CN112371151B - Composite photocatalytic material with high-efficiency photocatalytic activity - Google Patents

Composite photocatalytic material with high-efficiency photocatalytic activity Download PDF

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CN112371151B
CN112371151B CN202011207408.8A CN202011207408A CN112371151B CN 112371151 B CN112371151 B CN 112371151B CN 202011207408 A CN202011207408 A CN 202011207408A CN 112371151 B CN112371151 B CN 112371151B
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
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    • 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
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    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, wherein the composite photocatalytic material comprises modified nitrogen carbide, a first catalytic material, a second catalytic material, carbon fibers, sodium phosphate and the like, wherein the modified nitrogen carbide is prepared by a precursor self-assembly copolymerization modification method, and the adopted raw materials are melamine and cyanuric acid; the first catalytic material is Ag/Ag 3 PO 4 /BiPO 4 Composite material, wherein the second catalytic material is CdS microsphere @ TiO 2 The core-shell structure has excellent photocatalytic activity and visible light utilization rate, and the first catalytic material, the second catalytic material and the modified nitrogen carbide are compounded; according to the invention, the photocatalytic material is prepared by compounding the first catalytic material, the second catalytic material and the modified nitrogen carbide, so that the visible light utilization rate of the photocatalytic material is effectively improved, and the photocatalytic material has excellent reaction activity and photocatalytic reaction efficiency and high practicability.

Description

Composite photocatalytic material with high-efficiency photocatalytic activity
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a composite photocatalytic material with high-efficiency photocatalytic activity.
Background
The photocatalysis technology is a green technology with important application prospect in the fields of energy and environment, and the photocatalysis principle is based on the oxidation-reduction capability of the photocatalyst under the condition of illumination, so that the purposes of purifying pollutants, synthesizing substances, converting substances and the like can be achieved. In general, the photocatalytic oxidation reaction uses a semiconductor as a catalyst and light as energy to degrade organic matters into carbon dioxide and water, so that the photocatalytic technology is an efficient and safe environment-friendly environment purification technology.
At present, the photocatalysis technology is mostly used in the fields of environmental cleaning, wastewater treatment and the like, but the existing photocatalyst has higher utilization rate of sunlight, poor photocatalysis activity and low pollution degradation efficiency, which brings great inconvenience to us.
Aiming at the problems, a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof are designed, which is one of the problems to be solved urgently.
Disclosure of Invention
The invention aims to provide a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, so as to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a composite photocatalytic material with high-efficiency photocatalytic activity comprises the following raw materials in parts by weight: 10-25 parts of modified nitrogen carbide, 10-15 parts of first catalytic material, 10-15 parts of second catalytic material, 3-7 parts of carbon fiber and 10-18 parts of sodium phosphate.
More optimized scheme, each component raw material of the first catalytic material comprises: 8-16 parts of bismuth nitrate pentahydrate, 5-12 parts of silver nitrate, 10-20 parts of ethylene glycol and 3-8 parts of sodium hydrophosphate.
More optimized scheme, each component raw material of the second catalytic material comprises: 6-13 parts of tetrabutyl titanate, 2-10 parts of CdS microspheres, 10-20 parts of absolute ethyl alcohol and 3-5 parts of ammonia water.
In an optimized scheme, the CdS microsphere is prepared from cadmium nitrate tetrahydrate, thiourea and glutathione.
In an optimized scheme, the modified nitrogen carbide is prepared from melamine and cyanuric acid.
The invention discloses a composite photocatalytic material with high-efficiency photocatalytic activityThe material comprises modified nitrogen carbide, a first catalytic material, a second catalytic material, carbon fibers, sodium phosphate and the like, wherein the modified nitrogen carbide is prepared by a precursor self-assembly copolymerization modification method, and the adopted raw materials are melamine and cyanuric acid; the first catalytic material is Ag/Ag 3 PO 4 /BiPO 4 The composite material is a CdS microsphere@TiO2 core-shell structure, the first catalytic material and the second catalytic material have excellent photocatalytic activity and visible light utilization rate, and the first catalytic material, the second catalytic material and modified nitrogen carbide are compounded to prepare the photocatalytic material which has high visible light utilization rate and excellent photocatalytic activity and stability.
The preparation method of the composite photocatalytic material with high-efficiency photocatalytic activity comprises the following steps of:
1) Preparing materials;
2) Preparing a first catalytic material;
3) Preparing a second catalytic material;
4) Preparing modified nitrogen carbide;
5) And dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution and the sodium phosphate solution, and reacting to obtain the photocatalytic material.
The more optimized scheme comprises the following steps:
1) Preparing materials;
2) Preparation of the first catalytic material: dissolving bismuth nitrate pentahydrate and silver nitrate prepared in the step 1) in glycol, stirring, adding sodium hydrogen phosphate, continuously stirring, placing in an oil bath for heat preservation, wherein the temperature of the oil bath is 120-130 ℃, the heat preservation time is 2-3h, filtering, alternately washing with ionized water and ethanol, and placing in a drying oven for drying to obtain a first catalytic material;
3) Preparation of a second catalytic material:
a) Dissolving the cadmium nitrate tetrahydrate, thiourea and glutathione prepared in the step 1) in distilled water, stirring and reacting for 1-2h, then placing the mixture into a high-pressure reaction kettle for reacting for 3-4h at 250-260 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres;
b) Taking tetrabutyl titanate and absolute ethyl alcohol prepared in the step 1), and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving the CdS microspheres prepared in the step a) in ethanol, performing ultrasonic dispersion for 20-30min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at the constant temperature of 60-70 ℃ for 3-4 hours to obtain a second catalytic material;
4) Preparation of modified nitrogen carbide: dissolving the melamine prepared in the step 1) in distilled water, and performing ultrasonic dispersion to obtain a melamine solution; dissolving cyanuric acid prepared in the step 1) in distilled water, performing ultrasonic dispersion for 30-40min to obtain cyanuric acid solution, adding the prepared melamine solution and carbon fiber, mixing and stirring, standing, removing supernatant, alternately washing with deionized water and ethanol, drying in a drying oven, placing in a nitrogen environment after drying, heating to 550-560 ℃, and preserving heat for 4-5h to obtain modified nitrogen carbide;
5) Dissolving the modified nitrogen carbide prepared in the step 4) in distilled water, and performing ultrasonic dispersion to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding a modified nitrogen carbide solution, stirring for reaction in a dark place, adding a sodium phosphate solution, mixing, stirring, washing and drying to obtain the photocatalytic material.
The more optimized scheme comprises the following steps:
1) Preparing materials:
a) Weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate for standby;
b) Weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, cyanuric acid, carbon fiber and sodium phosphate for later use; preparing raw materials of each component in the step 1) for subsequent production and preparation;
2) Preparation of the first catalytic material: dissolving bismuth nitrate pentahydrate and silver nitrate prepared in the step 1) in glycol, stirring for 20-30min, adding sodium hydrogen phosphate, stirring for 30-40min, placing in oil bath at 120-130deg.C for 2-3 hr, filtering, adding ionized water, and stirring,Alternately washing with ethanol for 2-3 times, and drying in a drying oven at 70-80deg.C for 8-9 hr to obtain a first catalytic material; the preparation method adopts a one-step low-temperature chemical bath precipitation method in the step 2) and generates Ag/Ag through the reaction of the components such as bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate and the like 3 PO 4 /BiPO 4 A composite material, i.e., a first catalytic material;
3) Preparation of a second catalytic material:
a) Dissolving the cadmium nitrate tetrahydrate, thiourea and glutathione prepared in the step 1) in distilled water, stirring and reacting for 1-2h, then placing the mixture into a high-pressure reaction kettle for reacting for 3-4h at 250-260 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres; in the step 3), the CdS microspheres are synthesized and prepared by a hydrothermal method, and have obvious hollow structures, so that the reflection efficiency of absorbed light can be enhanced, and the solar energy utilization rate is improved;
b) Taking tetrabutyl titanate and absolute ethyl alcohol prepared in the step 1), and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving the CdS microspheres prepared in the step a) in ethanol, performing ultrasonic dispersion for 20-30min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at the constant temperature of 60-70 ℃ for 3-4 hours to obtain a second catalytic material; in the step b), a layer of titanium dioxide sol is wrapped on the surface of the CdS microsphere to form CdS microsphere @ TiO 2 A core-shell structure, namely a second catalytic material;
4) Preparation of modified nitrogen carbide: dissolving the melamine prepared in the step 1) in distilled water, and performing ultrasonic dispersion for 30-40min to obtain a melamine solution; dissolving cyanuric acid prepared in the step 1) by using distilled water, performing ultrasonic dispersion for 30-40min to obtain cyanuric acid solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 8-9h, standing, removing supernatant, alternately washing with deionized water and ethanol for 2-3 times, drying in a drying oven at 60-70 ℃ for 24-28h, heating to 550-560 ℃ at a heating rate of 2-3 ℃/min in a nitrogen environment, and preserving heat for 4-5h to obtain modified nitrogen carbide; according to the method, the precursor self-assembly copolymerization modification method is utilized to prepare the modified nitrogen carbide, and a plurality of holes with different sizes are formed in the surface of the modified nitrogen carbide, so that the modified nitrogen carbide can receive a radiation light source to a greater extent;
5) Dissolving the modified nitrogen carbide prepared in the step 4) in distilled water, and performing ultrasonic dispersion for 20-30min to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding a modified nitrogen carbide solution, stirring for 10-12 hours in a dark place, adding a sodium phosphate solution, mixing and stirring for 5-6 hours, washing and drying to obtain the photocatalytic material. In the step 5), the modified nitrogen carbide is compounded with the first catalytic material and the second catalytic material, and the first catalytic material and the second catalytic material can enter the modified nitrogen carbide through holes or can be adsorbed on the surface of the modified nitrogen carbide, so that the prepared photocatalytic material has high reaction activity and photocatalytic reaction efficiency.
Compared with the prior art, the invention has the beneficial effects that:
when the preparation method is adopted, firstly, the preparation is carried out by adopting a one-step low-temperature chemical bath precipitation method, the Ag/Ag is produced by the reaction of the components such as bismuth nitrate pentahydrate, silver nitrate, glycol, sodium hydrophosphate and the like 3 PO 4 /BiPO 4 The composite material, namely the first catalytic material, has excellent visible light absorption performance, and Ag is prepared in the preparation process 3 PO 4 、BiPO 4 Is formed of Ag/Ag on the surface of 3 PO 4 A heterojunction structure, the heterojunction containing a plurality of defects, and the defects being to inhibit recombination of electron-hole pairs; simultaneous Ag and Ag 3 PO 4 Is formed of Ag/Ag on the surface of 3 PO 4 The heterojunction structure and the heterojunction structure act synergistically, and the prepared first catalytic material has excellent photocatalytic performance and stability.
TiO 2 Is an important semiconductor photocatalysis material, has the characteristics of high activity of photocatalysis degradation of organic matters, stable photochemistry, chemical and photochemical corrosion resistance, no toxicity and the like, and is TiO 2 Although the light is stable, the band gap is wider, the light absorption is limited to the ultraviolet region, but the light can not reach 10% of the solar spectrum irradiated to the ground, thereby limiting the utilization of sunlight and compoundingThe preparation of semiconductors is currently improving TiO 2 A common and very efficient route to photocatalytic activity; cdS (cadmium sulfide) is a semiconductor with a narrower optical band gap, the visible light absorption range can be widened to 520nm, more solar energy can be utilized, and after the CdS microsphere is compounded with the semiconductor, the hollow structure can increase the specific surface area of the compound, enhance the light absorption reflection efficiency and improve the separation of photo-generated electrons and holes of the compound.
Therefore, the invention designs a second catalytic material, and the second catalytic material is CdS microsphere @ TiO 2 The core-shell structure is characterized in that the core-shell structure is formed by firstly preparing CdS microspheres through hydrothermal synthesis and then coating a layer of titanium dioxide sol on the surfaces of the CdS microspheres, so that the CdS microsphere@TiO2 core-shell structure is formed, and the second catalytic material has excellent photocatalytic performance and high visible light utilization rate.
The modified nitrogen carbide is prepared by a precursor self-assembly copolymerization modification method, is in a thinner tubular structure after high-temperature calcination, is in a hollow transparent state at a thinner pipe wall, and is distributed with holes with different pore diameters on the surface, wherein the holes are similar to the wavelength of solar spectrum, can receive incident photons to generate resonance, and can increase the absorption and utilization efficiency of light.
According to the invention, carbon fibers are added, the carbon fibers are carbonized and combusted in the high-temperature roasting process, the formation of holes is further improved, a plurality of holes are tightly connected with one another, the diffusion distance of carriers can be effectively reduced, a system can receive a radiation light source to a greater extent, the first catalytic material and the second catalytic material with smaller particle sizes can enter the modified nitrogen carbide tube in the subsequent compounding process with the first catalytic material and the second catalytic material, the first catalytic material and the second catalytic material with larger particle sizes can be adsorbed on the surface of the modified nitrogen carbide tube, and the first catalytic material and the second catalytic material are mutually cooperated, so that the reaction active site of the composite photocatalytic material is increased, and the reaction activity and the photocatalytic reaction efficiency of the composite photocatalytic material are improved.
The invention discloses a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, which are reasonable in process design and simple to operate, and the visible light utilization rate of the photocatalytic material is effectively improved by compounding a first catalytic material, a second catalytic material and modified nitrogen carbide to prepare the photocatalytic material.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
s1: preparing materials: weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate, and weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, cyanuric acid, carbon fiber and sodium phosphate for later use;
s2: preparation of the first catalytic material: dissolving bismuth nitrate pentahydrate and silver nitrate in ethylene glycol, stirring for 20min, adding sodium hydrogen phosphate, stirring for 30min, placing in an oil bath at 120deg.C for 3h, filtering, alternately washing with ionized water and ethanol for 2 times, and drying in a drying oven at 70deg.C for 9h to obtain a first catalytic material;
s3: preparation of a second catalytic material:
dissolving cadmium nitrate tetrahydrate, thiourea and glutathione in distilled water, stirring and reacting for 1h, then placing the mixture in a high-pressure reaction kettle for reacting for 4h at 250 ℃, cooling and centrifuging, washing with deionized water, and drying to obtain CdS microspheres;
mixing tetrabutyl titanate and absolute ethyl alcohol uniformly at normal temperature to obtain a solution A; dissolving CdS microspheres in ethanol, performing ultrasonic dispersion for 20min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at the constant temperature of 60 ℃ for 4 hours to obtain a second catalytic material;
s4: preparation of modified nitrogen carbide:
dissolving melamine in distilled water, and performing ultrasonic dispersion for 30min to obtain melamine solution; dissolving cyanuric acid in distilled water, performing ultrasonic dispersion for 30min to obtain cyanuric acid solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 8h, standing, removing supernatant, alternately washing with deionized water and ethanol for 2 times, drying in a drying oven at 60 ℃ for 28h, drying in a nitrogen environment, heating to 550 ℃, heating at a heating rate of 2 ℃/min, and preserving heat for 5h to obtain modified nitrogen carbide;
s5: dissolving modified nitrogen carbide in distilled water, and performing ultrasonic dispersion for 20min to obtain modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring for 10 hours in a dark place, adding the sodium phosphate solution, mixing and stirring for 5 hours, washing and drying to obtain the photocatalytic material.
In this embodiment, the raw materials of each component of the composite photocatalytic material include: 10 parts of modified nitrogen carbide, 10 parts of first catalytic material, 10 parts of second catalytic material, 3 parts of carbon fiber and 10 parts of sodium phosphate.
Wherein the first catalytic material comprises the following raw materials in parts by weight: 8 parts of bismuth nitrate pentahydrate, 5 parts of silver nitrate, 10 parts of ethylene glycol and 3 parts of sodium hydrogen phosphate; the second catalytic material comprises the following raw materials in parts by weight: 6 parts of tetrabutyl titanate, 2 parts of CdS microspheres, 10 parts of absolute ethyl alcohol and 3 parts of ammonia water.
Example 2:
s1: preparing materials: weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate, and weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, cyanuric acid, carbon fiber and sodium phosphate for later use;
s2: preparation of the first catalytic material: dissolving bismuth nitrate pentahydrate and silver nitrate in ethylene glycol, stirring for 25min, adding sodium hydrogen phosphate, stirring for 35min, placing in an oil bath at 125 ℃ for 2.5h, filtering, alternately washing with ionized water and ethanol for 2 times, placing in a drying oven, and drying at 75 ℃ for 8.5h to obtain a first catalytic material;
s3: preparation of a second catalytic material:
dissolving tetrahydrated cadmium nitrate, thiourea and glutathione in distilled water, stirring and reacting for 1.5 hours, then placing the mixture in a high-pressure reaction kettle for reacting for 3.5 hours at 255 ℃, cooling and centrifuging the mixture, washing the mixture with deionized water, and drying the mixture to obtain CdS microspheres;
mixing tetrabutyl titanate and absolute ethyl alcohol uniformly at normal temperature to obtain a solution A; dissolving CdS microspheres in ethanol, performing ultrasonic dispersion for 25min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at a constant temperature of 65 ℃ for 3.5 hours to obtain a second catalytic material;
s4: preparation of modified nitrogen carbide:
dissolving melamine in distilled water, and performing ultrasonic dispersion for 35min to obtain melamine solution; dissolving cyanuric acid in distilled water, performing ultrasonic dispersion for 35min to obtain cyanuric acid solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 8.5h, standing, removing supernatant, alternately washing with deionized water and ethanol for 2 times, drying in a drying oven at 65 ℃ for 26h, placing in a nitrogen environment after drying, heating to 555 ℃, heating to 2.5 ℃/min, and preserving heat for 4.5h to obtain modified nitrogen carbide;
s5: dissolving modified nitrogen carbide in distilled water, and performing ultrasonic dispersion for 25min to obtain modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding a modified nitrogen carbide solution, stirring for 11 hours in a dark place, adding a sodium phosphate solution, mixing and stirring for 5.5 hours, washing and drying to obtain the photocatalytic material.
In this embodiment, the raw materials of each component of the composite photocatalytic material include: 15 parts of modified nitrogen carbide, 12 parts of first catalytic material, 12 parts of second catalytic material, 5 parts of carbon fiber and 14 parts of sodium phosphate.
Wherein the first catalytic material comprises the following raw materials in parts by weight: 13 parts of bismuth nitrate pentahydrate, 8 parts of silver nitrate, 15 parts of ethylene glycol and 5 parts of sodium hydrogen phosphate; the second catalytic material comprises the following raw materials in parts by weight: 8 parts of tetrabutyl titanate, 6 parts of CdS microspheres, 15 parts of absolute ethyl alcohol and 4 parts of ammonia water.
Example 3:
s1: preparing materials: weighing cadmium nitrate tetrahydrate, thiourea, glutathione, absolute ethyl alcohol, ammonia water and tetrabutyl titanate, and weighing bismuth nitrate pentahydrate, silver nitrate, ethylene glycol, sodium hydrogen phosphate, melamine, cyanuric acid, carbon fiber and sodium phosphate for later use;
s2: preparation of the first catalytic material: dissolving bismuth nitrate pentahydrate and silver nitrate in ethylene glycol, stirring for 30min, adding sodium hydrogen phosphate, stirring for 40min, placing in an oil bath at 130 ℃ for 2h, filtering, alternately washing with ionized water and ethanol for 3 times, and drying in a drying oven at 80 ℃ for 8h to obtain a first catalytic material;
s3: preparation of a second catalytic material:
dissolving cadmium nitrate tetrahydrate, thiourea and glutathione in distilled water, stirring and reacting for 2 hours, then placing the mixture in a high-pressure reaction kettle for reacting for 3 hours at 260 ℃, cooling and centrifuging the mixture, washing the mixture with deionized water, and drying the mixture to obtain CdS microspheres;
mixing tetrabutyl titanate and absolute ethyl alcohol uniformly at normal temperature to obtain a solution A; dissolving CdS microspheres in ethanol, performing ultrasonic dispersion for 30min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at a constant temperature of 70 ℃ for 3 hours to obtain a second catalytic material;
s4: preparation of modified nitrogen carbide:
dissolving melamine in distilled water, and performing ultrasonic dispersion for 40min to obtain melamine solution; dissolving cyanuric acid in distilled water, performing ultrasonic dispersion for 40min to obtain cyanuric acid solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 9h, standing, removing supernatant, alternately washing with deionized water and ethanol for 3 times, drying in a drying oven at 70 ℃ for 24h, placing in a nitrogen environment after drying, heating to 560 ℃ at a heating rate of 3 ℃/min, and preserving heat for 4h to obtain modified nitrogen carbide;
s5: dissolving modified nitrogen carbide in distilled water, and performing ultrasonic dispersion for 30min to obtain modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring for 12 hours in a dark place, adding the sodium phosphate solution, mixing and stirring for 6 hours, washing and drying to obtain the photocatalytic material.
In this embodiment, the raw materials of each component of the composite photocatalytic material include: 25 parts of modified nitrogen carbide, 15 parts of first catalytic material, 15 parts of second catalytic material, 7 parts of carbon fiber and 18 parts of sodium phosphate.
Wherein the first catalytic material comprises the following raw materials in parts by weight: by weight, 16 parts of bismuth nitrate pentahydrate, 12 parts of silver nitrate, 20 parts of ethylene glycol and 8 parts of sodium hydrogen phosphate; the second catalytic material comprises the following raw materials in parts by weight: 13 parts of tetrabutyl titanate, 10 parts of CdS microspheres, 20 parts of absolute ethyl alcohol and 5 parts of ammonia water.
Experiment:
the composite photocatalytic material prepared in the examples 1 to 3 was taken and rhodamine was degraded under visible light at room temperature, respectively, wherein a 300WXe lamp with an ultraviolet filter was used as a light source, and the specific operation was:
0.10g of the composite photocatalytic material sample prepared in the examples 1-3 is respectively taken and mixed with 100ml of rhodamine in darkness, and the mixture is uniformly stirred, so that dynamic balance of adsorption-adsorption desorption is established between the composite photocatalytic material and the rhodamine.
In the illumination, 5ml of the solution is removed at regular intervals, the composite photocatalytic material is removed by centrifugation, and the change of the absorption peak is recorded at 554nm by a UV-2102PC photometer.
Conclusion: according to experimental operation, an ultraviolet-visible absorption spectrum diagram of the rhodamine degradation composite photocatalytic material is obtained, and along with the extension of illumination time, an absorption peak at 554nm on a curve is severely reduced, which shows that the composite photocatalytic material has excellent photocatalytic degradation performance on rhodamine under visible light.
The illumination experiment is carried out for 60min, and statistics shows that the degradation rate of the composite photocatalytic material to rhodamine can reach 99% at the highest and 98% at the lowest within 60min of illumination, which indicates that the composite photocatalytic material has high photocatalytic reaction activity to rhodamine and high catalytic efficiency.
The invention discloses a composite photocatalytic material with high-efficiency photocatalytic activity and a preparation method thereof, which are reasonable in process design and simple to operate, and the visible light utilization rate of the photocatalytic material is effectively improved by compounding a first catalytic material, a second catalytic material and modified nitrogen carbide to prepare the photocatalytic material.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (1)

1. A composite photocatalytic material with high-efficiency photocatalytic activity is characterized in that: the composite photocatalytic material comprises the following raw materials in parts by weight: 10 parts of modified nitrogen carbide, 10 parts of first catalytic material, 10 parts of second catalytic material, 3 parts of carbon fiber and 10 parts of sodium phosphate;
wherein the first catalytic material comprises the following raw materials in parts by weight: 8 parts of bismuth nitrate pentahydrate, 5 parts of silver nitrate, 10 parts of ethylene glycol and 3 parts of sodium hydrogen phosphate;
the second catalytic material comprises the following raw materials in parts by weight: 6 parts of tetrabutyl titanate, 2 parts of CdS microspheres, 10 parts of absolute ethyl alcohol and 3 parts of ammonia water by weight;
the modified nitrogen carbide is prepared from melamine and cyanuric acid;
the CdS microspheres are prepared from cadmium nitrate tetrahydrate, thiourea and glutathione;
the preparation method comprises the following steps:
1) Preparing materials;
2) Preparation of a first catalytic material: dissolving bismuth nitrate pentahydrate and silver nitrate prepared in the step 1) in ethylene glycol, stirring for 20min, adding sodium hydrogen phosphate, continuously stirring for 30min, placing in an oil bath for heat preservation, wherein the temperature of the oil bath is 120 ℃, the heat preservation time is 3h, filtering, alternately washing with deionized water and ethanol for 2 times, placing in a drying oven for drying, and the drying temperature is 70 ℃ and the drying time is 9h to obtain a first catalytic material;
3) Preparation of a second catalytic material:
a) Dissolving the cadmium nitrate tetrahydrate, thiourea and glutathione prepared in the step 1) in distilled water, stirring and reacting for 1h, then placing the mixture into a high-pressure reaction kettle for reacting for 4h at 250 ℃, cooling and centrifuging the mixture, washing the mixture with deionized water, and drying the mixture to obtain CdS microspheres;
b) Taking tetrabutyl titanate and absolute ethyl alcohol prepared in the step 1), and stirring and mixing uniformly at normal temperature to obtain a solution A; dissolving the CdS microspheres prepared in the step a) in ethanol, performing ultrasonic dispersion for 20min, adding ammonia water, and uniformly mixing to obtain a solution B; mixing the solution A and the solution B, and reacting at the constant temperature of 60 ℃ for 4 hours to obtain a second catalytic material;
4) Preparation of modified nitrogen carbide:
dissolving the melamine prepared in the step 1) in distilled water, and performing ultrasonic dispersion for 30min to obtain a melamine solution; dissolving cyanuric acid prepared in the step 1) by using distilled water, performing ultrasonic dispersion for 30min to obtain cyanuric acid solution, adding the prepared melamine solution and carbon fiber, mixing and stirring for 8h, standing, removing supernatant, alternately washing with deionized water and ethanol for 2 times, drying in a drying oven at 60 ℃ for 28h, placing in a nitrogen environment after drying, heating to 550 ℃, heating to 2 ℃/min, and preserving heat for 5h to obtain modified nitrogen carbide;
5) Dissolving the modified nitrogen carbide prepared in the step 4) in distilled water, and performing ultrasonic dispersion for 20min to obtain a modified nitrogen carbide solution; and (3) dissolving the first catalytic material and the second catalytic material in distilled water, slowly adding the modified nitrogen carbide solution, stirring for 10 hours in a dark place, adding the sodium phosphate solution, mixing and stirring for 5 hours, washing and drying to obtain the photocatalytic material.
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