CN110882713A - Conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material, preparation method thereof and application thereof in photocatalytic desulfurization - Google Patents
Conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material, preparation method thereof and application thereof in photocatalytic desulfurization Download PDFInfo
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- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 76
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000002096 quantum dot Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 238000006477 desulfuration reaction Methods 0.000 title abstract description 14
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- 239000000243 solution Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 20
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- 238000010586 diagram Methods 0.000 description 2
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
The invention belongs to the field of nano material preparation, and relates to a conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material, a preparation method thereof and application thereof in photocatalytic desulfurization. According to the invention, the conductive attapulgite is adopted, titanium oxide is hydrothermally grown on the conductive attapulgite to form a hairbrush-shaped composite material, then carbon nitride quantum dots are compounded on the hairbrush-shaped attapulgite/titanium oxide, and the carbon nitride quantum dots and the titanium oxide form a heterojunction, so that the separation of electrons and holes can be accelerated, the response of the material to visible light is improved, and the utilization rate of visible light is improved. The obtained composite material is used for photocatalytic desulfurization, and can achieve remarkable desulfurization effect.
Description
Technical Field
The invention belongs to the field of nano material preparation, and relates to a hydrothermal method for preparing a conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material with conductive attapulgite as a carrier and application of the composite material in photocatalytic desulfurization.
Background
Sulfur oxides (SOx) discharged from fuel combustion easily cause acid rain and haze, which become serious environmental pollution problems, and thus removal of sulfur-containing organic compounds in oil products is urgently needed. The traditional hydrodesulfurization process has harsh technological conditions, needs high temperature and high pressure and consumes a large amount of hydrogen, and oxidative desulfurization becomes a research hotspot due to the advantages of mild reaction conditions, no consumption of a large amount of hydrogen, low investment and the like. The photocatalytic desulfurization is a novel desulfurization technology for catalytic oxidation desulfurization by adopting a semiconductor catalyst with optical activity, has the advantages of mild reaction conditions, low energy consumption, environmental friendliness and the like, and is concerned. The principle is as follows: the semiconductor catalyst can generate electrons and holes under the excitation of light, and then reacts with an oxidant to generate superoxide anions and hydroxyl free radicals with strong oxidizing property, so that thiophene sulfides are oxidized into corresponding sulfone or sulfoxide polar sulfur-containing substances, and finally the sulfur-containing substances are removed through extraction.
Titanium oxide (TiO)2) It is attracting attention as an environmentally friendly semiconductor which is nontoxic and harmless, has high stability and excellent photosensitivity. But TiO 22Has a wide band gap of 3.0eV, and absorbs only ultraviolet rays constituting a small part of sunlight, and TiO2The photo-generated charge carriers in (1) are easily recombined, which is to TiO2Adversely affects the photoelectrochemical properties of the film. It is therefore necessary to modify it to increase its photoresponsive rangeAnd electron separation efficiency.
Therefore, how to further improve the photoresponse range and the electron separation efficiency of the titanium oxide is a problem which is urgently needed to be solved at present.
Disclosure of Invention
The invention provides a composite material for photo-generated cathode protection, namely a conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material.
The invention also provides a preparation method of the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material, which comprises the following steps:
firstly, synthesizing a brush-shaped conductive attapulgite/titanium oxide binary material by using a hydrothermal method by using conductive attapulgite as a carrier; and then loading the carbon nitride quantum dots on the one-dimensional titanium oxide rod to obtain the conductive electric attapulgite/titanium oxide/carbon nitride quantum dot composite material.
The method comprises the following specific steps:
1. weighing the nitrogen-rich precursor, sodium chloride and potassium chloride, mixing and grinding, then calcining for 3-5h in a muffle furnace at 650-700 ℃, and grinding the obtained carbon nitride intermediate into powder. Then washing the carbon nitride intermediate by using dilute hydrochloric acid, and centrifugally collecting a solid, wherein the solid is marked as a solid I; and then dispersing the solid I into deionized water, centrifuging at 6000-10000rpm to remove large carbon nitride particles, and finally obtaining a stable colloidal solution of the carbon nitride quantum dots, which is marked as CN-QD.
Wherein the nitrogen-rich precursor is one of melamine, dicyandiamide and urea, the molar ratio of sodium chloride to potassium chloride is 1:1, the molar ratio of the nitrogen-rich precursor to sodium chloride is 0.75:1, and the mass ratio of dilute hydrochloric acid to the carbon nitride intermediate is 10: 1, the mass ratio of deionized water to the solid I is 20:1, and the concentration of dilute hydrochloric acid is 1-2M.
2. Adding conductive attapulgite into a mixed solution of titanium salt and hydrochloric acid, performing ultrasonic treatment for 20-40min, transferring to a Teflon lining, performing hydrothermal treatment at 60-100 deg.C for 4-12h, cooling to room temperature, performing suction filtration, washing, and drying at 60-80 deg.C to obtain brush-shaped conductive attapulgite/titanium oxide.
Wherein the concentration of the hydrochloric acid is 2mol/L, the titanium salt solution is a titanium tetrachloride solution, the concentration is 3-5mol/L, and the mass ratio of the conductive attapulgite to the titanium salt solution is 2-0.5: 1, the volume ratio of the titanium salt solution to the hydrochloric acid solution is 1: 30.
The conductive attapulgite is prepared by coating Sb-doped tin oxide on the surface of attapulgite and has the function of guiding the generation of rod-shaped titanium oxide.
When the conventional attapulgite is used for loading titanium oxide, the titanium oxide can be loaded on the attapulgite only in the form of nano particles, and a plurality of free particles can form a heterojunction with subsequent carbon nitride quantum dots, so that the problems of low light utilization rate and high electron and hole recombination rate of the composite material can not be effectively solved.
3. Dispersing the colloidal solution of the conductive attapulgite/titanium oxide and the carbon nitride quantum dots into deionized water, carrying out ultrasonic treatment for 20-30 minutes, transferring the mixture to a Teflon lining, carrying out hydrothermal treatment for 2-6 hours at the temperature of 60-80 ℃, cooling to room temperature, carrying out suction filtration washing, and drying at the temperature of 60-80 ℃ to obtain the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material.
Wherein the mass ratio of the attapulgite/titanium oxide composite material to the deionized water is 1:20, and the mass ratio of the CN-QD sol to the attapulgite/titanium oxide composite material is 1-3: 10.
The invention has the beneficial effects that:
1. the conductive attapulgite is used as a carrier, the short rod-shaped titanium oxide is grown hydrothermally to form brush-shaped conductive attapulgite/titanium oxide, and the one-dimensional rod-shaped titanium oxide has larger specific surface area and excellent electron transport performance compared with titanium oxide particles, so that the photoelectrochemical performance can be greatly improved.
2. According to the invention, the carbon nitride quantum dots are compounded on the brush-shaped attapulgite/titanium oxide, and the one-dimensional rod-shaped titanium oxide has a larger specific surface area, so that a heterojunction can be formed with the carbon nitride quantum dots, the separation of electrons and holes can be accelerated, the response of the material to visible light is improved, and the utilization rate of the visible light is improved.
Drawings
FIG. 1 is a transmission electron micrograph of the material prepared in example 1;
FIG. 2 is a transmission electron micrograph of the material prepared in comparative example 4;
FIG. 3 is a graph showing the change of desulfurization degree with time in the use of the materials prepared in example 1 and comparative example 1, comparative example 2, comparative example 3, and comparative example 4;
FIG. 4 is a Uv-vis diagram for example 1 and comparative examples 1 and 2.
Detailed Description
The invention is further described below with reference to examples and comparative examples, but the scope of protection of the invention is not limited to the ranges referred to in the examples:
example 1
1. 6.26g of dicyandiamide, 5.8g of sodium chloride and 7.4g of potassium chloride were weighed, mixed and ground, and then calcined in a muffle furnace at 650 ℃ for 3 hours, and the resulting carbon nitride intermediate was ground into powder. Then washing 1g of the carbon nitride intermediate by using 10g of diluted hydrochloric acid (1M), and centrifugally collecting a solid, wherein the solid is marked as a solid I; then 0.5g of solid i was dispersed in 10g deionized water and centrifuged at 6000rpm to remove the large carbon nitride particles and finally to obtain a colloidal solution of stable carbon nitride quantum dots, designated CN-QD.
2. Adding 0.5g of conductive attapulgite into 0.8mL of a mixed solution of 4M titanium tetrachloride solution and 24mL of 2M hydrochloric acid, carrying out ultrasonic treatment for 30min, then transferring the mixture to a Teflon lining, carrying out hydrothermal treatment at 80 ℃ for 8h, cooling to room temperature, carrying out suction filtration washing, and drying at 70 ℃ to obtain the brush-shaped conductive attapulgite/titanium oxide.
3. Dispersing a colloidal solution of 100mg of conductive attapulgite/titanium oxide and 12mg of carbon nitride quantum dots into 20mL of deionized water, carrying out ultrasonic treatment for 20 minutes, transferring the mixture to a Teflon lining, carrying out hydrothermal treatment at 60 ℃ for 2 hours, cooling to room temperature, carrying out suction filtration washing, and drying at 60 ℃ to obtain the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material.
FIG. 4 is a Uv-vis diagram of conductive attapulgite/titanium oxide/carbon nitride quantum dots, whereinIt can be seen that the absorption edge of example 1 is red-shifted, mainly due to CNQDs and TiO2A heterojunction is formed.
Example 2
1. 9.71g of melamine, 6g of sodium chloride and 7.65g of potassium chloride were weighed, mixed and ground, and then calcined in a muffle furnace at 670 ℃ for 4 hours, and the resulting carbon nitride intermediate was ground into powder. Then washing 2g of the carbon nitride intermediate by using 20g of diluted hydrochloric acid (1M), and centrifugally collecting a solid, wherein the solid is marked as a solid I; 1.2g of solid I was then dispersed in 24g deionized water and centrifuged at 7000rpm to remove the large carbon nitride particles and finally to obtain a colloidal solution of stable carbon nitride quantum dots, designated CN-QD.
2. Adding 0.3g of conductive attapulgite into a mixed solution of 0.88mL of 3M titanium tetrachloride solution and 26.4mL of 2M hydrochloric acid, carrying out ultrasonic treatment for 20min, then transferring the mixture to a Teflon lining, heating the mixture at 60 ℃ for 4h, cooling the mixture to room temperature, carrying out suction filtration washing, and drying the cooled mixture at 60 ℃ to obtain brush-shaped conductive attapulgite/titanium oxide.
3. Dispersing 150mg of conductive attapulgite/titanium oxide and 30mg of carbon nitride quantum dot colloidal solution into 30mL of deionized water, carrying out ultrasonic treatment for 25 minutes, transferring the mixture to a Teflon lining, carrying out hydrothermal treatment for 4 hours at 70 ℃, cooling to room temperature, carrying out suction filtration washing, and drying at 80 ℃ to obtain the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material.
Example 3
1. 5.01g of urea, 6.5g of sodium chloride and 8.29g of potassium chloride were weighed, mixed and ground, and then calcined in a muffle furnace at 700 ℃ for 5 hours, and the resulting carbon nitride intermediate was ground into powder. Then washing 1.5g of the carbon nitride intermediate by using 15g of diluted hydrochloric acid (1M), and centrifugally collecting a solid, wherein the solid is marked as a solid I; then 0.8g of solid i was dispersed in 16g deionized water and centrifuged at 8000rpm to remove large carbon nitride particles, resulting in a stable colloidal solution of carbon nitride quantum dots, designated CN-QD.
2. Adding 1.2g of conductive attapulgite into 0.64mL of a mixed solution of 5M titanium tetrachloride solution and 19.2mL of 2M hydrochloric acid, performing ultrasonic treatment for 40min, transferring the mixture to a Teflon lining, performing hydrothermal treatment at 100 ℃ for 12h, cooling to room temperature, performing suction filtration washing, and drying at 80 ℃ to obtain brush-shaped conductive attapulgite/titanium oxide.
3. Dispersing 200mg of conductive attapulgite/titanium oxide and 62mg of carbon nitride quantum dot colloidal solution into 40mL of deionized water, carrying out ultrasonic treatment for 40 minutes, transferring the mixture to a Teflon lining, carrying out hydrothermal treatment for 6 hours at 80 ℃, cooling to room temperature, carrying out suction filtration washing, and drying at 80 ℃ to obtain the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material.
Comparative example 1
The operation of adding the carbon nitride quantum dots in the example 1 is removed, and other operations are the same as the example 1:
1. adding 0.3g of conductive attapulgite into a mixed solution of 0.88mL of 3M titanium tetrachloride solution and 26.4mL of 2M hydrochloric acid, carrying out ultrasonic treatment for 20min, then transferring the mixture to a Teflon lining, heating the mixture at 60 ℃ for 4h, cooling the mixture to room temperature, carrying out suction filtration washing, and drying the cooled mixture at 60 ℃ to obtain brush-shaped conductive attapulgite/titanium oxide.
2. Dispersing 150mg of conductive attapulgite/titanium oxide into 30mL of deionized water, carrying out ultrasonic treatment for 25 minutes, transferring the mixture to a Teflon liner, heating the mixture for 4 hours at 70 ℃, cooling the mixture to room temperature, carrying out suction filtration and washing, and drying the mixture at 80 ℃ to obtain the conductive attapulgite/titanium oxide composite material.
Comparative example 2
The operation of hydrothermally generating titanium oxide on the conductive attapulgite in the example 2 is omitted, and the other operations are the same as the example 2:
1. 9.71g of melamine, 6g of sodium chloride and 7.65g of potassium chloride were weighed, mixed and ground, and then calcined in a muffle furnace at 670 ℃ for 4 hours, and the resulting carbon nitride intermediate was ground into powder. Then washing 2g of the carbon nitride intermediate by using 20g of diluted hydrochloric acid (1M), and centrifugally collecting a solid, wherein the solid is marked as a solid I; 1.2g of solid I was then dispersed in 24g deionized water and centrifuged at 7000rpm to remove the large carbon nitride particles and finally to obtain a colloidal solution of stable carbon nitride quantum dots, designated CN-QD. 2. Dispersing 150mg of conductive attapulgite and 30mg of carbon nitride quantum dot colloidal solution into 30mL of deionized water, carrying out ultrasonic treatment for 25 minutes, transferring the mixture to a Teflon lining, heating the mixture at 70 ℃ for 4 hours, cooling the mixture to room temperature, carrying out suction filtration and washing, and drying the mixture at 80 ℃ to obtain the conductive attapulgite/carbon nitride quantum dot composite material.
Comparative example 3
Patent CN201810871400.8 discloses a preparation method of a TiO quantum dot/carbon nitride/attapulgite composite material and an example 1 of the application of the composite material in photocathode corrosion prevention.
1. Adding 5g of cyclohexane, 2g of oleic acid, 2g of tetrabutyl titanate and 1g of oleylamine into a three-neck flask in sequence, magnetically stirring for 0.5h, transferring the solution to a Teflon lining, carrying out hydrothermal treatment at 140 ℃ for 12h, and cooling to room temperature to obtain TiO2-a transparent brown sol of QDs.
2. 1g of melamine was dissolved in 50g of CCl4And (3) dispersing 1g of attapulgite into the solution under ultrasonic treatment, performing ultrasonic treatment for 1h, then pouring the suspension into a Teflon container, performing hydrothermal reaction for 12h at 180 ℃, cooling to room temperature, performing suction filtration, washing a filter cake, drying at 60 ℃, and calcining for 1h at 500 ℃ in a nitrogen atmosphere to obtain the attapulgite/carbon nitride composite material.
3. Adding 100mg of attapulgite/carbon nitride composite material and 10g of absolute ethyl alcohol into a three-neck flask, stirring for 1h, and then adding 5mg of TiO2Quickly injecting the-QD sol into a three-neck flask, stirring for 1h, centrifuging at 6000r/min, and drying at 60 ℃ to obtain TiO2The quantum dot/carbon nitride/attapulgite composite material. And (3) carrying out photocatalytic desulfurization test on the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material.
Comparative example 4
Comparative example 4 compared with example 1, the difference is that the conductive attapulgite is replaced by the conventional commercially available attapulgite (the surface of the attapulgite is not coated with Sb-doped tin oxide), and the other operations are the same as example 1. And preparing the attapulgite/titanium oxide/carbon nitride quantum dot composite material.
Preparing simulation oil, namely adding 0.2g of DBT powder into 250mL of n-octane to obtain the simulation oil with the sulfur content of 200 ppm. Weighing 100mg of catalyst, adding the catalyst, prepared simulation oil and hydrogen peroxide into a photochemical reaction instrument (HGX-3), starting magnetic stirring, introducing air for bubbling, adsorbing for 30min under dark conditions, establishing adsorption-desorption balance, starting a 300W xenon lamp, sampling for 10mL at intervals of 30min, performing centrifugal separation, taking supernatant, extracting a product in the simulation oil by using DMF, taking the supernatant, and detecting the sulfur content by using an ultraviolet fluorescence sulfur measuring instrument (KY-3000S), wherein the test result is shown in figure 3. As can be seen from FIG. 3, the desulfurization efficiency of the conductive attapulgite/titanium oxide/carbon nitride quantum dot in the embodiment 1 of the invention is the highest.
Desulfurization efficiency D ═ 100% (1-Ct/C0)%
Wherein: c0 is the sulfur content of the initial solution, Ct is the sulfur content after t-time of reaction.
Table 1:
the raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in all kinds of fields suitable for this invention, and further modifications can be readily made by those skilled in the art, so that the invention is not limited to the specific details and embodiments shown and described herein, without departing from the general concept defined by the claims and their equivalents.
Claims (9)
1. A conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material is characterized in that: the composite material is composed of conductive attapulgite, titanium oxide and carbon nitride quantum dots.
2. The conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material of claim 1, wherein: the conductive attapulgite refers to the attapulgite with antimony-doped tin oxide coated on the surface.
3. The preparation method of the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material according to claim 2, wherein the preparation steps of the composite material are as follows:
(1) preparing a stable colloidal solution of the carbon nitride quantum dots, and marking the solution as CN-QD;
(2) adding conductive attapulgite into a mixed solution of titanium salt and hydrochloric acid, ultrasonically mixing, transferring into a reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, carrying out suction filtration, washing and drying to obtain brush-shaped conductive attapulgite/titanium oxide;
(3) dispersing the conductive attapulgite/titanium oxide and the colloidal solution of the carbon nitride quantum dots in the step (1) into deionized water, ultrasonically mixing, transferring to a reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, carrying out suction filtration, washing and drying to obtain the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material.
4. The preparation method of the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material according to claim 3, wherein the preparation method comprises the following steps: the hydrothermal reaction condition of the step (2) is hydrothermal for 4-12h at 60-100 ℃.
5. The preparation method of the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material according to claim 3, wherein the preparation method comprises the following steps: the concentration of the hydrochloric acid in the step (2) is 2mol/L, and the titanium salt solution is a titanium tetrachloride solution with the concentration of 3-5 mol/L; the mass ratio of the conductive attapulgite to the titanium salt solution is 2-0.5: 1; the volume ratio of the titanium salt solution to the hydrochloric acid solution is 1: 30.
6. The preparation method of the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material according to claim 3, wherein the preparation method comprises the following steps: the hydrothermal reaction condition of the step (3) is that the hydrothermal reaction is carried out for 2-6h at the temperature of 60-80 ℃.
7. The preparation method of the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material according to claim 3, wherein the preparation method comprises the following steps: the preparation method of the colloidal solution of the carbon nitride quantum dots comprises the following steps:
(1) mixing and grinding a nitrogen precursor, sodium chloride and potassium chloride, and calcining for 3-5h at the temperature of 650-700 ℃ in a muffle furnace after grinding to obtain a carbon nitride intermediate;
(2) grinding the carbon nitride intermediate into powder, washing the carbon nitride intermediate by using dilute hydrochloric acid, and centrifugally collecting a solid, wherein the solid is marked as a solid I; and then dispersing the solid I into deionized water, and centrifuging at 6000-10000rpm to remove large carbon nitride particles, thereby finally obtaining the stable colloidal solution of the carbon nitride quantum dots.
8. The preparation method of the conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material according to claim 3, wherein the preparation method comprises the following steps: the mass ratio of the CN-QD sol to the attapulgite/titanium oxide composite material is 1-3: 10.
9. The use of the electrically conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material according to any one of claims 1-8 as a catalyst in photocatalytic desulphurization.
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