CN114671407A - Method for producing hydrogen peroxide based on quantum dot photocatalysis of cadmium-based colloid and application - Google Patents

Method for producing hydrogen peroxide based on quantum dot photocatalysis of cadmium-based colloid and application Download PDF

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CN114671407A
CN114671407A CN202210259229.1A CN202210259229A CN114671407A CN 114671407 A CN114671407 A CN 114671407A CN 202210259229 A CN202210259229 A CN 202210259229A CN 114671407 A CN114671407 A CN 114671407A
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李洋
侯小琪
戴宁
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Hangzhou Institute of Advanced Studies of UCAS
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Abstract

The invention discloses a method for producing hydrogen peroxide based on cadmium-based colloid quantum dot photocatalysis and application thereof, wherein the preparation method of a quantum dot catalyst comprises the following steps: the cadmium selenide quantum dots are synthesized by a thermal injection method, and are coated with cadmium sulfide and zinc sulfide shells after purification. The quantum dot catalyst prepared by the invention is applied to photocatalytic hydrogen peroxide production for the first time, and detection shows that the quantum dot catalyst has excellent photocatalytic hydrogen peroxide production performance, the yield of hydrogen peroxide in 2 hours is up to 126mmol/L, and the quantum dot catalyst has extremely high application prospect in photocatalytic hydrogen peroxide production.

Description

Method for producing hydrogen peroxide based on quantum dot photocatalysis of cadmium-based colloid and application
Technical Field
The invention belongs to the technical field of material preparation and application, and particularly relates to a quantum dot photocatalytic hydrogen peroxide production method based on cadmium-based colloid and application.
Background
Hydrogen peroxide is an environment-friendly oxidant and has wide application in the fields of industry, medicine, environmental protection, war industry, food, environment and the like. At present, the most mature method for industrially producing the hydrogen peroxide on a large scale is the anthraquinone method, but the anthraquinone method not only relates to an expensive palladium catalyst, but also causes environmental pollution, so that the green and efficient new method for producing the hydrogen peroxide is urgently found.
Photocatalysis can convert solar energy resources into valuable chemicals, and the synthesis of hydrogen peroxide by using solar photocatalysis is very promising. In the last decades, great efforts have been made to achieve this goal, and a series of catalysts, such as titanium dioxide, carbon nitride, bismuth vanadate, metal organic frameworks, etc., have been studied. However, the wide band gap of the above photocatalyst causes extremely poor absorption capability of visible light, which limits further applications.
The quantum dots are semiconductor materials with quantum confinement effect, have wide and cheap preparation raw material sources, and have the advantages of adjustable band gap, good visible light absorption capacity, abundant surface reaction sites and easy surface modification. However, quantum dot catalysts having excellent photocatalytic hydrogen peroxide generation performance have not been disclosed in the prior art.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a preparation method and application of a quantum dot catalyst for photocatalytic hydrogen peroxide generation, and the preparation method is realized by the following technical scheme:
the invention discloses a method for producing hydrogen peroxide based on cadmium-based colloidal quantum dot photocatalysis.
As a further improvement, the method specifically comprises the following steps:
1) adding the quantum dot precursor into a three-neck flask;
2) exhausting the materials in the step 1) in an argon atmosphere, then heating and maintaining until the solution is clear and transparent, and then cooling and maintaining; injecting a selenium precursor such as selenium powder-octadecylene suspension into the obtained transparent solution, sampling and detecting at intervals, stopping reaction when the solution grows to a required size, cooling the obtained quantum dot solution, and purifying to obtain cadmium selenide quantum dots on the surface of the aliphatic carboxylate ligand;
3) ligand exchange is carried out on the cadmium selenide quantum dots on the surfaces of the ligands of the aliphatic carboxylic acid salts obtained after purification in the step 2) to obtain quantum dots with different surface ligands, such as aliphatic amine ligands, thiol ligands and the like;
4) and (3) carrying out cladding treatment on the cadmium selenide quantum dots on the surface of the aliphatic carboxylate ligand obtained after purification in the step 2), and obtaining the quantum dots with different shell thicknesses and structures after purification.
As a further improvement, the quantum dot precursor in step 1) is cadmium oxide or cadmium acetate or cadmium carbonate or cadmium hydroxide or cadmium nitrate; octanoic acid or decanoic acid or dodecanoic acid or tetradecanoic acid or hexadecanoic acid or stearic acid; and octadecene or squalene or squalane or octadecane or hexadecane or tetradecane or dodecane or paraffin; the amount of the cadmium precursor and the acid and the type of the acid are determined by the quantum dot catalyst to be synthesized.
As a further improvement, in the step 2), the temperature is maintained at 200-320 ℃, the temperature is maintained at the reduced temperature, and the growth time is determined by the size of the needed cadmium selenide quantum dots, wherein the size of the needed cadmium selenide quantum dots is 1-20 nm; the exchange ligand in the step 3) is octylmercaptol or dodecylmercaptol or hexadecylmercaptol or octadecylmercaptol and butylamine or octylamine or hexadecylamine or octadecylamine or oleylamine.
As a further improvement, the size of the cadmium selenide quantum dot is 1-20nm, and the exchange ligand is butylamine, octylamine, hexadecylamine, octadecylamine or oleylamine.
As a further improvement, the shell epitaxial growth in step 4) of the present invention specifically comprises:
adding the purified cadmium selenide quantum dots and butylamine, octylamine, hexadecylamine, octadecylamine, oleylamine, octadecene, squalene, squalane, octadecane, hexadecane, tetradecane, dodecane or paraffin into a three-neck flask together, exhausting for 1-20min under the atmosphere of argon or nitrogen, and injecting cadmium diethyldithiocarbamate, cadmium diethyldithiocarbamate or cadmium diethyldithiocarbamate to prepare the cadmium selenide/cadmium sulfide core-shell quantum dots with the cadmium sulfide shell thickness of 1-10 layers, wherein the cadmium sulfide shell thickness is preferably 5 layers; the cadmium sulfide shell layer with the thickness of 1-10 layers is obtained by injecting zinc diethyldithiocarbamate or zinc diethyldithiocarbamate, the quantum dots with the thickness of 1-4 layers of zinc sulfide shell layer are obtained, the thickness of the zinc sulfide shell layer is preferably 2 layers, the temperature is set to be 20-80 ℃ when the precursor is injected for the first time, then the temperature is increased to 140-220 ℃ and maintained for 5-30min, then the heating is stopped, the temperature is reduced to be 20-80 ℃, and the subsequent shell layer growth mode is the same as that of the first time. The preparation of a proper shell layer greatly improves the catalytic effect.
As a further improvement, the catalyst prepared by the method is cadmium selenide/cadmium sulfide/zinc sulfide core-shell quantum dots.
The invention also discloses application of the colloidal quantum dot catalyst in photocatalytic preparation of hydrogen peroxide, namely the quantum dot catalyst is dissolved in an oil/water two-phase system, oxygen is introduced, and hydrogen peroxide is generated under illumination.
As a further improvement, the wavelength of the xenon lamp is 300-800nm, the catalytic reaction solvent system is water, or toluene, hexane or chloroform, or a mixed system of toluene, hexane or chloroform/water, and the reaction time is 1-8 h.
As a further improvement, the wavelength of the xenon lamp is a visible light wave band of 420-800nm, a reaction system is a toluene/water two-phase system, and the reaction time is 2 h.
Compared with the prior art, the invention has the following advantages:
1) the invention discloses a preparation method and application of a quantum dot catalyst for photocatalytic hydrogen peroxide production, wherein the preparation method of the quantum dot catalyst comprises the following steps: cadmium selenide quantum dots are synthesized by a thermal injection method, and are coated with cadmium sulfide and a zinc sulfide shell after purification. The quantum dot catalyst prepared by the invention is applied to photocatalytic hydrogen peroxide production for the first time, and detection finds that the quantum dot catalyst has excellent photocatalytic hydrogen peroxide production performance, the yield of hydrogen peroxide in 2 hours is up to 126mmol/L, and the quantum dot catalyst has extremely high application prospect of photocatalytic hydrogen peroxide production.
2) According to the invention, the quantum dots not only have good stability, but also have excellent performance of generating hydrogen peroxide by photocatalysis by controlling the size, ligand, shell structure, thickness and the like of the quantum dots.
3) The invention realizes the enrichment and separation of hydrogen peroxide by constructing a toluene-water two-phase system, and the pure hydrogen peroxide solution can be obtained by disordered subsequent purification treatment. The reaction system construction of the invention is proved to have better application prospect in practical application.
Drawings
FIG. 1 is a TEM image of quantum dot catalysts prepared in examples 1 to 3, 8 and 10;
FIG. 2 is an infrared spectrum of a quantum dot catalyst prepared in examples 1, 4 and 5;
FIGS. 3 and 4 are absorption spectra before and after the reaction of the quantum dot catalysts prepared in examples 1 to 5;
FIGS. 5 to 8 are summary graphs of test data of photocatalytic hydrogen peroxide production by quantum dot catalysts prepared in examples 1 to 10;
FIGS. 9 to 11 are summary graphs of data of the photocatalytic hydrogen peroxide production test according to the embodiments 1 to 6.
Detailed Description
The invention discloses a preparation method of a quantum dot catalyst for photocatalytic hydrogen peroxide production, which synthesizes cadmium selenide quantum dots by a thermal injection method, and wraps cadmium sulfide and a zinc sulfide shell after purification, and comprises the following specific preparation steps:
1) Adding the quantum dot precursor into a three-neck flask; the precursor in the three-neck flask is cadmium oxide, myristic acid/stearic acid and octadecene, and the amount of cadmium oxide and acid and the type of acid are determined by the needed synthetic quantum dot catalyst.
2) Exhausting the materials in the step 1) in an argon atmosphere, then heating and maintaining until the solution is clear and transparent, and then cooling and maintaining; and injecting the selenium powder-octadecylene suspension into the obtained transparent solution, sampling at intervals, detecting, supplementing a certain amount of selenium powder-octadecylene suspension, and stopping reaction when the selenium powder-octadecylene suspension grows to a proper size. And cooling and purifying the obtained quantum dot solution to obtain the cadmium selenide quantum dots on the surface of the myristate/stearate ligand. The temperature is maintained at 280 ℃ by heating, the temperature is maintained by cooling, and the growth time is determined by the size of the required quantum dot, so that the cadmium selenide quantum dot with the size of 2.2nm, 3.0nm and 4.2nm can be obtained, and the preferred size of the cadmium selenide quantum dot is 3.0 nm.
3) Ligand exchange is carried out on the cadmium selenide quantum dots on the surface of the tetradecanoate ligand obtained after purification in the step 2) to obtain quantum dots with different surface ligands; the quantum dots are cadmium selenide quantum dots with the surface size of the myristic acid ligand being 3.0nm, the exchange ligands are dodecyl mercaptan and oleylamine, and the preferred quantum dot ligand is oleylamine.
4) Carrying out cladding treatment on the cadmium selenide quantum dots on the surface of the stearate ligand obtained after purification in the step 2), and obtaining quantum dots with different shell thicknesses and structures after purification; wherein the cladding treatment is a single precursor method, taking 3 x 10-7The method comprises the steps of adding mol purified cadmium selenide quantum dots with the size of 3.0nm, 3.8mL of oleylamine and 1mL of octadecene into a three-neck flask, exhausting for 10min under the atmosphere of argon, and synthesizing the cadmium selenide quantum dots with the thickness of 1-6 cadmium sulfide shells by controlling the injection amount of 0.14, 0.20, 0.27, 0.35, 0.45 and 0.55mL of 0.1M cadmium diethyldithiocarbamate, wherein the thickness of the cadmium sulfide shells is preferably 5. By controlling the amount of 0.55 and 0.67mL of 0.1M zinc diethyldithiocarbamate injected, 5 cadmium sulfide shells with thickness can be obtained, and 2 zinc sulfide layers of cadmium selenide quantum dots are wrapped outside the cadmium sulfide shells. The temperature was set at 80 ℃ for the first injection of the precursor, then increased to 160 ℃ and maintained for 20min, after which the heating was stopped by lowering the temperature to 80 ℃ and the subsequent shell growth was carried out in the same manner as for the first injection, but the temperature was maintained at 150 ℃.
The invention also discloses application of the quantum dot catalyst in photocatalytic preparation of hydrogen peroxide, wherein the wavelength of a xenon lamp is 300-800nm, and the preferable wavelength is a visible light wave band of 420-800 nm; the catalytic reaction solvent system is water, toluene/water, preferably the reaction system is a toluene/water two-phase system, the reaction time is 1-8h, preferably 2h, the used sacrificial agent is ethanol, benzyl alcohol, phenethyl alcohol, preferably the sacrificial agent is benzyl alcohol.
The technical solutions of the present invention are further described by the following embodiments with reference to the drawings of the specification, but the scope of the present invention is not limited thereto.
Example 1: preparation method of quantum dot catalyst for photocatalytic hydrogen peroxide production
(1) Weighing 0.0128g of cadmium oxide, 0.057g of tetradecanoic acid and 4mL of octadecene, and placing the mixture into a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 240 ℃ for maintaining;
(3) and (3) injecting 0.6mL of 0.1M selenium powder-octadecene suspension into the transparent solution obtained in the step (2), timing, sampling at intervals, detecting, and supplementing 0.1mL of 0.1M selenium powder-octadecene suspension for 12 min. Stopping the reaction after 20min, cooling the obtained quantum dot solution, adding 1.5mL of the quantum dot solution into a 4mL glass bottle, adding 2.5mL of acetone for precipitation, carrying out centrifugal precipitation at 7500r/min, pouring out the supernatant, adding 0.5mL of toluene for dissolution, adding 0.005mL of decacid, heating to be clear, adding 0.75mL of methanol for precipitation, repeating the steps for two times, and then adding no decacid once to obtain the quantum dot catalyst 1.
Example 2
A preparation method of a quantum dot catalyst comprises the following steps:
(1) Weighing 0.0128g of cadmium oxide, 0.057g of tetradecanoic acid and 4mL of octadecene, and placing the mixture into a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 250 ℃ for maintaining;
(3) and (3) injecting 0.7mL of 0.1M selenium powder-octadecene suspension into the transparent solution obtained in the step (2), timing, maintaining the temperature at 230 ℃, stopping the reaction after 1min, cooling the obtained quantum dot solution, adding 1.5mL of the quantum dot solution into a 4mL glass bottle, adding 2.5mL of acetone for precipitation, carrying out 7500r/min centrifugal precipitation, pouring out supernatant, adding 0.5mL of toluene for dissolution, adding 0.005mL of decanoic acid for heating to be clear, adding 0.75mL of methanol for precipitation, repeating the steps for two times, and obtaining the quantum dot catalyst 2 without adding decanoic acid in the next step.
Example 3
A preparation method of a quantum dot catalyst comprises the following steps:
(1) 0.0256g of cadmium oxide, 0.1026g of myristic acid and 4mL of octadecene are weighed and placed in a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 250 ℃ for maintaining;
(3) and (3) injecting 1mL of 0.05M selenium powder-octadecene suspension into the transparent solution obtained in the step (2), timing, maintaining the temperature at 240 ℃, and injecting 0.05M selenium powder-octadecene/oleic acid (2: 1) suspension into the reaction solution at the speed of 0.01mL/min after the growth is carried out for about 5 min. The injection is repeated every 2-3min, and the reaction is stopped about 15 min. And cooling the obtained quantum dot solution, adding 1.5mL of the quantum dot solution into a 4mL glass bottle, adding 2.5mL of acetone for precipitation, centrifuging at 7500r/min for precipitation, pouring out supernatant, adding 0.5mL of toluene for dissolution, adding 0.005mL of decanoic acid, heating to be clear, adding 0.75mL of methanol for precipitation, repeating the steps for two times, and then obtaining the quantum dot catalyst 3 without adding decanoic acid.
Example 4
A preparation method of a quantum dot catalyst comprises the following steps:
(1) weighing 0.0128g of cadmium oxide, 0.057g of tetradecanoic acid and 4mL of octadecene, and placing the mixture into a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 240 ℃ for maintaining;
(3) and (3) injecting 0.6mL of 0.1M selenium powder-octadecene suspension into the transparent solution obtained in the step (2), timing, sampling at intervals, detecting, and supplementing 0.1mL of 0.1M selenium powder-octadecene suspension for 12 min. Stopping the reaction after 20min, cooling the obtained quantum dot solution, adding 1.5mL of the quantum dot solution into a 4mL glass bottle, adding 2.5mL of acetone for precipitation, carrying out centrifugal precipitation at 7500r/min, pouring out the supernatant, adding 0.5mL of toluene for dissolution, adding 0.005mL of decacid, heating to be clear, adding 0.75mL of methanol for precipitation, repeating the steps for two times, and then adding no decacid.
(4) Dissolving the obtained quantum dot precipitate in 0.3mL of hexane, introducing argon to remove air, injecting 0.3mL of dodecanethiol, stirring at 50 ℃ for 4 hours, adding acetone into the obtained quantum dot solution, and precipitating twice to obtain the quantum dot catalyst 4.
Example 5
A preparation method of a quantum dot catalyst comprises the following steps:
(1) Weighing 0.0128g of cadmium oxide, 0.057g of tetradecanoic acid and 4mL of octadecene, and placing the mixture into a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 240 ℃ for maintaining;
(3) and (3) injecting 0.6mL of 0.1M selenium powder-octadecene into the transparent solution obtained in the step (2), timing, sampling at intervals, detecting, stopping reaction for 10min, cooling the obtained quantum dot solution, adding 1.5mL of the quantum dot solution into a 4mL glass bottle, adding 2.5mL of acetone for precipitation, 7500r/min for centrifugal precipitation, pouring out supernate, adding 0.5mL of toluene for dissolving, adding 0.005mL of decanoic acid, heating to be clear, adding 0.75mL of methanol for precipitation, repeating twice, and not adding decanoic acid for the next time. The above method is repeated to obtain three quantum dot precipitates.
(4) Dissolving the quantum dot precipitate in 0.5mL octadecene, introducing Ar for 10min in 2.3mL LODE and 0.7mL oleylamine, heating to 210 ℃, injecting 0.5mL 0.2M Se-SUS, maintaining for 10min, cooling to 165 ℃, injecting quantum dot-octadecene solution, and monitoring until the first absorption peak of the absorption spectrum is 550. And (3) taking 1.5mL of the obtained quantum dot solution, and precipitating with acetone twice to obtain the quantum dot catalyst 5.
Example 6
A preparation method of a quantum dot catalyst comprises the following steps:
(1) weighing 0.0256g of cadmium oxide, 0.1422g of stearic acid and 3mL of octadecene, and placing the mixture into a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 250 ℃ for maintaining;
(3) and (3) injecting 0.6mL of 0.1M selenium powder-octadecene into the transparent solution obtained in the step (2), timing, and supplementing 0.1mL of 0.1M selenium powder-octadecene suspension for 8 min. 0.05mL of 0.1M selenium powder-octadecene suspension is added after 12min, and the reaction is stopped after about 15 min. When the solution was cooled to 50 ℃, 0.2mL each of octylamine and tributyl phosphate was injected and stirred for 5min, and then 4mL of hexane and 8mL of methanol were injected into the three-necked flask and stirred for 2.5 min. After the stirring is stopped and the solution is layered, taking the lower clear liquid away by using an injector to finish the primary extraction. The extraction was repeated four times, with octylamine and tributyl phosphate being added only for the first and third times. After the purification was completed, the remaining hexane and methanol were purged with a stream of argon at 60 ℃.
(4) Adding 1.2mL, 3.8mL oleylamine and 1mL octadecene of the obtained quantum dot solution into a three-necked flask, introducing Ar for 10min, heating to 80 ℃, injecting 0.14mL of 0.1M cadmium diethyldithiocarbamate, and heating to 160 ℃ for 20 min. And after the obtained quantum dot solution is cooled to 80 ℃, repeating the steps, raising the temperature to maintain the temperature to be 150 ℃, subsequently dropwise adding 0.1M cadmium diethyldithiocarbamate with the amount of 0.20-0.27 mL, and precipitating the obtained quantum dot solution 1.5mL twice by using acetone to obtain the quantum dot catalyst 6.
Example 7
A preparation method of a quantum dot catalyst comprises the following steps:
(1) weighing 0.0256g of cadmium oxide, 0.1422g of stearic acid and 3mL of octadecene, and placing the mixture in a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 250 ℃ for maintaining;
(3) and (3) injecting 0.6mL of 0.1M selenium powder-octadecene into the transparent solution obtained in the step (2), timing, and supplementing 0.1mL of 0.1M selenium powder-octadecene suspension for 8 min. 0.05mL of 0.1M selenium powder-octadecene suspension is added after 12min, and the reaction is stopped after about 15 min. When the solution was cooled to 50 ℃, 0.2mL each of octylamine and tributyl phosphate was injected and stirred for 5min, and then 4mL of hexane and 8mL of methanol were injected into the three-necked flask and stirred for 2.5 min. After the stirring is stopped and the solution is layered, taking the lower clear liquid away by using an injector to finish the primary extraction. The extraction was repeated four times, with octylamine and tributyl phosphate being added only for the first and third times. After the purification was completed, the remaining hexane and methanol were purged with a stream of argon at 60 ℃.
(4) Adding 1.2mL, 3.8mL oleylamine and 1mL octadecene of the obtained quantum dot solution into a three-necked flask, introducing Ar for 10min, heating to 80 ℃, injecting 0.14mL of 0.1M cadmium diethyldithiocarbamate, and heating to 160 ℃ for 20 min. And after the obtained quantum dot solution is cooled to 80 ℃, repeating the steps, raising the temperature to maintain the temperature to be 150 ℃, subsequently dropwise adding 0.1M cadmium diethyldithiocarbamate with the amount of 0.20, 0.27 and 0.35mL, and precipitating the obtained quantum dot solution 1.5mL twice by using acetone to obtain the quantum dot catalyst 7.
Example 8
A preparation method of a quantum dot catalyst comprises the following steps:
(1) weighing 0.0256g of cadmium oxide, 0.1422g of stearic acid and 3mL of octadecene, and placing the mixture in a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 250 ℃ for maintaining;
(3) and (3) injecting 0.6mL of 0.1M selenium powder-octadecene into the transparent solution obtained in the step (2), timing, and supplementing 0.1mL of 0.1M selenium powder-octadecene suspension for 8 min. 0.05mL of 0.1M selenium powder-octadecene suspension is added after 12min, and the reaction is stopped after about 15 min. When the solution was cooled to 50 ℃, 0.2mL each of octylamine and tributyl phosphate was injected and stirred for 5min, and then 4mL of hexane and 8mL of methanol were injected into the three-necked flask and stirred for 2.5 min. After the stirring is stopped and the solution is layered, taking the lower clear liquid away by using an injector to finish the primary extraction. The extraction was repeated four times, with octylamine and tributyl phosphate being added only for the first and third times. After the purification was completed, the remaining hexane and methanol were purged with a stream of argon at 60 ℃.
(4) Adding 1.2mL, 3.8mL oleylamine and 1mL octadecene of the obtained quantum dot solution into a three-necked flask, introducing Ar for 10min, heating to 80 ℃, injecting 0.14mL of 0.1M cadmium diethyldithiocarbamate, and heating to 160 ℃ for 20 min. And after the obtained quantum dot solution is cooled to 80 ℃, repeating the steps, raising the temperature to maintain the temperature to be 150 ℃, subsequently dropwise adding 0.1M cadmium diethyldithiocarbamate with the amount of 0.20, 0.27, 0.35 and 0.45mL, and precipitating 1.5mL of the obtained quantum dot solution twice by using acetone to obtain the quantum dot catalyst 8.
Example 9
A preparation method of a quantum dot catalyst comprises the following steps:
(1) weighing 0.0256g of cadmium oxide, 0.1422g of stearic acid and 3mL of octadecene, and placing the mixture into a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 250 ℃ for maintaining;
(3) and (3) injecting 0.6mL of 0.1M selenium powder-octadecene into the transparent solution obtained in the step (2), timing, and supplementing 0.1mL of 0.1M selenium powder-octadecene suspension for 8 min. 0.05mL of 0.1M selenium powder-octadecene suspension is added after 12min, and the reaction is stopped after about 15 min. When the solution was cooled to 50 ℃, 0.2mL each of octylamine and tributyl phosphate was injected and stirred for 5min, and then 4mL of hexane and 8mL of methanol were injected into the three-necked flask and stirred for 2.5 min. After the stirring is stopped and the solution is layered, taking the lower clear liquid away by using an injector to finish the primary extraction. The extraction was repeated four times, with octylamine and tributyl phosphate being added only for the first and third times. After the purification was completed, the remaining hexane and methanol were purged with a stream of argon at 60 ℃.
(4) Adding 1.2mL, 3.8mL oleylamine and 1mL octadecene of the obtained quantum dot solution into a three-necked flask, introducing Ar for 10min, heating to 80 ℃, injecting 0.14mL of 0.1M cadmium diethyldithiocarbamate, and heating to 160 ℃ for 20 min. And after the obtained quantum dot solution is cooled to 80 ℃, repeating the steps, raising the temperature to maintain the temperature to be 150 ℃, subsequently dropwise adding 0.1M cadmium diethyldithiocarbamate with the amount of 0.20, 0.27, 0.35, 0.45 and 0.55mL, and precipitating 1.5mL of the obtained quantum dot solution twice by using acetone to obtain the quantum dot catalyst 9.
Example 10
A preparation method of a quantum dot catalyst comprises the following steps:
(1) weighing 0.0256g of cadmium oxide, 0.1422g of stearic acid and 3mL of octadecene, and placing the mixture in a three-neck flask;
(2) exhausting the material in the step (1) for 10min in an argon atmosphere, then heating to 280 ℃ for maintaining until the solution is clear and transparent, and then cooling to 250 ℃ for maintaining;
(3) and (3) injecting 0.6mL of 0.1M selenium powder-octadecene into the transparent solution obtained in the step (2), timing, and supplementing 0.1mL of 0.1M selenium powder-octadecene suspension for 8 min. 0.05mL of 0.1M selenium powder-octadecene suspension is added after 12min, and the reaction is stopped after about 15 min. When the solution was cooled to 50 ℃, 0.2mL each of octylamine and tributyl phosphate was injected and stirred for 5min, and then 4mL of hexane and 8mL of methanol were injected into the three-necked flask and stirred for 2.5 min. After the stirring is stopped and the solution is layered, taking the lower clear liquid away by using an injector to finish the primary extraction. The extraction was repeated four times, with octylamine and tributyl phosphate being added only for the first and third times. After the purification was completed, the remaining hexane and methanol were purged with a stream of argon at 60 ℃.
(4) Adding 1.2mL, 3.8mL oleylamine and 1mL octadecene of the obtained quantum dot solution into a three-necked flask, introducing Ar for 10min, heating to 80 ℃, injecting 0.14mL of 0.1M cadmium diethyldithiocarbamate, and heating to 160 ℃ for 20 min. And after the obtained quantum dot solution is cooled to 80 ℃, repeating the steps, raising the temperature to maintain the temperature to be 150 ℃, subsequently dropwise adding 0.1M diethyl dithiocarbamate with the cadmium content of 0.20, 0.27, 0.35 and 0.45, dropwise adding 0.1M diethyl dithiocarbamate with the zinc content of 0.55 and 0.67mL, and precipitating 1.5mL of the obtained quantum dot solution twice by using acetone to obtain the quantum dot catalyst 10.
FIG. 1 is a TEM image of quantum dot catalysts prepared in examples 1 to 3, 8 and 10; as can be seen from a Transmission Electron Microscope (TEM) image of FIG. 1, the prepared quantum dot catalyst is uniform in size and keeps good dispersibility.
FIG. 2 is an infrared spectrum of a quantum dot catalyst prepared in examples 1, 4 and 5; characteristic peaks of the different ligands can be seen from the Fourier transform infrared (FT-IR) spectrum of FIG. 2. The photocatalytic performance of the quantum dot catalysts prepared in examples 1-10 was verified respectively.
The used photocatalytic evaluation device was a glass bottle, and the quantum dots of examples 1 to 10 were used as catalysts, and first, catalyst 1 x 10 was taken-7mol, transferred to a 20mL glass bottleThen 4mL of toluene, 2mL of water, 1mL of phenethyl alcohol and 0.2mL of oleylamine were added. Adding magnetons, magnetically stirring, sealing, bubbling oxygen at a rate of 3mL/min, and pre-introducing gas for 30 min. Then a 300w xenon lamp light source is used, a visible light filter with the cut-off wavelength of 420nm is taken, the wavelength control bit of the visible light output by the xenon lamp light source is larger than the visible light with the wavelength of 420nm, and a photocatalytic glass bottle is irradiated on the side surface to perform the catalytic hydrogen peroxide production reaction.
And (3) taking reaction liquid after reacting for a certain time, and detecting the concentration of hydrogen peroxide by a titanium potassium oxalate colorimetric method. Collecting the lower layer 1mL of centrifuged supernatant, 2mL of 0.05mol L -1And finally adding 2mL of deionized water to dilute the titanium potassium oxalate solution, detecting the absorbance at the wavelength of 400nm, and comparing the absorbance with a standard curve to obtain the relationship between the concentration of hydrogen peroxide and the absorbance.
The calculation formula is as follows: c [ H ]2O2]＝5.1354*Abs
FIGS. 3 and 4 are absorption spectra before and after the reaction of the quantum dot catalysts prepared in examples 1 to 5; from the ultraviolet-visible diffuse reflectance graphs (fig. 3, fig. 4), it can be seen that the change before and after the reaction of the absorption spectra of different kinds of quantum dots reflects the stability of the quantum dots, and it can be seen that the quantum dots are more unstable as the size is smaller, and the quantum dots on the surface of the thiol ligand are extremely unstable.
FIGS. 5 to 8 are summary graphs of test data of photocatalytic hydrogen peroxide production by quantum dot catalysts prepared in examples 1 to 10; the hydrogen peroxide production experiment (fig. 5 and 6) of the quantum dot catalyst shows that the smaller the size, the better the catalytic effect of the quantum dots, the best the catalytic effect of the quantum dots on the surface of the dodecanethiol ligand, and the worst the catalytic effect of the quantum dots on the surface of the carboxylate ligand.
Experiments (figures 7 and 8) of quantum dot catalysts with different shell structures and thicknesses show that the catalytic effect of the cadmium selenide quantum dots coated with 5 layers of cadmium sulfide to generate hydrogen peroxide is the best, and the catalytic effect of the cadmium selenide quantum dots coated with the zinc sulfide shell is the better.
In conclusion, the final photocatalytic hydrogen peroxide production is greatly influenced by changing the size, the ligand, the shell thickness and the structure of the quantum dot material, an optimal experimental condition can be obtained by regulating and controlling, the cost is saved, the hydrogen peroxide yield is improved, and the application of photocatalytic hydrogen peroxide production can be realized.
Application example 1 (test catalyst life):
application example 1
The photocatalytic evaluation device used was a glass bottle, first 1 × 10-7mol quantum dot catalyst, transferred to a 20mL glass bottle, and then added with 4mL toluene, 2mL deionized water, 1mL benzyl alcohol, 0.2mL oleylamine. Adding magnetons, magnetically stirring, sealing, bubbling oxygen at a rate of 3mL/min, and pre-introducing gas for 30 min. Then, a 300w xenon lamp light source is used, a visible light filter with the cut-off wavelength of 420nm is taken, the visible light with the wavelength control bit of more than 420nm output by the xenon lamp light source is irradiated on the side surface of a glass bottle, and the catalytic hydrogen peroxide production reaction is carried out for 3 hours.
Application example 2
The photocatalytic evaluation device used was a glass bottle, first 1 × 10-7mol quantum dot catalyst, transferring to a 20mL glass bottle, adding 4mL toluene, 2mL deionized water, 1mL phenethyl alcohol and 0.2mL oleylamine. Adding magnetons, magnetically stirring, sealing, bubbling oxygen at a rate of 3mL/min, and pre-introducing gas for 30 min. Then, a 300w xenon lamp light source is used, a visible light filter with the cut-off wavelength of 420nm is taken, the visible light with the wavelength control bit of more than 420nm output by the xenon lamp light source is irradiated on the side surface of a glass bottle, and the catalytic hydrogen peroxide production reaction is carried out for 3 hours.
Application example 3
The photocatalytic evaluation device used was a glass bottle, first 1 x 10-7mol quantum dot catalyst, transferred to a 20mL glass bottle, then 4mL toluene, 2mL deionized water, 1mL ethanol, 0.2mL oleylamine. Adding magnetons, stirring by magnetic force, sealing, bubbling oxygen at a rate of 3mL/min, and introducing gas for 30 min. Then, a 300w xenon lamp light source is used, a visible light filter with the cut-off wavelength of 420nm is taken, the visible light with the wavelength control bit of more than 420nm output by the xenon lamp light source is irradiated on the side surface of a glass bottle, and the catalytic hydrogen peroxide production reaction is carried out for 3 hours.
Application example 4
The photocatalytic evaluation device used was a glass bottle, first 1 x 10-7mol quantum dot catalysisTransfer to a 20mL glass vial, add 4mL toluene, 2mL deionized water, 1mL benzyl alcohol, 0.2mL oleylamine. Adding magnetons, stirring by magnetic force, sealing, bubbling oxygen at a rate of 3mL/min, and introducing gas for 30 min. Then, a 300w xenon lamp light source is used, a visible light filter with the cut-off wavelength of 420nm is taken, the visible light with the wavelength control bit of more than 420nm output by the xenon lamp light source is irradiated on the side surface of a glass bottle, and the catalytic hydrogen peroxide production reaction is carried out for 8 hours.
Application example 5
The photocatalytic evaluation device used was a glass bottle, first 1 × 10 -7mol quantum dot catalyst, transferred to a 20mL glass bottle, then 4mL toluene, 1mL benzyl alcohol, 0.2mL oleylamine. Adding magnetons, stirring by magnetic force, sealing, bubbling oxygen at a rate of 3mL/min, and introducing gas for 30 min. Then, a 300w xenon lamp light source is used, a visible light filter with the cut-off wavelength of 420nm is taken, the visible light with the wavelength control bit of more than 420nm output by the xenon lamp light source is irradiated on the side surface of a glass bottle, and the catalytic hydrogen peroxide production reaction is carried out for 3 hours.
Application example 6
The photocatalytic evaluation device used was a glass bottle, first 1 x 10-7mol quantum dot catalyst, transferred to a 20mL glass bottle, then 2mL deionized water, 1mL benzyl alcohol, 0.2mL oleylamine. Adding magnetons, stirring by magnetic force, sealing, bubbling oxygen at a rate of 3mL/min, and introducing gas for 30 min. Then, a 300w xenon lamp light source is used, a visible light filter with the cut-off wavelength of 420nm is taken, the visible light with the wavelength control bit of more than 420nm output by the xenon lamp light source is irradiated on the side surface of a glass bottle, and the catalytic hydrogen peroxide production reaction is carried out for 3 hours.
Fig. 9 to 11 are summary graphs of data obtained by testing photocatalytic hydrogen peroxide production according to application examples 1 to 6, and it can be seen from fig. 9 that the yield of hydrogen peroxide is the highest within 2 hours, and fig. 10 that benzyl alcohol has the best effect as a sacrificial agent, and fig. 11 that the catalytic effect of toluene/water is the best in a two-phase system.
The description is given for the sole purpose of illustrating the invention concept in its implementation form and the scope of the invention should not be considered as being limited to the particular form set forth in the examples.

Claims (10)

1. A method for producing hydrogen peroxide based on cadmium-based colloidal quantum dot photocatalysis is characterized by comprising the steps of firstly synthesizing cadmium selenide nuclear quantum dots, purifying, then epitaxially growing cadmium sulfide and a zinc sulfide shell layer, and producing hydrogen peroxide by taking the cadmium sulfide nuclear quantum dots as a photocatalyst.
2. The method for producing hydrogen peroxide based on the photocatalysis of the colloidal cadmium-based quantum dots according to claim 1, which comprises the following steps:
1) adding the quantum dot precursor into a three-neck flask;
2) exhausting the materials in the step 1) in an argon atmosphere, then heating and maintaining until the solution is clear and transparent, and then cooling and maintaining; injecting a selenium precursor such as selenium powder-octadecene suspension into the obtained transparent solution, sampling and detecting at intervals, stopping reaction when the solution grows to the required size, cooling the obtained quantum dot solution, and purifying to obtain cadmium selenide quantum dots on the surface of the aliphatic carboxylate ligand;
3) ligand exchange is carried out on the cadmium selenide quantum dots on the surfaces of the ligands of the aliphatic carboxylic acid salt obtained after purification in the step 2) to obtain quantum dots with different surface ligands, such as aliphatic amine ligands, mercaptan ligands and the like;
4) And (3) carrying out cladding treatment on the cadmium selenide quantum dots on the surface of the aliphatic carboxylate ligand obtained after purification in the step 2), and obtaining the quantum dots with different shell thicknesses and structures after purification.
3. The method for producing hydrogen peroxide based on cadmium-based colloid quantum dot photocatalysis as claimed in claim 2, wherein the quantum dot precursor in step 1) is cadmium oxide or cadmium acetate or cadmium carbonate or cadmium hydroxide or cadmium nitrate; octanoic acid or decanoic acid or dodecanoic acid or tetradecanoic acid or hexadecanoic acid or stearic acid; and octadecene or squalene or squalane or octadecane or hexadecane or tetradecane or dodecane or paraffin; the amount of the cadmium precursor and the acid and the type of the acid are determined by the needed synthetic quantum dot catalyst.
4. The method for producing hydrogen peroxide based on cadmium-based colloid quantum dot photocatalysis as claimed in claim 2, wherein in the step 2), the temperature rise and maintenance temperature is 200-320 ℃, the temperature drop and maintenance temperature and the growth time are determined by the size of the required cadmium selenide quantum dot, and the size of the required cadmium selenide quantum dot is 1-20 nm; the exchange ligand in the step 3) is octylmercaptol or dodecylmercaptol or hexadecylmercaptol or octadecylmercaptol and butylamine or octylamine or hexadecylamine or octadecylamine or oleylamine.
5. The method for producing hydrogen peroxide based on cadmium-based colloid quantum dot photocatalysis as claimed in claim 4, wherein the size of the cadmium selenide quantum dot is 1-20nm, and the exchange ligand is butylamine, octylamine, hexadecylamine, octadecylamine or oleylamine.
6. The method for producing hydrogen peroxide based on quantum dot photocatalysis of cadmium-based colloid according to claim 2, wherein the shell layer in the step 4) is epitaxially grown by the following specific method:
adding the purified cadmium selenide quantum dots and butylamine, octylamine, hexadecylamine, octadecylamine, oleylamine, octadecene, squalene, squalane, octadecane, hexadecane, tetradecane, dodecane or paraffin into a three-neck flask together, exhausting for 1-20min under the atmosphere of argon or nitrogen, and injecting cadmium diethyldithiocarbamate, cadmium diethyldithiocarbamate or cadmium diethyldithiocarbamate to prepare the cadmium selenide/cadmium sulfide core-shell quantum dots with the cadmium sulfide shell thickness of 1-10 layers, wherein the cadmium sulfide shell thickness is preferably 5 layers; the cadmium sulfide shell layer with the thickness of 1-10 layers is obtained by injecting zinc diethyldithiocarbamate or zinc diethyldithiocarbamate, the quantum dots with the thickness of 1-4 layers of zinc sulfide shell layer are obtained, the thickness of the zinc sulfide shell layer is preferably 2 layers, the temperature is set to be 20-80 ℃ when the precursor is injected for the first time, then the temperature is increased to 140-220 ℃ and maintained for 5-30min, then the heating is stopped, the temperature is reduced to be 20-80 ℃, and the subsequent shell layer growth mode is the same as that of the first time.
7. The quantum dot catalyst prepared by the method for producing hydrogen peroxide based on cadmium-based colloidal quantum dot photocatalysis according to claim 1, 2, 3, 4, 5 or 6, and is characterized in that the catalyst prepared by the method is cadmium selenide/cadmium sulfide/zinc sulfide core-shell quantum dots.
8. The application of the colloidal quantum dot catalyst in preparing hydrogen peroxide through photocatalysis as claimed in claim 7, wherein the quantum dot catalyst is dissolved in an oil/water two-phase system, and oxygen is introduced to generate hydrogen peroxide under illumination.
9. The application of the quantum dot catalyst in the photocatalytic preparation of hydrogen peroxide as claimed in claim 8, wherein the wavelength of the xenon lamp is 300-800nm, the solvent system of the catalytic reaction is water, or toluene, hexane, chloroform, or a mixed system of toluene, hexane, or chloroform/water, and the reaction time is 1-8 h.
10. The application of the quantum dot catalyst in the photocatalytic preparation of hydrogen peroxide as claimed in claim 9, wherein the xenon lamp wavelength is in the visible light band of 420-800nm, the reaction system is a toluene/water two-phase system, and the reaction time is 2 h.
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