CN114260006A - Nano titanium dioxide photocatalyst and preparation method thereof - Google Patents
Nano titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nanometer titanium dioxide photocatalyst and a preparation method thereof; the method comprises the following steps: s1: uniformly mixing beta-cyclodextrin and a sodium hydroxide solution, and adding chloroacetic acid to obtain modified cyclodextrin; s2: mixing the modified cyclodextrin with the nano titanium dioxide, adjusting the pH value of the system by using a phosphate solution, and adding cyanamide to obtain modified titanium dioxide; s3: uniformly mixing concentrated sulfuric acid potassium permanganate, adding water and hydrogen peroxide, and uniformly mixing to obtain graphene oxide; s4: compounding graphene oxide and modified titanium dioxide to obtain a modified photocatalyst; s5: the modified photocatalyst is soaked in a hydrogen iodide solution to obtain the nano titanium dioxide photocatalyst, and the nano titanium dioxide photocatalyst prepared by the process has good photocatalytic performance and adsorbability, is high in stability, avoids the aggregation of nano titanium dioxide, and is simple in process, green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a nano titanium dioxide photocatalyst and a preparation method thereof.
Background
With the development of the 21 st century industrialization, more and more waste gases and waste liquids are put into the environment, which has great influence on the environment and human body, and the demand for energy is increasing, so that the energy crisis is approaching continuously, and therefore, abundant and cheap new energy is urgently needed to solve the problem of environmental pollution.
Titanium dioxide has high photocatalytic activity, stable property and small influence on environment and human bodies, can oxidize most pollutants, and is widely applied to photocatalytic materials.
Disclosure of Invention
The present invention aims at providing a nanometer titania photocatalyst and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
comprises the following steps
S1: uniformly mixing beta-cyclodextrin and a sodium hydroxide solution, adding chloroacetic acid, adjusting the pH of the solution by fuming hydrochloric acid, standing, cooling, adding methanol, extracting, centrifuging and drying to obtain modified cyclodextrin;
s2: mixing the modified cyclodextrin with the nano titanium dioxide, adjusting the pH value of a system by using a phosphate solution, adding cyanamide, standing, cooling, centrifuging, washing and drying to obtain modified titanium dioxide;
s3: uniformly mixing concentrated sulfuric acid potassium permanganate, heating, adding water and hydrogen peroxide, uniformly mixing, washing, adjusting the pH value of the solution, adding water, and performing ultrasonic treatment, centrifugation and freeze drying to obtain graphene oxide;
s4: compounding graphene oxide and modified titanium dioxide to obtain a modified photocatalyst;
s5: soaking the modified photocatalyst in hydrogen iodide solution to obtain the nanometer titania photocatalyst.
Further, the method comprises the following steps:
s1: dissolving beta-cyclodextrin in water, carrying out ultrasonic reaction for 5-10min, adding a sodium hydroxide solution, mixing uniformly, adding chloroacetic acid, mixing uniformly, adjusting the pH value of the solution to 3-4 by using fuming hydrochloric acid, reacting for 3-4h at 60-70 ℃, standing, cooling, adding methanol, mixing uniformly, extracting the solution by using acetone, centrifuging for 5-10min, and drying to obtain modified cyclodextrin;
s2: dissolving modified cyclodextrin in water, adding nano titanium dioxide, adjusting pH value of the system to 6-7 by using phosphate solution, adding cyanamide, reacting for 10-20min, reacting for 6-8h at 90-100 ℃, standing, cooling, centrifuging for 10-20min, washing the solution with water, repeating for 3-5 times, and drying for 12-24h to obtain modified titanium dioxide;
s3: carrying out ice-bath on concentrated sulfuric acid for 15min, controlling the temperature of a system, adding graphite powder, uniformly mixing, reacting for 0.5-1h, adding potassium permanganate, heating to 35-50 ℃, stirring for reacting for 12-14h, slowly adding water, reacting for 2h at 35 ℃, adding hydrogen peroxide, reacting for 15min, filtering while hot, centrifuging, washing with water and hydrochloric acid solution until the pH value is 7, adding water, uniformly mixing, carrying out ultrasonic reaction for 15-30min, centrifuging for 5-10min, and freeze-drying to obtain graphene oxide;
s4: uniformly mixing the modified titanium dioxide with ethanol, glacial acetic acid and water to obtain a solution A, and uniformly mixing the metal ion aqueous solution with the ethanol to obtain a solution B;
s5: adding graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, carrying out ultrasonic reaction for 12-15h, centrifuging for 5-10min, and carrying out freeze drying to obtain a modified photocatalyst;
s6: adding the modified photocatalyst into a hydrogen iodide solution, reacting for 2-4h at the temperature of 100-110 ℃, standing, cooling, centrifuging for 5-10min, washing with water, and drying to obtain the nano titanium dioxide photocatalyst.
Further, the potassium permanganate should be added in portions over 1 h.
Further, the modified photocatalyst has a pH of 7.
Further, the metal ions are one or more of sodium, iron, potassium, silver, calcium, aluminum, zinc, manganese, copper, lanthanum, magnesium, lithium, cobalt, nickel and gold.
Further, the system temperature in the step S3 does not exceed 5 ℃.
Further, the materials required by the modified cyclodextrin comprise, by weight: 1-6 parts of beta-cyclodextrin, 5-10 parts of water, 20-25 parts of sodium hydroxide, 4-10 parts of chloroacetic acid, 0.1-0.5 part of fuming hydrochloric acid, 50-60 parts of methanol and 110 parts of acetone.
Further, the materials required for the modified titanium dioxide include, by weight: 2-10 parts of modified cyclodextrin, 50-60 parts of water, 1-5 parts of nano titanium dioxide, 0.1-0.5 part of phosphate and 2-10 parts of cyanamide.
Further, the graphene oxide required materials comprise, by weight: 60-70 parts of concentrated sulfuric acid, 1-5 parts of graphite powder, 6-12 parts of potassium permanganate, 300 parts of water 200-containing materials and 20-30 parts of hydrogen peroxide.
Further, the materials required by the modified photocatalyst comprise, by weight: 15-20 parts of modified titanium dioxide, 200 parts of ethanol 140-.
Further, the materials required by the nano titanium dioxide photocatalyst comprise, by weight: 0.1-0.5 part of modified photocatalyst and 10-20 parts of hydrogen iodide.
Further, the nano titanium dioxide photocatalyst is prepared by the preparation method of the nano titanium dioxide photocatalyst.
Compared with the prior art, the invention has the following beneficial effects: (1) the beta-cyclodextrin modified by carboxymethyl is compounded with the nano titanium dioxide, the modified cyclodextrin can be fixed on the surface of the nano titanium dioxide to promote the interface bonding capability of a photocatalyst and a substance, along with the increase of the amount of the modified cyclodextrin, the chemical bond provided by the modified cyclodextrin enhances the conveying efficiency of the surface charge of the nano titanium dioxide, and further improves the catalytic performance of the photocatalyst, but the amount of the modified cyclodextrin is not too much, so that the modified cyclodextrin covers active sites on the surface of the nano titanium dioxide to reduce the catalytic performance, and meanwhile, the modified cyclodextrin provides stable glucopyranose units, thereby improving the stability of the photocatalyst.
(2) In the process of preparing the graphene oxide, the high manganese acid agent is added in batches for the purpose of improving the oxidability of graphite and reducing the introduction of impurities in subsequent loading, the graphene oxide is used as a carrier of the nano titanium dioxide, the two-dimensional structure in the graphene oxide can be converted to a three-dimensional structure, so that the inside of the graphene oxide can be folded, the nano titanium dioxide is stably loaded on the folds, meanwhile, a chemical bond Ti-O-C can be formed, the utilization efficiency of a catalyst to light is enhanced, the recombination of electron and hole pairs in the nano titanium dioxide can be inhibited by the graphene oxide, therefore, the utilization rate of light energy is improved, a large number of oxygen-containing groups are introduced into the graphene oxide in the process of preparing the graphene oxide, the distance in the graphene oxide is enlarged, the hydrophilicity of the photocatalyst is enhanced, the centrifugal step is adopted, and the nano titanium dioxide particles which are not successfully loaded are removed, to improve the adsorption performance of the photocatalyst.
(3) The nanometer titanium dioxide is doped with the metal ion aqueous solution, so that the adsorbability of the photocatalyst is enhanced, the metal ions can slow down the distortion of the crystal form of the nanometer titanium dioxide, the separation of electron-hole pairs on the surface of the nanometer titanium dioxide is improved, the spectrum absorption range of the photocatalyst is expanded, the concentration of an oxidizing group is improved, and the absorption of the photocatalyst on visible light and ultraviolet light is enhanced.
(4) The prepared photocatalysis is added into hydroiodic acid, iodide ions can be attached to the surface of the graphene oxide, the loading effect of the graphene oxide on the nano titanium dioxide and the crystal form of the nano titanium dioxide cannot be damaged, the band gap width of the nano titanium dioxide is reduced, the hydroiodic acid is favorable for enhancing the reduction reaction in the graphene oxide, the separation of electron-hole pairs on the surface of the nano titanium dioxide is further enhanced, and simultaneously the SP of the graphene oxide is enabled to be in a SP state2The hybridization area is enlarged, the transmission efficiency of electrons on the surface of the graphene oxide is improved, and the addition of iodide ions enables the graphite oxide to be oxidizedThe absorption of the visible light by the alkene-loaded nano titanium dioxide is enhanced, and meanwhile, the alkene-loaded nano titanium dioxide is conjugated with a pi-pi structure in the graphene oxide, so that the photocatalytic performance is improved, the stability of the photocatalyst is enhanced by adding the modified cyclodextrin, and iodine ions are prevented from being separated from the surface of the graphene oxide.
(5) The nano titanium dioxide photocatalyst prepared by the invention has good photocatalytic performance and adsorptivity and strong stability, avoids the aggregation of nano titanium dioxide, and has simple process and environmental protection.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: the method comprises the following steps:
s1: dissolving 1 part of beta-cyclodextrin in 5 parts of water, carrying out ultrasonic reaction for 5min, adding 20 parts of 7mol/L sodium hydroxide solution, uniformly mixing, adding 4 parts of chloroacetic acid, uniformly mixing, adjusting the pH value of the solution to 3 by using 0.1 part of fuming hydrochloric acid, reacting for 3h at 60 ℃, standing, cooling, adding 50 parts of methanol, uniformly mixing, extracting the solution by using 100 parts of acetone, centrifuging for 5-10min, and drying to obtain modified cyclodextrin;
s2: dissolving 2 parts of modified cyclodextrin in 50 parts of water, adding 1 part of nano titanium dioxide, adjusting the pH value of a system to be 6 by using 0.1 part of phosphate solution with the pH value of 6, adding 2 parts of cyanamide, reacting for 10min, reacting for 6-8h at 90 ℃, standing, cooling, centrifuging for 10min, washing the solution with water, repeating for 3 times, and drying for 12h to obtain the modified titanium dioxide;
s3: carrying out ice bath on 60 parts of concentrated sulfuric acid for 15min, controlling the temperature of the system to be not more than 5 ℃, adding 1 part of graphite powder, uniformly mixing, reacting for 0.5h, adding 6 parts of potassium permanganate in 1h in batches, heating to 35 ℃, stirring and reacting for 12h, slowly adding 100 parts of water, reacting for 2h at 35 ℃, adding 20 parts of hydrogen peroxide, reacting for 15min, filtering while hot, centrifuging, washing with water and a hydrochloric acid solution until the pH value is 7, adding 100 parts of water, uniformly mixing, carrying out ultrasonic reaction for 15min, centrifuging for 5min, and freeze-drying to obtain graphene oxide;
s4: uniformly mixing 15 parts of modified titanium dioxide, 70 parts of ethanol, 3 parts of glacial acetic acid and 100 parts of water to obtain a solution A, and uniformly mixing 5 parts of silver ion aqueous solution and 70 parts of ethanol to obtain a solution B;
s5: adding 15 parts of graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, adjusting the pH value of the solution to 7, carrying out ultrasonic reaction for 12 hours, centrifuging for 5min, and freeze-drying to obtain the modified photocatalyst;
s6: adding 0.1 part of modified photocatalyst into 10 parts of 55% hydrogen iodide solution, reacting for 2-4h at the temperature of 100-.
Example 2: the method comprises the following steps:
s1: dissolving 2 parts of beta-cyclodextrin in 6 parts of water, carrying out ultrasonic reaction for 6min, adding 21 parts of 7mol/L sodium hydroxide solution, uniformly mixing, adding 5 parts of chloroacetic acid, uniformly mixing, adjusting the pH value of the solution to 3.1 by using 0.2 part of fuming hydrochloric acid, reacting for 3-4h at 61 ℃, standing, cooling, adding 51 parts of methanol, uniformly mixing, extracting the solution by using 101 parts of acetone, centrifuging for 6min, and drying to obtain modified cyclodextrin;
s2: dissolving 3 parts of modified cyclodextrin in 51 parts of water, adding 2 parts of nano titanium dioxide, adjusting the pH value of a system to be 6.1 by using 0.2 part of phosphate solution with the pH value of 6, adding 3 parts of cyanamide, reacting for 11min, reacting for 6.2h at 91 ℃, standing, cooling, centrifuging for 11min, washing the solution with water, repeating for 4 times, and drying for 13h to obtain the modified titanium dioxide;
s3: carrying out ice bath on 61 parts of concentrated sulfuric acid for 15min, controlling the temperature of the system to be not more than 5 ℃, adding 2 parts of graphite powder, uniformly mixing, reacting for 0.6h, adding 7 parts of potassium permanganate in 1h in batches, heating to 38 ℃, stirring, reacting for 12.5h, slowly adding 110 parts of water, reacting for 2h at 35 ℃, adding 21 parts of hydrogen peroxide, reacting for 15min, filtering while hot, centrifuging, washing with water and a hydrochloric acid solution until the pH value is 7, adding 110 parts of water, uniformly mixing, carrying out ultrasonic reaction for 18min, centrifuging for 6min, and freeze-drying to obtain graphene oxide;
s4: uniformly mixing 16 parts of modified titanium dioxide, 80 parts of ethanol, 4 parts of glacial acetic acid and 105 parts of water to obtain a solution A, and uniformly mixing 6 parts of silver ion aqueous solution and 80 parts of ethanol to obtain a solution B;
s5: adding 16 parts of graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, adjusting the pH value of the solution to 7, carrying out ultrasonic reaction for 12.5h, centrifuging for 6min, and carrying out freeze drying to obtain the modified photocatalyst;
s6: adding 0.2 part of modified photocatalyst into 11 parts of 55% hydrogen iodide solution, reacting for 2.2h at 101 ℃, standing and cooling, centrifuging for 6min, washing with water, and drying to obtain the nano titanium dioxide photocatalyst.
Example 3: the method comprises the following steps:
s1: dissolving 3 parts of beta-cyclodextrin in 7 parts of water, carrying out ultrasonic reaction for 7min, adding 22 parts of 7mol/L sodium hydroxide solution, uniformly mixing, adding 6 parts of chloroacetic acid, uniformly mixing, adjusting the pH value of the solution to 3.3 by using 0.3 part of fuming hydrochloric acid, reacting at 63 ℃ for 3.4h, standing, cooling, adding 52 parts of methanol, uniformly mixing, extracting the solution by using 103 parts of acetone, centrifuging for 7min, and drying to obtain modified cyclodextrin;
s2: dissolving 4 parts of modified cyclodextrin in 53 parts of water, adding 3 parts of nano titanium dioxide, adjusting the pH value of a system to be 6-7 by using 0.3 part of phosphate solution with the pH value of 6, adding 4 parts of cyanamide, reacting for 13min, reacting for 6.4h at 93 ℃, standing, cooling, centrifuging for 13min, washing the solution with water, repeating for 4 times, and drying for 15h to obtain the modified titanium dioxide;
s3: carrying out ice bath on 63 parts of concentrated sulfuric acid for 15min, controlling the temperature of the system to be not more than 5 ℃, adding 3 parts of graphite powder, uniformly mixing, reacting for 0.5-1h, adding 8 parts of potassium permanganate in 1h in batches, heating to 40 ℃, stirring, reacting for 12.5h, slowly adding 120 parts of water, reacting for 2h at 35 ℃, adding 22 parts of hydrogen peroxide, reacting for 15min, filtering while hot, centrifuging, washing with water and a hydrochloric acid solution until the pH value is 7, adding 120 parts of water, uniformly mixing, carrying out ultrasonic reaction for 20min, centrifuging for 7min, and freeze-drying to obtain graphene oxide;
s4: uniformly mixing 17 parts of modified titanium dioxide, 85 parts of ethanol, 5 parts of glacial acetic acid and 106 parts of water to obtain a solution A, and uniformly mixing 7 parts of silver ion aqueous solution and 85 parts of ethanol to obtain a solution B;
s5: adding 17 parts of graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, adjusting the pH value of the solution to 7, carrying out ultrasonic reaction for 13 hours, centrifuging for 7min, and carrying out freeze drying to obtain the modified photocatalyst;
s6: adding 0.3 part of modified photocatalyst into 12 parts of 55% hydrogen iodide solution, reacting for 2.5h at 105 ℃, standing and cooling, centrifuging for 7min, washing with water, and drying to obtain the nano titanium dioxide photocatalyst.
Example 4: the method comprises the following steps:
s1: dissolving 4 parts of beta-cyclodextrin in 8 parts of water, carrying out ultrasonic reaction for 8min, adding 23 parts of 7mol/L sodium hydroxide solution, uniformly mixing, adding 7 parts of chloroacetic acid, uniformly mixing, adjusting the pH value of the solution to 3.8 by using 0.4 part of fuming hydrochloric acid, reacting for 3.8h at 67 ℃, standing, cooling, adding 55 parts of methanol, uniformly mixing, extracting the solution by using 106 parts of acetone, centrifuging for 8min, and drying to obtain modified cyclodextrin;
s2: dissolving 5 parts of modified cyclodextrin in 55 parts of water, adding 4 parts of nano titanium dioxide, adjusting the pH value of a system to be 6.8 by using 0.4 part of phosphate solution with the pH value of 6, adding 5 parts of cyanamide, reacting for 18min, reacting for 7.5h at 98 ℃, standing, cooling, centrifuging for 16min, washing the solution with water, repeating for 5 times, and drying for 18h to obtain the modified titanium dioxide;
s3: carrying out ice bath on 65 parts of concentrated sulfuric acid for 15min, controlling the temperature of the system to be not more than 5 ℃, adding 4 parts of graphite powder, uniformly mixing, reacting for 0.5-1h, adding 10 parts of potassium permanganate in 1h in batches, heating to 45 ℃, stirring and reacting for 13h, slowly adding 130 parts of water, reacting for 2h at 35 ℃, adding 25 parts of hydrogen peroxide, reacting for 15min, filtering while hot, centrifuging, washing with water and a hydrochloric acid solution until the pH value is 7, adding 130 parts of water, uniformly mixing, carrying out ultrasonic reaction for 24min, centrifuging for 8min, and carrying out freeze drying to obtain graphene oxide;
s4: uniformly mixing 1618 parts of modified titanium dioxide, 90 parts of ethanol, 6 parts of glacial acetic acid and 230 parts of water to obtain a solution A, and uniformly mixing 8 parts of silver ion aqueous solution and 90 parts of ethanol to obtain a solution B;
s5: adding 18 parts of graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, adjusting the pH value of the solution to 7, carrying out ultrasonic reaction for 14 hours, centrifuging for 8min, and carrying out freeze drying to obtain the modified photocatalyst;
s6: adding 0.4 part of modified photocatalyst into 18 parts of 55% hydrogen iodide solution, reacting for 3.5h at 108 ℃, standing and cooling, centrifuging for 8min, washing with water, and drying to obtain the nano titanium dioxide photocatalyst.
Example 5: the method comprises the following steps:
s1: dissolving 5 parts of beta-cyclodextrin in 9 parts of water, carrying out ultrasonic reaction for 9min, adding 24 parts of 7mol/L sodium hydroxide solution, uniformly mixing, adding 9 parts of chloroacetic acid, uniformly mixing, adjusting the pH value of the solution to 3.9 by using 0.5 part of fuming hydrochloric acid, reacting for 3.9h at 68 ℃, standing, cooling, adding 58 parts of methanol, uniformly mixing, extracting the solution by using 108 parts of acetone, centrifuging for 9min, and drying to obtain modified cyclodextrin;
s2: dissolving 9 parts of modified cyclodextrin in 59 parts of water, adding 4.5 parts of nano titanium dioxide, adjusting the pH value of a system to be 6.9 by using 0.4 part of phosphate solution with the pH value of 6, adding 9 parts of cyanamide, reacting for 19min, reacting for 6.8h at 98 ℃, standing, cooling, centrifuging for 18min, washing the solution with water, repeating for 4 times, and drying for 22h to obtain the modified titanium dioxide;
s3: carrying out ice bath on 69 parts of concentrated sulfuric acid for 15min, controlling the temperature of the system to be not more than 5 ℃, adding 4.5 parts of graphite powder, uniformly mixing, reacting for 0.9h, adding 11 parts of potassium permanganate in 1h in batches, heating to 48 ℃, stirring, reacting for 13.5h, slowly adding 140 parts of water, reacting for 2h at 35 ℃, adding 29 parts of hydrogen peroxide, reacting for 15min, filtering while hot, centrifuging, washing with water and a hydrochloric acid solution until the pH value is 7, adding 140 parts of water, uniformly mixing, carrying out ultrasonic reaction for 28min, centrifuging for 9min, and freeze-drying to obtain graphene oxide;
s4: uniformly mixing 19 parts of modified titanium dioxide, 95 parts of ethanol, 7 parts of glacial acetic acid and 118 parts of water to obtain a solution A, and uniformly mixing 9 parts of silver ion aqueous solution and 95 parts of ethanol to obtain a solution B;
s5: adding 19 parts of graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, adjusting the pH value of the solution to 7, carrying out ultrasonic reaction for 14.5h, centrifuging for 9min, and carrying out freeze drying to obtain the modified photocatalyst;
s6: adding 0.5 part of modified photocatalyst into 19 parts of 55% hydrogen iodide solution, reacting for 3.9h at 109 ℃, standing and cooling, centrifuging for 9min, washing with water, and drying to obtain the nano titanium dioxide photocatalyst.
Example 6: the method comprises the following steps:
s1: dissolving 6 parts of beta-cyclodextrin in 10 parts of water, carrying out ultrasonic reaction for 10min, adding 25 parts of 7mol/L sodium hydroxide solution, uniformly mixing, adding 10 parts of chloroacetic acid, uniformly mixing, adjusting the pH value of the solution to 4 by using 0.5 part of fuming hydrochloric acid, reacting for 4h at 70 ℃, standing, cooling, adding 60 parts of methanol, uniformly mixing, extracting the solution by using 110 parts of acetone, centrifuging for 10min, and drying to obtain modified cyclodextrin;
s2: dissolving 10 parts of modified cyclodextrin in 60 parts of water, adding 5 parts of nano titanium dioxide, adjusting the pH value of a system to 7 by using 0.5 part of phosphate solution with the pH value of 6, adding 10 parts of cyanamide, reacting for 20min, reacting for 6-8h at 100 ℃, standing, cooling, centrifuging for 20min, washing the solution with water, repeating for 5 times, and drying for 24h to obtain the modified titanium dioxide;
s3: carrying out ice bath on 70 parts of concentrated sulfuric acid for 15min, controlling the temperature of the system to be not more than 5 ℃, adding 5 parts of graphite powder, uniformly mixing, reacting for 1h, adding 12 parts of potassium permanganate in 1h in batches, heating to 50 ℃, stirring and reacting for 14h, slowly adding 150 parts of water, reacting for 2h at 35 ℃, adding 30 parts of hydrogen peroxide, reacting for 15min, filtering while hot, centrifuging, washing with water and a hydrochloric acid solution until the pH value is 7, adding 150 parts of water, uniformly mixing, carrying out ultrasonic reaction for 30min, centrifuging for 10min, and freeze-drying to obtain graphene oxide;
s4: uniformly mixing 20 parts of modified titanium dioxide, 100 parts of ethanol, 8 parts of glacial acetic acid and 120 parts of water to obtain a solution A, and uniformly mixing 10 parts of silver ion aqueous solution and 100 parts of ethanol to obtain a solution B;
s5: adding 20 parts of graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, adjusting the pH value of the solution to 7, carrying out ultrasonic reaction for 15 hours, centrifuging for 10min, and freeze-drying to obtain the modified photocatalyst;
s6: and adding 0.5 part of modified photocatalyst into 20 parts of 55% hydrogen iodide solution, reacting for 4 hours at 110 ℃, standing, cooling, centrifuging for 10min, washing with water, and drying to obtain the nano titanium dioxide photocatalyst.
Comparative example
Comparative example 1: in comparison with example 3, the process, without the addition of modified cyclodextrin, comprises the following steps:
s1: uniformly mixing 17 parts of nano titanium dioxide, 85 parts of ethanol, 5 parts of glacial acetic acid and 106 parts of water to obtain a solution A, and uniformly mixing 7 parts of silver ion aqueous solution and 85 parts of ethanol to obtain a solution B;
s2: adding 17 parts of graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, adjusting the pH value of the solution to 7, carrying out ultrasonic reaction for 13 hours, centrifuging for 7min, and carrying out freeze drying to obtain the modified photocatalyst;
s3: adding 0.3 part of modified photocatalyst into 12 parts of 55% hydrogen iodide solution, reacting for 2.5h at 105 ℃, standing and cooling, centrifuging for 7min, washing with water, and drying to obtain the nano titanium dioxide photocatalyst.
Comparative example 2: in contrast to example 3, the modified photocatalyst was not subjected to the iodohydric acid treatment, comprising the steps of:
s1: uniformly mixing 17 parts of modified titanium dioxide, 85 parts of ethanol, 5 parts of glacial acetic acid and 106 parts of water to obtain a solution A, and uniformly mixing 7 parts of silver ion aqueous solution and 85 parts of ethanol to obtain a solution B;
s2: and adding 17 parts of graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, adjusting the pH value of the solution to 7, carrying out ultrasonic reaction for 13 hours, centrifuging for 7min, and freeze-drying to obtain the nano titanium dioxide photocatalyst.
Experimental data
Degradation rate of methylene blue: placing the nano titanium dioxide photocatalyst in 0.01g/L methylene blue solution, reacting for 1h in a dark place, illuminating for 1h by using a xenon lamp, sampling, centrifuging, measuring the absorbance of the solution at 664nm, and calculating the degradation rate.
Degradation rate of rhodamine B: and (3) placing the nano titanium dioxide photocatalyst in 20mg/L rhodamine B solution, reacting for 1h in a dark place, irradiating for 4h by using an ultraviolet lamp, measuring the absorbance of the solution at 554nm, and calculating the degradation rate.
The stability of the photocatalyst is as follows: the nano titanium dioxide photocatalyst is used for carrying out continuous 5 degradation experiments on rhodamine B.
And (4) conclusion: the nano titanium dioxide photocatalyst prepared by the application has good photocatalytic performance and adsorptivity, is strong in stability, avoids the condition that nano titanium dioxide gathers, and is simple in process and green.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a nanometer titanium dioxide photocatalyst is characterized by comprising the following steps: comprises the following steps
S1: uniformly mixing beta-cyclodextrin and a sodium hydroxide solution, adding chloroacetic acid, adjusting the pH of the solution by fuming hydrochloric acid, standing, cooling, adding methanol, extracting, centrifuging and drying to obtain modified cyclodextrin;
s2: mixing the modified cyclodextrin with the nano titanium dioxide, adjusting the pH value of a system by using a phosphate solution, adding cyanamide, standing, cooling, centrifuging, washing and drying to obtain modified titanium dioxide;
s3: uniformly mixing concentrated sulfuric acid potassium permanganate, heating, adding water and hydrogen peroxide, uniformly mixing, washing, adjusting the pH value of the solution, adding water, and performing ultrasonic treatment, centrifugation and freeze drying to obtain graphene oxide;
s4: compounding graphene oxide and modified titanium dioxide to obtain a modified photocatalyst;
s5: soaking the modified photocatalyst in hydrogen iodide solution to obtain the nanometer titania photocatalyst.
2. The method for preparing a nano titanium dioxide photocatalyst according to claim 1, characterized in that: the method comprises the following steps:
s1: dissolving beta-cyclodextrin in water, carrying out ultrasonic reaction for 5-10min, adding a sodium hydroxide solution, mixing uniformly, adding chloroacetic acid, mixing uniformly, adjusting the pH value of the solution to 3-4 by using fuming hydrochloric acid, reacting for 3-4h at 60-70 ℃, standing, cooling, adding methanol, mixing uniformly, extracting the solution by using acetone, centrifuging for 5-10min, and drying to obtain modified cyclodextrin;
s2: dissolving modified cyclodextrin in water, adding nano titanium dioxide, adjusting pH value of the system to 6-7 by using phosphate solution, adding cyanamide, reacting for 10-20min, reacting for 6-8h at 90-100 ℃, standing, cooling, centrifuging for 10-20min, washing the solution with water, repeating for 3-5 times, and drying for 12-24h to obtain modified titanium dioxide;
s3: carrying out ice-bath on concentrated sulfuric acid for 15min, controlling the temperature of a system, adding graphite powder, uniformly mixing, reacting for 0.5-1h, adding potassium permanganate, heating to 35-50 ℃, stirring for reacting for 12-14h, slowly adding water, reacting for 2h at 35 ℃, adding hydrogen peroxide, reacting for 15min, filtering while hot, centrifuging, washing with water and hydrochloric acid solution until the pH value is 7, adding water, uniformly mixing, carrying out ultrasonic reaction for 15-30min, centrifuging for 5-10min, and freeze-drying to obtain graphene oxide;
s4: uniformly mixing the modified titanium dioxide with ethanol, glacial acetic acid and water to obtain a solution A, and uniformly mixing the metal ion aqueous solution with the ethanol to obtain a solution B;
s5: adding graphene oxide into the solution A, uniformly mixing, slowly dropwise adding the solution B, carrying out ultrasonic reaction for 12-15h, centrifuging for 5-10min, and carrying out freeze drying to obtain a modified photocatalyst;
s6: adding the modified photocatalyst into a hydrogen iodide solution, reacting for 2-4h at the temperature of 100-110 ℃, standing, cooling, centrifuging for 5-10min, washing with water, and drying to obtain the nano titanium dioxide photocatalyst.
3. The method for preparing a nano titanium dioxide photocatalyst according to claim 1, characterized in that: the potassium permanganate should be added in portions over 1 h.
4. The method for preparing a nano titanium dioxide photocatalyst according to claim 1, characterized in that: the modified photocatalyst has a pH value of 7.
5. The method for preparing a nano titanium dioxide photocatalyst according to claim 1, characterized in that: the materials required by the modified cyclodextrin comprise, by weight: 1-6 parts of beta-cyclodextrin, 5-10 parts of water, 20-25 parts of sodium hydroxide, 4-10 parts of chloroacetic acid, 0.1-0.5 part of fuming hydrochloric acid, 50-60 parts of methanol and 110 parts of acetone.
6. The method for preparing a nano titanium dioxide photocatalyst according to claim 1, characterized in that: the materials required by the modified titanium dioxide comprise, by weight: 2-10 parts of modified cyclodextrin, 50-60 parts of water, 1-5 parts of nano titanium dioxide, 0.1-0.5 part of phosphate and 2-10 parts of cyanamide.
7. The method for preparing a nano titanium dioxide photocatalyst according to claim 1, characterized in that: the materials required by the modified photocatalyst comprise, by weight: 15-20 parts of modified titanium dioxide, 200 parts of ethanol 140-.
8. The method for preparing a nano titanium dioxide photocatalyst according to claim 2, characterized in that: the metal ions are one or more of sodium, iron, potassium, silver, calcium, aluminum, zinc, manganese, copper, lanthanum, magnesium, lithium, cobalt, nickel and gold.
9. The method for preparing a nano titanium dioxide photocatalyst according to claim 2, characterized in that: the system temperature in the step S3 does not exceed 5 ℃.
10. The nano titanium dioxide photocatalyst prepared by the preparation method of the nano titanium dioxide photocatalyst according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114735944A (en) * | 2022-06-10 | 2022-07-12 | 南通广欣玻璃有限公司 | Optical glass coated with nano material on surface and preparation method thereof |
| CN115340992A (en) * | 2022-08-01 | 2022-11-15 | 河北工业大学 | Immobilized carrier and preparation method thereof, photocatalyst, preparation method and application thereof, and synthesis method of chiral alcohol |
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2021
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114735944A (en) * | 2022-06-10 | 2022-07-12 | 南通广欣玻璃有限公司 | Optical glass coated with nano material on surface and preparation method thereof |
| CN115340992A (en) * | 2022-08-01 | 2022-11-15 | 河北工业大学 | Immobilized carrier and preparation method thereof, photocatalyst, preparation method and application thereof, and synthesis method of chiral alcohol |
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