less than or equal to 3), and the chemical structural formula of the graphene is R in parts by weight. The effect of the iron-doped nano titanium dioxide and the iron-doped nano zinc oxide in composite use is higher than that of the iron-doped nano zinc oxide in single use, and the response range of the iron ion modified photocatalyst composite material to light can be expanded to a visible light region, so that the iron ion modified photocatalyst composite material has a better application prospect.

Description

Iron ion modified photocatalyst composite material and preparation method thereof
Technical Field
The invention relates to the technical field of photocatalysts, in particular to an iron ion modified photocatalyst composite material and a preparation method thereof.
Background
People usually spend most of their time indoors, and indoor air quality is very important to humans. Formaldehyde (HCHO) is considered a major indoor air pollutant because long term exposure to formaldehyde can cause serious health problems. Therefore, it is important to develop an economically efficient and simple technique for removing formaldehyde from indoor.
Adsorption is widely used for the removal of formaldehyde in rooms, whose concentration can be successfully reduced to very low levels by some adsorbents. For example, the problem group in the other countries synthesizes porous boron nitride consisting of hexagonal boron nitride nanosheet flexible networks by carrying out heat treatment on a boric acid/urea mixture, and the prepared spongy porous boron nitride shows a rapid adsorption rate and ultrahigh adsorption capacity on gaseous formaldehyde. See Environmental Science & Technolo parts by weight y Letters, 2016, pp 20-25, however, the application of adsorption technology is limited by the adsorption capacity and the possibility of secondary contamination.
The photocatalytic technology is widely used for indoor air purification, formaldehyde can be decomposed into harmless substances such as water and carbon dioxide by the photocatalytic technology, and a large amount of energy is not required to be input. Titanium dioxide is widely researched and used for degrading formaldehyde as a common semiconductor photocatalyst, for example, Zhang Ying task group takes tetrabutyl titanate as a precursor, a titanium dioxide fiber is prepared by adopting a sol-gel method, the titanium dioxide fiber is of a eutectic structure and comprises an anatase phase and a rutile phase, and the formaldehyde degradation rate under the irradiation of ultraviolet light reaches 98.6%. See Applied surface science, 2012, 258, 3469-3474, however, because of the limitation of wide forbidden band, electrons from titanium dioxide valence band can only be activated under the ultraviolet radiation, which limits its practical application.
For example, patent No. 201710730786.6 discloses a ferrored near red highly reflective material and a preparation method thereof, wherein 201710730786.6 has a chemical formula of Ti1-xfex o2, wherein x is 0.05 to 0.20, and the ferrored near red highly reflective material prepared by a sol method emits sunlight, but does not involve formaldehyde decomposition by using the ferrored near red highly reflective material as a catalyst, and cannot be doped with other materials, so that the response range of the photocatalyst composite material to light cannot be expanded.
For example, patent No. 201510518590.1 discloses a visible light-responsive composite photocatalyst, which is formed by compounding a photocatalyst layer, an inorganic protective layer and a connecting layer, wherein the photocatalyst layer is doped with metal ions through a modified titanium dioxide photocatalyst, the inorganic protective layer is nano titanium dioxide, the connecting layer is an inorganic adhesive, strictly speaking, the photocatalyst layer is only mechanically mixed, the inorganic protective layer is not doped in a true chemical sense, the effect is poor, and the light absorption range of titanium dioxide cannot be expanded.
For example, a graphene-iron ion modified TiO2 photocatalyst composite material with patent number 201510061741.5, which mainly comprises graphene and modified TiO2, is not involved in the complex doping of the graphene and the modified TiO2 with zinc oxide, and the doping ratio of the mixture of the graphene and the modified TiO is not considered.
In summary, the prior art still lacks a photocatalyst composite material which can expand the response range of light to the visible light region, has high-efficiency photocatalytic activity under the visible light, and can efficiently purify air to harmful gases such as formaldehyde, benzene and the like under the sunlight.
Disclosure of Invention
The invention aims to provide an iron ion modified photocatalyst composite material. The response range of the photocatalyst composite material to light can be expanded to a visible light region, and the photocatalyst composite material has a good application prospect.
The technical scheme adopted by the invention for solving the problems is as follows: an iron ion modified photocatalyst composite material comprises the following components in parts by weight: 5-20 parts of iron-doped nano zinc oxide: 1-10 parts of nano silver: 1-8 parts of nano platinum: 0.025-0.2 parts of graphene: 0.1-5 parts of penetrant: 0.1-2 parts of dispersant: 0.5-3 parts of deionized water: 200 portions of 450 portions, wherein the chemical structural formula of the iron-doped nano titanium dioxide is Fe-TiO with the concentration of x mol percent2(x is more than or equal to 0.05 and less than or equal to 2), the chemical structural formula of the iron-doped nano zinc oxide is ymol% Fe-ZnO (y is more than or equal to 0.05 and less than or equal to 3), and the chemical structural formula of the graphene is R in parts by weight.
Further, the chemical structural formula of the iron-doped nano titanium dioxide is xmol% Fe-TiO2(x is more than or equal to 0.1 and less than or equal to 1.5), and the chemical structural formula of the iron-doped nano zinc oxide is ymol percent Fe-ZnO (y is more than or equal to 0.1 and less than or equal to 2.2).
A preparation method of an iron ion modified photocatalyst composite material comprises the following steps:
a: preparing iron-doped nano titanium dioxide by a sol-gel method, wherein the doping amount of iron ions is controlled by the addition amount of ferric nitrate;
b: loading nano platinum on the surface of the iron-doped nano titanium dioxide obtained in the step a by a thermal deposition method;
c: preparing iron-doped nano zinc oxide by a hydrothermal method, wherein the doping amount of iron ions is controlled by the adding amount of ferric nitrate;
d: accurately weighing the nano platinum-loaded iron-doped nano titanium dioxide obtained in the step b, the iron-doped nano zinc oxide obtained in the step c, nano silver, graphene, a penetrating agent and a dispersing agent in proportion, mixing, adding deionized water, and stirring the mixture in a stirrer at the rotating speed of 800-1200rpm/min for 1-2 hours to uniformly mix and obtain a mixed solution;
e: and dispersing the mixed solution for 2-3 hours by using an ultrasonic disperser.
Further, the iron-doped nano titanium dioxide in the step a is prepared by a sol-gel method, and the method specifically comprises the following steps: 8.526 parts by weight of isopropyl titanate were weighed into 55-78 parts by weight of absolute ethanol under magnetic stirring to obtain solution S1. According to the doping amount of iron ions, a certain amount of ferric nitrate is dissolved in 80-100 parts by weight of deionized water, 5.25-10.5 parts by weight of glacial acetic acid is added dropwise, and stirring is continued to obtain a solution S2. The solution S2 was added dropwise to the S1 solution with stirring, stirring was continued for 2-4 hours, and then aged at room temperature for 48-96 hours. Washing the obtained product with deionized water and absolute ethyl alcohol, drying, grinding, and then transferring to a muffle furnace at 400-600 ℃ for calcining for 4-6 hours to obtain the iron-doped nano titanium dioxide.
Further, the iron-doped nano titanium dioxide in the step a can perform a photocatalytic reaction under visible light, wherein the doping amount of iron ions is 0.5-2 mol%.
Further, the loading amount of the nano platinum in the step b is 0.5-1% of the weight of the iron-doped nano titanium dioxide.
Further, the iron-doped nano zinc oxide in the step c is prepared by a hydrothermal method, and the method specifically comprises the following steps: firstly, 2.195 parts by weight of zinc acetate is accurately weighed, 120 parts by weight of deionized water and 160 parts by weight of deionized water are added, magnetic stirring is carried out for 5-10 minutes, then a certain amount of ferric nitrate is added into the solution according to the doping amount of ferric ions, and stirring is continued for 5-10 minutes. And then dripping 56-134 parts by weight of 3mol/L sodium hydroxide aqueous solution into the mixed solution, continuously stirring for 15-30 minutes, and then transferring into a high-pressure reaction kettle for hydrothermal reaction, wherein the reaction temperature is set at 150-. After the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, washing and drying the obtained mixture by using deionized water and absolute ethyl alcohol, and then transferring the mixture to a muffle furnace at the temperature of 600-800 ℃ for calcining for 3-5 hours to obtain the iron-doped nano zinc oxide.
Further, the iron-doped nano zinc oxide in the step c can perform a photocatalytic reaction under visible light, wherein the doping amount of iron ions is 0.5-3 mol%.
Further, in the step d, the dispersant is any one of polyvinylpyrrolidone, sodium polyacrylate and ammonium polymethacrylate.
Further, in the step d, the dispersant is a mixture of any two of polyvinylpyrrolidone, sodium polyacrylate and ammonium polymethacrylate, or a mixture of the three.
The invention has the beneficial effects that:
(1) according to the invention, the composite iron-doped nano titanium dioxide, the nano silver, the nano platinum, the graphene and the like are subjected to composite doping according to a proportion after research and development tests, so that the photocatalyst composite material has good photocatalytic activity under visible light, and can play a role in efficiently purifying harmful gases such as formaldehyde, benzene and the like under sunlight.
(2) Can adsorb antibacterial ions and has the function of disinfection.
Detailed Description
Example 1
An iron ion modified photocatalyst composite material comprises the following components in parts by weight: 5-20 parts of iron-doped nano titanium dioxide: 1-10 parts of nano silver: 1-8 parts of nano platinum: 0.025-0.2 parts of graphene: 0.1-5 parts of penetrant: 0.1-2 parts of dispersant: 0.5-3 parts of deionized water: 200 portions of 450 portions, wherein the chemical structural formula of the iron-doped nano titanium dioxide is Fe-TiO with the concentration of x mol percent2(x is more than or equal to 0.05 and less than or equal to 2), the chemical structural formula of the iron-doped nano zinc oxide is ymol% Fe-ZnO (y is more than or equal to 0.05 and less than or equal to 3), and the chemical structural formula of the graphene is R in parts by weight.
Example 2:
the difference from example 1 is: an iron ion modified photocatalyst composite material comprises the following components in parts by weight: 10-15 parts of iron-doped nano zinc oxide: 3-8 parts of nano silver: 3-6 parts of nano platinum: 0.1-0.18 parts, graphene: 2-3 parts of a penetrating agent: 0.8-1.5 parts of dispersant: 1-2 parts, deionized water: 300 portion to 400 portion, wherein the chemical structural formula of the iron-doped nano titanium dioxide is Fe-TiO with the concentration of x mol percent2(x is more than or equal to 0.1 and less than or equal to 1), the chemical structural formula of the iron-doped nano zinc oxide is ymol% Fe-ZnO (y is more than or equal to 0.1 and less than or equal to 2), and the grapheneThe chemical structural formula of (1) is weight portion R.
Example 3:
the difference from the first embodiment is that: the chemical structural formula of the iron-doped nano titanium dioxide is xmol% Fe-TiO2(x is more than or equal to 0.1 and less than or equal to 1.5), and the chemical structural formula of the iron-doped nano zinc oxide is ymol percent Fe-ZnO (y is more than or equal to 0.1 and less than or equal to 2.2).
An iron ion modified photocatalyst composite material comprises the following preparation steps:
the first embodiment:
a. the iron-doped nano titanium dioxide is prepared by a sol-gel method.
b. B, loading nano platinum on the surface of the iron-doped nano titanium dioxide obtained in the step a by a thermal deposition method, wherein the loading amount is 0.5 percent of the weight of the iron-doped nano titanium dioxide; and c, preparing the iron-doped nano zinc oxide by a hydrothermal method.
d. And (c) accurately weighing 16 parts of the nano platinum-loaded iron-doped nano titanium dioxide obtained in the step (b), 6 parts of the iron-doped nano zinc oxide obtained in the step (c), 4 parts of nano silver, 2 parts of graphene, 1 part of penetrating agent and 1 part of polyvinylpyrrolidone according to a ratio, adding the materials into 300 parts of deionized water, and stirring at the rotating speed of 1000rpm/min for 2 hours to uniformly mix the materials.
e. D, dispersing the mixed solution obtained in the step d for 2 hours by using an ultrasonic disperser to obtain the photocatalyst composite material, wherein the doping amount of iron ions in the iron-doped nano titanium dioxide in the step a is 0.5 mol%, and the photocatalyst composite material is prepared by the following steps: 8.526 parts by weight of isopropyl titanate were weighed into 63 parts by weight of absolute ethanol under magnetic stirring to obtain solution S1. 0.06 part by weight of ferric nitrate was dissolved in 80 parts by weight of deionized water, 6.3 parts by weight of glacial acetic acid was added dropwise thereto, and stirring was continued to obtain a solution S2. Under vigorous stirring, the solution S2 was added dropwise to the S1 solution, stirring was continued for 3 hours, and then aged at room temperature for 2 days. Washing the obtained product with deionized water and absolute ethyl alcohol, drying, grinding, transferring to a muffle furnace at 500 ℃ and calcining for 5 hours to obtain 0.5 mol% Fe-TiO2
The doping amount of iron ions in the iron-doped nano zinc oxide in the step c is 0.5 mol%, and the preparation method comprises the following steps: 2.195 parts by weight of zinc acetate is accurately weighed, 120 parts by weight of deionized water is added, magnetic stirring is carried out for 10 minutes, then 0.02 part by weight of ferric nitrate is added into the solution, and stirring is continued for 10 minutes. And then, dripping 89.6 parts by weight of 3mol/L sodium hydroxide aqueous solution into the mixed solution, continuously stirring for 20 minutes, transferring into a high-pressure reaction kettle for hydrothermal reaction, setting the reaction temperature at 160 ℃, and reacting for 10 hours. After the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, washing the obtained product with deionized water and absolute ethyl alcohol, drying, and then transferring the product to a muffle furnace at 600 ℃ to calcine for 4 hours to obtain 0.5 mol% Fe-ZnO.
The second embodiment:
the invention provides an iron ion modified photocatalyst composite material, which comprises the following preparation steps:
a. the iron-doped nano titanium dioxide is prepared by a sol-gel method.
b. And (b) loading nano platinum on the surface of the iron-doped nano titanium dioxide obtained in the step a by a thermal deposition method, wherein the loading amount is 1% of the weight of the iron-doped nano titanium dioxide.
c. Preparing iron-doped nano zinc oxide by a hydrothermal method; and d, accurately weighing 18 parts of the nano platinum-loaded iron-doped nano titanium dioxide obtained in the step b, 5 parts of the iron-doped nano zinc oxide obtained in the step c, 2 parts of nano silver, 2 parts of graphene, 1.5 parts of a penetrating agent and 1.5 parts of sodium polyacrylate according to a proportion, adding the obtained materials into 300 parts of deionized water, and stirring at the rotating speed of 1200rpm/min for 1 hour to uniformly mix the materials.
e, dispersing the mixed liquid obtained in the step d for 3 hours by using an ultrasonic disperser to obtain the photocatalyst composite material.
The doping amount of iron ions in the iron-doped nano titanium dioxide in the step a is 1 mol%, and the preparation method comprises the following steps: 8.526 parts by weight of isopropyl titanate were weighed into 63 parts by weight of absolute ethanol under magnetic stirring to obtain solution S1. Dissolving 0.121 weight part of ferric nitrate in 90 weight parts of deionized water, dripping 7.35 weight parts of glacial acetic acid,stirring was continued to obtain a solution S2. Under vigorous stirring, the solution S2 was added dropwise to the S1 solution, stirring was continued for 3 hours, and then aged at room temperature for 3 days. Washing the obtained product with deionized water and absolute ethyl alcohol, drying, grinding, transferring to a muffle furnace at 400 ℃ and calcining for 6 hours to obtain 1 mol% Fe-TiO2
The doping amount of iron ions in the iron-doped nano zinc oxide in the step c is 1 mol%, and the preparation method comprises the following steps: 2.195 parts by weight of zinc acetate is accurately weighed, 150 parts by weight of deionized water is added, magnetic stirring is carried out for 10 minutes, then 0.04 part by weight of ferric nitrate is added into the solution, and stirring is carried out for 10 minutes. And then, dripping 56 parts by weight of 3mol/L sodium hydroxide aqueous solution into the mixed solution, continuously stirring for 20 minutes, transferring the mixed solution into a high-pressure reaction kettle for hydrothermal reaction, setting the reaction temperature at 150 ℃ and the reaction time for 12 hours. After the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, washing the obtained product with deionized water and absolute ethyl alcohol, drying, and then transferring the product to a muffle furnace at 650 ℃ to calcine for 3 hours to obtain 1 mol% Fe-ZnO.
Third embodiment:
the invention provides an iron ion modified photocatalyst composite material, which comprises the following components in parts by weight, iron-doped nano titanium dioxide 2 mol% Fe-TiO2: 15 parts of Fe-doped nano zinc oxide 2 mol% Fe-ZnO: 4 parts of nano-silver: 4 parts, nano platinum: 0.15 part, graphene: 3 parts of penetrant: 1.5 parts, dispersant: 2.5 parts, deionized water: 300 parts, the preparation comprises the following preparation steps:
step a, preparing iron-doped nano titanium dioxide by a sol-gel method; b, loading nano platinum on the surface of the iron-doped nano titanium dioxide obtained in the step a by a thermal deposition method, wherein the loading amount is 1% of the weight of the iron-doped nano titanium dioxide; c, preparing the iron-doped nano zinc oxide by a hydrothermal method; and d, accurately weighing 15 parts of the nano platinum-loaded iron-doped nano titanium dioxide obtained in the step b, 4 parts of the iron-doped nano zinc oxide obtained in the step c, 4 parts of nano silver, 3 parts of graphene, 1.5 parts of a penetrating agent and 2.5 parts of ammonium polymethacrylate according to a proportion, adding the obtained mixture into 300 parts of deionized water, and stirring the mixture at the rotating speed of 1100rpm/min for 1.5 hours to uniformly mix the mixture. e, dispersing the mixed liquid obtained in the step d for 3 hours by using an ultrasonic disperser to obtain the photocatalyst composite material.
The doping amount of iron ions in the iron-doped nano titanium dioxide in the step a is 2 mol%, and the preparation method comprises the following steps: 8.526 parts by weight of isopropyl titanate were weighed into 63 parts by weight of absolute ethanol under magnetic stirring to obtain solution S1. 0.242 parts by weight of ferric nitrate was dissolved in 100 parts by weight of deionized water, and 9.45 parts by weight of glacial acetic acid was added dropwise thereto, followed by continued stirring to obtain a solution S2. Under vigorous stirring, the solution S2 was added dropwise to the S1 solution, stirring was continued for 4 hours, and then aged at room temperature for 4 days. Washing the obtained product with deionized water and absolute ethyl alcohol, drying, grinding, transferring to a muffle furnace at 550 ℃ and calcining for 4 hours to obtain 2 mol% Fe-TiO2
The doping amount of iron ions in the iron-doped nano zinc oxide in the step c is 2 mol%, and the preparation method comprises the following steps: 2.195 parts by weight of zinc acetate is accurately weighed, 150 parts by weight of deionized water is added, magnetic stirring is carried out for 5 minutes, then 0.08 part by weight of ferric nitrate is added into the solution, and stirring is carried out for 5 minutes. And then, dripping 56 parts by weight of 3mol/L sodium hydroxide aqueous solution into the mixed solution, continuously stirring for 30 minutes, transferring the mixed solution into a high-pressure reaction kettle for hydrothermal reaction, setting the reaction temperature at 150 ℃ and the reaction time for 12 hours. After the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, washing the obtained product with deionized water and absolute ethyl alcohol, drying, and then transferring the product to a muffle furnace at 600 ℃ to calcine for 4 hours to obtain 2 mol% Fe-ZnO.
The formaldehyde removing effect of the iron ion modified photocatalyst composite material prepared in the first example is detected according to the method of B/T16129, and the detection results are shown in Table 1:
serial number Formaldehyde removal rate (%) Toluene removal Rate (%) Ether removal rate (%) Phenol removal rate (%)
Test time 3h 93.5 93.4 95 99.3
Test time 6h 94.5 95.3 95.8 99.5
Test time 9h 97.6 97.8 97.2 99.5
Test time 12h 98.5 97.9 98.1 99.5
Test time 15h 98.6 98.1 99.1 99.5
Test time 18h 98.9 98.5 99.1 99.5
Test time 21h 99.2 98.5 99.2 99.6
Test time 24h 99.2 98.6 99.3 99.6
TABLE 1
The formaldehyde removing effect of the iron ion modified photocatalyst composite material prepared in the second example is detected according to the method of B/T16129, and the detection results are shown in Table 2:
serial number Formaldehyde removal rate (%) Toluene removal Rate (%) Ether removal rate (%) Phenol removal rate (%)
Test time 3h 94.5 94.4 95 91.2
Test time 6h 95.5 95.3 95.8 91.3
Test time 9h 98.6 97.8 97.2 91.5
Test time 12h 99.1 98.5 99.1 91.7
Test time 15h 99.1 98.5 99.1 92.5
Test time 18h 99.1 98.6 99.1 92.7
Test time 21h 99.2 98.6 99.3 92.6
Test time 24h 99.3 98.7 99.3 92.6
TABLE 2
The formaldehyde removing effect of the iron ion modified photocatalyst composite material prepared in the second example is detected according to the method of B/T16129, and the detection results are shown in Table 2:
serial number Formaldehyde removal rate (%) Toluene removal Rate (%) Ether removal rate (%) Phenol removalRemoval rate (%)
Test time 3h 94.5 94.4 95 98.1
Test time 6h 95.5 95.3 95.8 98.5
Test time 9h 96.5 97.8 97.2 99.2
Test time 12h 98.7 98.5 99.1 99.3
Test time 15h 98.9 98.5 99.1 99.5
Test time 18h 99.1 98.5 99.1 99.5
Test time 21h 99.3 98.5 99.3 99.5
Test time 24h 99.3 98.5 99.3 99.6
TABLE 3
As can be seen from tables 1-3, in the first to third embodiments, the removal rate of the photocatalyst composite material reaches 93% or more after 3 hours, and the removal rate of the photocatalyst composite material reaches 99% after 21 hours; after 3 hours, the removal rate of the toluene, the ether and the phenol can reach more than 93 percent, and after 21 hours, the removal rate of the toluene, the ether and the phenol can reach more than 98 percent, which shows that the photocatalyst composite material has high-efficiency removal effect on formaldehyde.

Claims (10)

1. An iron ion modified photocatalyst composite material is characterized in that: the photocatalyst composite material comprises the following components in parts by weight: 5-20 parts of iron-doped nano zinc oxide: 1-10 parts of nano silver: 1-8 parts of nano platinum: 0.025-0.2 parts of graphene: 0.1-5 parts of penetrant: 0.1-2 parts of dispersant: 0.5-3 parts of deionized water: 200 portions of 450 portions, wherein the chemical structural formula of the iron-doped nano titanium dioxide is Fe-TiO with the concentration of x mol percent2(x is more than or equal to 0.05 and less than or equal to 2), the chemical structural formula of the iron-doped nano zinc oxide is ymol% Fe-ZnO (y is more than or equal to 0.05 and less than or equal to 3), and the chemical structural formula of the graphene is R in parts by weight.
2. An iron ion modified photocatalyst composite material is characterized in that: the chemical structural formula of the iron-doped nano titanium dioxide is xmol% Fe-TiO2(x is more than or equal to 0.1 and less than or equal to 1.5), and the chemical structural formula of the iron-doped nano zinc oxide is ymol percent Fe-ZnO (y is more than or equal to 0.1 and less than or equal to 2.2).
3. The method for preparing the iron ion modified photocatalyst composite material as claimed in claim 1, wherein: the method comprises the following steps:
a: preparing iron-doped nano titanium dioxide by a sol-gel method, wherein the doping amount of iron ions is controlled by the addition amount of ferric nitrate;
b: loading nano platinum on the surface of the iron-doped nano titanium dioxide obtained in the step a by a thermal deposition method;
c: preparing iron-doped nano zinc oxide by a hydrothermal method, wherein the doping amount of iron ions is controlled by the adding amount of ferric nitrate;
d: accurately weighing the nano platinum-loaded iron-doped nano titanium dioxide obtained in the step b, the iron-doped nano zinc oxide obtained in the step c, nano silver, graphene, a penetrating agent and a dispersing agent in proportion, mixing, adding deionized water, and stirring the mixture in a stirrer at the rotating speed of 800-1200rpm/min for 1-2 hours to uniformly mix and obtain a mixed solution;
e: and dispersing the mixed solution for 2-3 hours by using an ultrasonic disperser.
4. The method for preparing the iron ion modified photocatalyst composite material as claimed in claim 3, wherein the iron-doped nano titanium dioxide in the step a is prepared by a sol-gel method, and the method comprises the following specific steps: 8.526 parts by weight of isopropyl titanate were weighed into 55-78 parts by weight of absolute ethanol under magnetic stirring to obtain solution S1. According to the doping amount of iron ions, a certain amount of ferric nitrate is dissolved in 80-100 parts by weight of deionized water, 5.25-10.5 parts by weight of glacial acetic acid is added dropwise, and stirring is continued to obtain a solution S2. The solution S2 was added dropwise to the S1 solution with stirring, stirring was continued for 2-4 hours, and then aged at room temperature for 48-96 hours. Washing the obtained product with deionized water and absolute ethyl alcohol, drying, grinding, and then transferring to a muffle furnace at 400-600 ℃ for calcining for 4-6 hours to obtain the iron-doped nano titanium dioxide.
5. The method of claim 3, wherein the iron-doped nano titanium dioxide in step a can perform a photocatalytic reaction under visible light, wherein the doping amount of iron ions is 0.5-2 mol%.
6. The method of claim 3, wherein the amount of the nano platinum loaded in step b is 0.5-1% by weight of the iron-doped nano titanium dioxide.
7. The method for preparing the iron ion modified photocatalyst composite material as claimed in claim 3, wherein the iron-doped nano zinc oxide in the step c is prepared by a hydrothermal method, and the method comprises the following specific steps: firstly, 2.195 parts by weight of zinc acetate is accurately weighed, 120 parts by weight of deionized water and 160 parts by weight of deionized water are added, magnetic stirring is carried out for 5-10 minutes, then a certain amount of ferric nitrate is added into the solution according to the doping amount of ferric ions, and stirring is continued for 5-10 minutes. And then dripping 56-134 parts by weight of 3mol/L sodium hydroxide aqueous solution into the mixed solution, continuously stirring for 15-30 minutes, and then transferring into a high-pressure reaction kettle for hydrothermal reaction, wherein the reaction temperature is set at 150-. After the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, washing and drying the obtained mixture by using deionized water and absolute ethyl alcohol, and then transferring the mixture to a muffle furnace at the temperature of 600-800 ℃ for calcining for 3-5 hours to obtain the iron-doped nano zinc oxide.
8. The method of claim 3, wherein the iron-doped nano zinc oxide in the step c can perform a photocatalytic reaction under visible light, and the doping amount of the iron ions is 0.5-3 mol%.
9. The method as claimed in claim 3, wherein the dispersant in step d is any one of polyvinylpyrrolidone, sodium polyacrylate and ammonium polymethacrylate.
10. The method according to claim 3, wherein the dispersant in step d is a mixture of any two of polyvinylpyrrolidone, sodium polyacrylate, and ammonium polymethacrylate, or a mixture of the two.
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