Functional attapulgite loaded NiO-g-C3N4The photocatalytic-adsorbent and the preparation method
阅读说明：本技术 一种功能化凹凸棒石负载NiO-g-C3N4的光催化-吸附剂和制法 (Functional attapulgite loaded NiO-g-C3N4The photocatalytic-adsorbent and the preparation method ) 是由 陈东丽 程芳 程丽丽 于 2021-01-18 设计创作，主要内容包括：本发明涉及污水处理技术领域,且公开了一种功能化凹凸棒石负载NiO-g-C-3N-4的光催化-吸附剂,在凹凸棒石表面引入丰富的巯基官能团,巯基-SH容易发生电离,失去质子氢,形成-S～-阴离子,与阳离子染料甲基橙具有良好的静电作用,g-C-3N-4纳米片表面生成中空多孔形貌的NiO,两者之间形成异质结结构,通过异质结载流子传输机制,促进了光生电子和空穴的分离,减少了重组的现象,对甲基橙具有良好的光催化降解活性,通过水热法进行复合,得到光催化-吸附复合材料,先通过凹凸棒石修饰的巯基将甲基橙进行静电吸引,吸附到复合材料表面,进一步再被凹凸棒石表面负载的NiO-g-C-3N-4异质结光催化剂降解。(The invention relates to the technical field of sewage treatment and discloses a functional attapulgite loaded NiO-g-C 3 N 4 The photocatalyst-adsorbent introduces abundant sulfydryl functional groups on the surface of attapulgite, and sulfydryl-SH is easy to ionize and lose proton hydrogen to form-S ‑ Anion, has good electrostatic effect with cationic dye methyl orange, g-C 3 N 4 NiO with a hollow porous shape is generated on the surface of the nano sheet, a heterojunction structure is formed between the NiO and the nano sheet, the separation of photo-generated electrons and holes is promoted through a heterojunction carrier transmission mechanism, the recombination phenomenon is reduced, and the nano-sheet has good photocatalysis effect on methyl orangeDegrading activity, compounding by a hydrothermal method to obtain a photocatalytic-adsorption composite material, firstly performing electrostatic attraction on methyl orange by using attapulgite-modified sulfydryl, adsorbing the methyl orange onto the surface of the composite material, and further loading NiO-g-C on the surface of the attapulgite 3 N 4 The heterojunction photocatalyst degrades.)
1. Functional attapulgite loaded NiO-g-C3N4The photocatalytic adsorbent of (1), characterized in that: the functionalized attapulgite loaded with NiO-g-C3N4The preparation method of the photocatalysis-adsorbent comprises the following steps:
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi；
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent, performing modification treatment after uniform ultrasonic dispersion, performing centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain episulfide attapulgite;
(3) adding cyclosulfurized attapulgite and sodium hydrosulfide into a distilled water solvent, performing ring-opening reaction after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing a product by using distilled water to obtain sulfydryl functionalized attapulgite;
(4) adding g-C to distilled water solvent3N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 8-9, pouring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction, filtering the solvent, washing the solution to be neutral by distilled water, placing the mixed product in a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4；
(5) Adding sulfydryl functionalized attapulgite and NiO hollow microsphere loaded g-C into distilled water solvent3N4After dispersing uniformly, pouring the solution into a water heaterPerforming hydrothermal reaction in a reaction kettle, filtering the solvent and drying to obtain the functional attapulgite supported NiO-g-C3N4The photocatalyst-adsorbent of (1).
2. The functionalized attapulgite supported NiO-g-C according to claim 13N4The photocatalytic adsorbent of (1), characterized in that: the mass ratio of the activated attapulgite to the episulfide silane coupling agent in the step (2) is 100: 80-150.
3. The functionalized attapulgite supported NiO-g-C according to claim 13N4The photocatalytic adsorbent of (1), characterized in that: the temperature of the modification treatment in the step (2) is 40-60 ℃, and the time of the modification treatment is 5-10 h.
4. The functionalized attapulgite supported NiO-g-C according to claim 13N4The photocatalytic adsorbent of (1), characterized in that: the mass ratio of the attapulgite hydrosulfide in the step (3) to the sodium hydrosulfide is 100: 120-200.
5. The functionalized attapulgite supported NiO-g-C according to claim 13N4The photocatalytic adsorbent of (1), characterized in that: the temperature of the ring-opening reaction in the step (3) is 20-35 ℃, and the reaction time is 12-24 h.
6. The functionalized attapulgite supported NiO-g-C according to claim 13N4The photocatalytic adsorbent of (1), characterized in that: g to C in the step (4)3N4Nanosheet, NiCl2The mass ratio of the glucose is 100:180-260: 320-460.
7. The functionalized attapulgite supported NiO-g-C according to claim 13N4The photocatalytic adsorbent of (1), characterized in that: the temperature of the hydrothermal reaction in the step (4) is 170-190 ℃, and the reaction time is 3-6 h.
8. The functionalized attapulgite supported NiO-g-C according to claim 13N4The photocatalytic adsorbent of (1), characterized in that: the mercapto-functionalized attapulgite and the NiO hollow microspheres in the step (5) are loaded with g-C3N4The mass ratio of (A) to (B) is 100: 30-80.
9. The functionalized attapulgite supported NiO-g-C according to claim 13N4The photocatalytic adsorbent of (1), characterized in that: the temperature of the hydrothermal reaction in the step (5) is 100-130 ℃, and the reaction time is 2-6 h.
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a functional attapulgite loaded NiO-g-C3N4The photocatalytic adsorbent and the preparation method.
Background
In recent years, industries such as paper making industry, dye industry, textile industry and the like are rapidly developed, a large amount of dye wastewater is generated, the dye wastewater has the characteristics of complex components, difficult degradation, great toxicity hazard and the like, if the dye wastewater is not effectively treated, the dye wastewater is discharged into rivers, lakes and seas, great environmental pollution can be caused, the traditional dye wastewater mainly contains methyl orange, rhodamine B, gentian violet and the like, and the treatment methods of organic dye pollutants mainly comprise an adsorption method, an oxidation-reduction method, a biodegradation method, a membrane separation method and the like.
The adsorption method has the advantages of simplicity, high efficiency, low cost and the like, the adsorbent mainly comprises active carbon, diatomite and the like, the attapulgite has a layer chain-shaped regular structure, a unique porous structure and high surface area, and has good adsorption performance and wide application prospects in the aspects of adsorption, separation, catalyst carriers and the like; the photocatalytic degradation method is a new sewage treatment method in recent years, and the traditional photocatalyst mainly comprises TiO2、BiVO4CdS, etc., wherein the graphite phase carbon nitride is g-C3N4Has the advantages of high specific surface area, strong visible light activity, simple preparation method and the like, has important application in the field of photocatalytic degradation, but has g-C3N4The photogenerated carriers are easy to recombine, the photocatalytic degradation activity of the photogenerated carriers is seriously influenced, the construction of the heterojunction is an effective method for solving the problem, and attapulgite with high specific surface area can be used as a photocatalyst carrier to load g-C3N4The photocatalyst can simultaneously have the double functions of adsorption and photocatalytic degradation.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a functional attapulgite loaded NiO-g-C3N4The photocatalyst-adsorbent and the preparation method solve the problem of poor adsorption performance of single attapulgite and simultaneously solve the problem of poor adsorption performance of the single attapulgiteDetermine g-C3N4The problem of easy recombination of photogenerated carriers.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: functional attapulgite loaded NiO-g-C3N4The functionalized attapulgite is loaded with NiO-g-C3N4The preparation method of the photocatalysis-adsorbent comprises the following steps:
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi。
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent, performing modification treatment after uniform ultrasonic dispersion, performing centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain the episulfide attapulgite.
(3) Adding cyclosulfide attapulgite and sodium hydrosulfide into a distilled water solvent, performing ring-opening reaction after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing the product with distilled water to obtain the sulfydryl functionalized attapulgite.
(4) Adding g-C to distilled water solvent3N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 8-9, pouring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction, filtering the solvent, washing the solution to be neutral by distilled water, placing the mixed product in a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4。
(5) Adding sulfydryl functionalized attapulgite and NiO hollow microsphere loaded g-C into distilled water solvent3N4After being dispersed uniformly, the solution is poured into a hydrothermal reaction kettle for hydrothermal reaction, the solvent is filtered and dried to obtain the functional attapulgite supported NiO-g-C3N4The photocatalyst-adsorbent of (1).
Preferably, the mass ratio of the activated attapulgite to the episulfide silane coupling agent in the step (2) is 100: 80-150.
Preferably, the temperature of the modification treatment in the step (2) is 40-60 ℃, and the time of the modification treatment is 5-10 h.
Preferably, the mass ratio of the attapulgite sulfide ring to the sodium hydrosulfide in the step (3) is 100: 120-200.
Preferably, the temperature of the ring-opening reaction in the step (3) is 20-35 ℃, and the reaction time is 12-24 h.
Preferably, g to C in said step (4)3N4Nanosheet, NiCl2The mass ratio of the glucose is 100:180-260: 320-460.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 170-190 ℃, and the reaction time is 3-6 h.
Preferably, the mercapto-functionalized attapulgite and the NiO hollow microspheres in the step (5) are loaded with g-C3N4The mass ratio of (A) to (B) is 100: 30-80.
Preferably, the temperature of the hydrothermal reaction in the step (5) is 100-130 ℃, and the reaction time is 2-6 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the functional attapulgite loaded NiO-g-C3N4The photocatalytic-adsorbent is prepared by modifying activated attapulgite by using episulfide silane coupling agent to obtain episulfide attapulgite, performing ring-opening addition reaction on the introduced episulfide group and sodium hydrosulfide to generate two mercapto functional groups, thereby introducing abundant mercapto functional groups to realize functional modification of the attapulgite, and forming-S due to easy ionization of mercapto-SH and loss of proton hydrogen-The anion and the methyl orange are cationic dyes, show cation in water, and have good positive and negative charge attraction static effects with-S-anion, so that the mercapto-functionalized attapulgite has higher adsorption effect on the methyl orange.
The functional attapulgite loaded NiO-g-C3N4In g-C of the photocatalytic-adsorbent of3N4Nano-sheetAs a growth carrier, glucose is used as a structure directing agent at g-C3N4NiO precursor coated carbon microspheres are generated on the surfaces of the nano sheets, and the carbon microspheres are removed through high-temperature annealing, so that NiO forms a unique hollow porous shape, the specific surface area is higher, the absorption and the responsiveness to light energy can be improved, and g-C3N4And a heterojunction structure is formed between the NiO and the organic silicon oxide, the separation of photo-generated electrons and holes is promoted through a heterojunction carrier transmission mechanism, the recombination phenomenon is reduced, the organic silicon oxide further reacts with oxygen and water to generate oxygen free radicals and hydroxyl free radicals with extremely strong activity, the high-efficiency redox reaction is carried out on the organic silicon oxide and methyl orange, and the organic silicon oxide and the methyl orange are degraded into non-toxic micromolecules, so that the organic silicon oxide has good photocatalytic degradation activity on the methyl orange.
The functional attapulgite loaded NiO-g-C3N4The photocatalyst-adsorbent is prepared by loading g-C on sulfydryl functionalized attapulgite and NiO hollow microspheres3N4Compounding by a hydrothermal method to obtain a photocatalytic-adsorption composite material, firstly performing electrostatic attraction on methyl orange through attapulgite-modified sulfydryl, adsorbing the methyl orange onto the surface of the composite material, and further loading NiO-g-C on the surface of the attapulgite3N4The heterojunction photocatalyst is degraded, so that the double functions of adsorption and photocatalytic degradation are achieved, and the degradation efficiency of the methyl orange is higher.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: functional attapulgite loaded NiO-g-C3N4The preparation method of the photocatalysis-adsorbent comprises the following steps:
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi。
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent, wherein the mass ratio of the episulfide silane coupling agent to the activated attapulgite is 80-150:100, carrying out modification treatment at 40-60 ℃ for 5-10h after uniform ultrasonic dispersion, carrying out centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain the episulfide attapulgite.
(3) Adding the attapulgite sulfide and sodium hydrosulfide with the mass ratio of 100:120-200 into a distilled water solvent, performing ring-opening reaction at 20-35 ℃ for 12-24h after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing a product by using distilled water to obtain the attapulgite sulfide with the mercapto group functionalized.
(4) Adding g-C with the mass ratio of 100:180-260:320-460 into the distilled water solvent3N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 8-9, pouring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 3-6h at the temperature of 170-190 ℃, filtering the solvent, washing the solution to neutrality by distilled water, placing the mixed product into a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4。
(5) Adding mercapto-functionalized attapulgite and NiO hollow microsphere loaded g-C into a distilled water solvent in a mass ratio of 100:30-803N4After being dispersed uniformly, the solution is poured into a hydrothermal reaction kettle for hydrothermal reaction for 2 to 6 hours at the temperature of 100 ℃ and 130 ℃, the solvent is filtered and dried to obtain the functional attapulgite loaded NiO-g-C3N4The photocatalyst-adsorbent of (1).
Example 1
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi。
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent, wherein the mass ratio of the episulfide silane coupling agent to the activated attapulgite is 80:100, performing modification treatment at 40 ℃ for 5 hours after uniform ultrasonic dispersion, performing centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain the episulfide attapulgite.
(3) Adding the attapulgite sulfide and sodium hydrosulfide in a mass ratio of 100:120 into a distilled water solvent, performing ring-opening reaction for 12 hours at 20 ℃ after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing the product with distilled water to obtain the sulfhydryl-functionalized attapulgite.
(4) Adding g-C into distilled water solvent at a mass ratio of 100:180:3203N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 8, pouring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 3 hours at 170 ℃, filtering the solvent, washing the solution to be neutral by distilled water, placing the mixed product in a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4。
(5) Adding sulfydryl functionalized attapulgite and NiO hollow microsphere loaded g-C with the mass ratio of 100:30 into a distilled water solvent3N4After being dispersed uniformly, the solution is poured into a hydrothermal reaction kettle for hydrothermal reaction for 2 hours at the temperature of 100 ℃, and the solvent is filtered and dried to obtain the functional attapulgite loaded NiO-g-C3N4The photocatalyst-adsorbent of (1).
Example 2
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi。
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent, wherein the mass ratio of the episulfide silane coupling agent to the activated attapulgite is 1:1, performing ultrasonic dispersion uniformly, performing modification treatment at 50 ℃ for 8h, performing centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain the episulfide attapulgite.
(3) Adding the attapulgite sulfide and sodium hydrosulfide with the mass ratio of 100:150 into a distilled water solvent, performing ring-opening reaction for 18h at 25 ℃ after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing the product with distilled water to obtain the sulfhydryl functionalized attapulgite.
(4) Adding g-C into distilled water solvent at a mass ratio of 100:200:3603N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 9, pouring the solution into a hydrothermal reaction kettle, and adding the solution into the hydrothermal reaction kettle at 1Carrying out hydrothermal reaction for 4h at the temperature of 80 ℃, filtering the solvent, washing the mixture to be neutral by distilled water, putting the mixed product into a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4。
(5) Adding sulfydryl functionalized attapulgite and NiO hollow microsphere loaded g-C with the mass ratio of 100:45 into a distilled water solvent3N4After being dispersed uniformly, the solution is poured into a hydrothermal reaction kettle for hydrothermal reaction for 4 hours at the temperature of 120 ℃, and the solvent is filtered and dried to obtain the functional attapulgite supported NiO-g-C3N4The photocatalyst-adsorbent of (1).
Example 3
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi。
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent, wherein the mass ratio of the episulfide silane coupling agent to the activated attapulgite is 120:100, performing ultrasonic dispersion uniformly, performing modification treatment at 50 ℃ for 8h, performing centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain the episulfide attapulgite.
(3) Adding the attapulgite sulfide and sodium hydrosulfide with the mass ratio of 100:170 into a distilled water solvent, performing ring-opening reaction for 18h at 30 ℃ after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing the product with distilled water to obtain the sulfhydryl functionalized attapulgite.
(4) Adding g-C into distilled water solvent at a mass ratio of 100:230:4103N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 8.5, pouring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4 hours at 180 ℃, filtering the solvent, washing the solution to be neutral by distilled water, placing the mixed product in a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4。
(5) Adding sulfydryl functionalized attapulgite and NiO hollow microspheres with the mass ratio of 100:60 into a distilled water solventLoad g-C3N4After being dispersed uniformly, the solution is poured into a hydrothermal reaction kettle for hydrothermal reaction for 4 hours at the temperature of 120 ℃, and the solvent is filtered and dried to obtain the functional attapulgite supported NiO-g-C3N4The photocatalyst-adsorbent of (1).
Example 4
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi。
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent, wherein the mass ratio of the episulfide silane coupling agent to the activated attapulgite is 150:100, performing modification treatment at 60 ℃ for 10 hours after uniform ultrasonic dispersion, performing centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain the episulfide attapulgite.
(3) Adding the attapulgite sulfide and sodium hydrosulfide with the mass ratio of 100:200 into a distilled water solvent, performing ring-opening reaction for 24 hours at 35 ℃ after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing the product with distilled water to obtain the sulfhydryl functionalized attapulgite.
(4) Adding g-C into distilled water solvent at a mass ratio of 100:260:4603N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 9, pouring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 6 hours at 190 ℃, filtering the solvent, washing the solution to be neutral by distilled water, placing the mixed product in a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4。
(5) Adding sulfydryl functionalized attapulgite and NiO hollow microsphere loaded g-C with the mass ratio of 100:80 into a distilled water solvent3N4After being dispersed uniformly, the solution is poured into a hydrothermal reaction kettle, hydrothermal reaction is carried out for 6 hours at the temperature of 130 ℃, the solvent is filtered and dried, and the functionalized attapulgite loaded NiO-g-C is obtained3N4The photocatalyst-adsorbent of (1).
Comparative example 1
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi。
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent with the mass ratio of 60:100 to the activated attapulgite, performing modification treatment at 50 ℃ for 5h after uniform ultrasonic dispersion, performing centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain the episulfide attapulgite.
(3) Adding the attapulgite sulfide and sodium hydrosulfide with the mass ratio of 100:90 into a distilled water solvent, performing ring-opening reaction for 24 hours at 20 ℃ after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing the product with distilled water to obtain the sulfhydryl functionalized attapulgite.
(4) Adding g-C into distilled water solvent at a mass ratio of 100:150:2803N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 9, pouring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 4 hours at 180 ℃, filtering the solvent, washing the solution to be neutral by distilled water, placing the mixed product in a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4。
(5) Adding sulfydryl functionalized attapulgite and NiO hollow microsphere loaded g-C with the mass ratio of 100:15 into a distilled water solvent3N4After being dispersed uniformly, the solution is poured into a hydrothermal reaction kettle for hydrothermal reaction for 4 hours at the temperature of 120 ℃, and the solvent is filtered and dried to obtain the functional attapulgite supported NiO-g-C3N4The photocatalyst-adsorbent of (1).
Comparative example 2
(1) 3-glycidoxy propyl trimethoxy silane and potassium thiocyanate are used as raw materials to obtain the episulfide silane coupling agent with the molecular formula of C9H20O4SSi。
(2) Pretreating attapulgite by using a hydrochloric acid solution to obtain activated attapulgite, then placing the activated attapulgite in a toluene solvent, adding an episulfide silane coupling agent, wherein the mass ratio of the episulfide silane coupling agent to the activated attapulgite is 180:100, performing ultrasonic dispersion uniformly, performing modification treatment at 50 ℃ for 8h, performing centrifugal separation to remove the solvent, and washing the product by using distilled water and ethanol in sequence to obtain the episulfide attapulgite.
(3) Adding the attapulgite sulfide and sodium hydrosulfide in a mass ratio of 100:230 into a distilled water solvent, performing ring-opening reaction for 18h at 30 ℃ after uniform ultrasonic dispersion, centrifugally separating to remove the solvent, and washing the product with distilled water to obtain the sulfhydryl-functionalized attapulgite.
(4) Adding 100:290:500 g-C by mass into distilled water solvent3N4Nanosheet, NiCl2And glucose, dropwise adding sodium hydroxide after uniform dispersion, adjusting the pH value of the solution to 9, pouring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 6 hours at 180 ℃, filtering the solvent, washing the solution to be neutral by distilled water, placing the mixed product in a resistance furnace for annealing treatment to obtain NiO hollow microsphere load g-C3N4。
(5) Adding sulfydryl functionalized attapulgite and NiO hollow microsphere loaded g-C with the mass ratio of 1:1 into a distilled water solvent3N4After being dispersed uniformly, the solution is poured into a hydrothermal reaction kettle for hydrothermal reaction for 2 hours at the temperature of 130 ℃, and the solvent is filtered and dried to obtain the functional attapulgite supported NiO-g-C3N4The photocatalyst-adsorbent of (1).
Adding 25mg of methyl orange into 500mL of distilled water, stirring and dissolving, and adding 500mg of functional attapulgite loaded NiO-g-C3N4The photocatalytic adsorbent is irradiated for 3 hours under a 200W xenon lamp, the upper layer liquid is taken, the concentration of methyl orange is tested by a 754N ultraviolet-visible spectrophotometer, and the degradation rate is calculated.
Adding 25mg of methyl orange into 500mL of distilled water, stirring and dissolving, and adding 500mg of functional attapulgite loaded NiO-g-C3N4Stirring and adsorbing the photocatalyst-adsorbent for 3h in the dark, and taking the upper layerAnd (3) testing the concentration of methyl orange by using an 754N ultraviolet-visible spectrophotometer, calculating the adsorption rate, then irradiating the solution for 3 hours under a 200W xenon lamp, detecting the concentration of the methyl orange, and calculating the adsorption-degradation rate.