CN109046328B - Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction - Google Patents

Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction Download PDF

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CN109046328B
CN109046328B CN201810664224.0A CN201810664224A CN109046328B CN 109046328 B CN109046328 B CN 109046328B CN 201810664224 A CN201810664224 A CN 201810664224A CN 109046328 B CN109046328 B CN 109046328B
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卢春山
王昊
季豪克
朱倩文
张雪洁
周烨彬
李小年
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a photo-thermal catalytic hydrogenation catalyst, a preparation method thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction. The photo-thermal catalytic hydrogenation catalyst consists of a mesoporous carbon microsphere carrier, and carbon quantum dots and metal quantum dots which are loaded on the surface of the carrier, wherein the size of the catalyst is 50-100 nm, the particle size range of the carbon quantum dots is 4.5-6.5 nm, the metal quantum dots are one or the combination of two of palladium quantum dots and platinum quantum dots, and the particle size range of the metal quantum dots is 10-15 nm; in the catalyst, the mass fractions of the carbon quantum dots and the metal quantum dots are respectively 10-30% and 1-2%. The invention provides application of the photo-thermal catalytic hydrogenation catalyst in the reaction of synthesizing 3, 4-dichloroaniline through selective catalytic hydrogenation of 3, 4-dichloronitrobenzene under the irradiation of 280-350 nm ultraviolet light, and the photo-thermal catalytic hydrogenation catalyst has the characteristics of high conversion rate, good selectivity, high hydrogenation reaction rate and good stability.

Description

Photo-thermal catalytic hydrogenation catalyst, preparation thereof and application thereof in 3, 4-dichloronitrobenzene selective hydrogenation reaction
(I) technical field
The invention relates to a photo-thermal catalytic hydrogenation catalyst, and preparation and application thereof, in particular to application of the catalyst in photo-thermal catalytic 3, 4-dichloronitrobenzene selective hydrogenation reaction.
(II) technical background
3, 4-dichloroaniline is an important medicine, pesticide, dye and daily chemical organic intermediate, and is widely applied to synthesis of herbicides and azo dyes. 3, 4-dichloroaniline is usually prepared by reducing 3, 4-dichloronitrobenzene by an iron powder reduction method, a sodium sulfide reduction method and a catalytic hydrogenation reduction method. Because the iron powder reduction method can generate a large amount of metal residues, and the sodium sulfide reduction method can generate organic waste water containing hydrochloric acid, which causes serious damage to the environment and is gradually eliminated. The catalytic hydrogenation reduction method has simple operation process and environmental protection, and is more concerned by researchers. However, the catalytic hydrogenation reduction method has a process of hydrogenolysis dechlorination, and how to effectively inhibit dechlorination is always concerned.
There are two main solutions at present: one is adding antichlor to inhibit the generation of dechlorination product in the catalytic hydrogenation reaction; the other is to develop a catalyst with high selectivity to inhibit the dechlorination reaction. For example, the Chinese invention patent CN1962608 discloses a method for preparing 3, 4-dichloroaniline by catalytic hydrogenation, which takes alcoholic solution as a solvent system, and introduces H under the conditions of 0.5-1.5MPa and 80-120 ℃ in the presence of Raney-Ni catalyst and dechlorination inhibitor ethanolamine2The selectivity of the prepared 3, 4-dichloroaniline is more than 99 percent and the dechlorination amount is less than 2 percent by carrying out catalytic hydrogenation reduction reaction. In the invention of the United states patent US3546297A1, Pt-Ni-Cr/C is used as a catalyst, ammonia water, morpholine or piperazine which is a dechlorination inhibitor is added at the same time, and 3, 4-dichloronitrobenzene is subjected to catalytic hydrogenation under the conditions of 30-150 ℃ and 1.4-4.1MPa, wherein the dechlorination rate is less than 0.03%. The selectivity of catalytic hydrogenation can be improved by adding the dechlorinating inhibitor, but the problems that the separation of the catalyst after reaction and the dechlorinating inhibitor is difficult, the recycling performance of the catalyst is reduced, the quality of the obtained product is reduced, the cost is increased and the like exist at the same time. Chinese patent CN200510050594.8 with Ru-Fe/Al2O3The selectivity of 3, 4-dichloroaniline is 99.3 percent when the catalyst is used for catalytic hydrogenation reaction. However, the binary active component used in the patent has a complex preparation process and high recovery cost of the noble metal Ru. The Chinese patent CN02148509.7 uses Pd/NCT and Pt/NCT as catalysts respectively, and the selectivity of 3, 4-dichloroaniline is99.2 percent and 99 percent, but the carbon nano tube is used as a carrier, so the price is high and the cost is high. The Chinese patent CN102241595A provides a method for preparing 3, 4-dichloroaniline by photocatalytic reduction, the method selects a photocatalytic reactor, the reactor is provided with an air inlet system, an air outlet system, a cooling water inlet system and a cooling water outlet system, the wall of the reactor is required to be capable of transmitting ultraviolet light with the wavelength less than 387.5nm, the photocatalytic reactor is filled with an organic solvent, and 3, 4-dichloronitrobenzene and a solid powder catalyst TiO are added2Adding the mixture into an organic solvent, simultaneously adding surfactant subwet159 as an additive, dissolving the 3, 4-dichloronitrobenzene and solid powdery catalyst TiO in the organic solvent in an inert gas nitrogen atmosphere2Dark adsorbing for 10min, and irradiating with ultraviolet light at power of 250W and radiation intensity of 4120 μ W/cm in inert gas nitrogen atmosphere2Irradiating under the irradiation with 3, 4-dichloronitrobenzene and solid powdery TiO2The yield of 3, 4-dichloroaniline in the light-transmitting reactor of the catalyst is 71.30%. The method has complex operation steps and low yield of the 3, 4-dichloroaniline obtained by single photocatalytic hydrogenation reaction.
This patent invents a light and heat catalytic hydrogenation catalyst, introduces the light source in traditional thermal reaction catalytic hydrogenation's reation kettle, utilizes not unidimensional carbon quantum dot and metal quantum dot to constitute two ingredient active ingredient, is 200 ~ 400nm condition at ultraviolet illumination wavelength for carbon quantum dot stores and electron transfer with higher speed, and hydrogen forms rich electron adsorption state H after the dissociation absorption on active metal particle surface-Attack of N in nitro groups+The center inhibits the dechlorination reaction, thereby greatly improving the selectivity of the reaction.
Disclosure of the invention
The invention aims to provide a photo-thermal catalytic hydrogenation catalyst, which comprises 4.5-6.5 nm carbon dots and 10-15 nm metal dots, and under the action of 280-350 nm ultraviolet light and thermal coupling, excited photoelectrons modulate the electronic characteristics of an active site, so that adsorbed hydrogen is modulated, and the photo-thermal catalytic hydrogenation catalyst is particularly suitable for the reaction of synthesizing 3, 4-dichloroaniline by selective hydrogenation of 3, 4-dichloronitrobenzene.
The invention also aims to provide a method for preparing the photo-thermal catalytic hydrogenation catalyst, which is simple to operate, can realize the generation and growth of the carbon quantum dots on the surface of the carbon sphere in situ in one step, and has a precise and controllable particle size distribution range.
The invention further aims to provide the application of the photo-thermal catalytic hydrogenation catalyst in the photo-thermal catalytic hydrogenation reaction of 3, 4-dichloronitrobenzene, and the photo-thermal catalytic hydrogenation catalyst has the characteristics of high conversion rate, good selectivity, high hydrogenation reaction rate and good stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a photo-thermal catalytic hydrogenation catalyst comprises a mesoporous carbon microsphere carrier, and carbon quantum dots and metal quantum dots which are loaded on the surface of the carrier, wherein the size of the catalyst is 50-100 nm, the particle size range of the carbon quantum dots is 4.5-6.5 nm, the metal quantum dots are one or the combination of two of palladium quantum dots and platinum quantum dots, and the particle size range of the metal quantum dots is 10-15 nm; in the catalyst, the mass fractions of the carbon quantum dots and the metal quantum dots are respectively 10-30% and 1-2%.
A preparation method of a photo-thermal catalytic hydrogenation catalyst comprises the following steps:
1) carrying out polycondensation reaction in an alcohol-water solution system by using 3-aminophenol and formaldehyde as carbon source precursors and ammonia water as a catalyst to obtain polymer microspheres;
2) preparing mixed slurry from the polymer microspheres obtained in the step 1) and deionized water, placing the prepared mixed slurry into a microwave digestion instrument, carrying out microwave reaction for 20-30 minutes at 180-210 ℃, cooling, taking out the mixed slurry, and carrying out vacuum drying to obtain the polymer microspheres modified by the carbon quantum dots, wherein the carbon quantum dots are distributed on the surfaces of the polymer microspheres and have particle sizes ranging from 4.5 nm to 6.5 nm;
3) loading metal salt to the carbon quantum dot modified polymer microspheres obtained in the step 2) through wet impregnation, and drying to obtain a catalyst precursor;
4) calcining and cooling the catalyst precursor obtained in the step 3) in an inert atmosphere to obtain the photo-thermal catalytic hydrogenation catalyst, wherein the calcining process is a temperature programming process: raising the temperature from room temperature to 200-300 ℃ at a heating rate of 0.5-3.5 ℃/min, and keeping the temperature for 1-4 hours; raising the temperature from 200-300 ℃ to 400-600 ℃ at a heating rate of 3.5-8.5 ℃/min, and keeping the temperature for 3-6 hours.
The step 1) of the invention, namely the polymerization of the phenolic resin microspheres, can refer to the existing documents, and the invention specifically recommends the step 1) to be carried out as follows: preparing a mixed solution consisting of 20-25% by mass of ammonia water, alcohol, deionized water, 3-aminophenol and 33-38% by mass of formaldehyde aqueous solution, wherein the volume ratio of the ammonia water to the formaldehyde aqueous solution to the alcohol to the deionized water is 1: 2-8: 20-60: 70-100, and the molar ratio of the 3-aminophenol to the formaldehyde is 1: 2-5; stirring the prepared mixed solution at room temperature for 2-10 h, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100-300 ℃ for 12-48 h, and drying to obtain the polymer microspheres. Further, the alcohol is preferably ethanol or propanol. The drying conditions are preferably as follows: drying the mixture for 12 to 48 hours at a temperature of between 20 and 80 ℃.
In the step 2), the size of the carbon quantum dots is controlled by controlling the microwave reaction conditions. The feeding ratio of the polymer microspheres to the deionized water is preferably 1g: 10-25 ml. The vacuum drying conditions are preferably: and drying the mixed slurry obtained by the microwave method for 12-48 hours at the temperature of 20-80 ℃ under the relative vacuum degree of-0.099-0.05 MPa.
The wet impregnation of step 3) of the present invention is a conventional step in the art. Wherein the metal salt can be one or more of the following in combination: palladium nitrate, chloropalladic acid, ethylenediamine palladium chloride, ammonium tetrachloropalladate, sodium chloropalladate, tetraamminepalladium nitrate, tetraamminepalladium dihydrogencarbonate, chloroplatinic acid, platinum nitrate, sodium chloroplatinate, tetraammineplatinum nitrate, dinitrosoplatinum, potassium trichloroammoplatinate, sodium hexachloroplatinate and the like. The step 3) is preferably performed as follows: preparing an aqueous solution of metal salt with the metal mass concentration of 0.001-0.05 g/mL, mixing the polymer microsphere modified by the carbon quantum dots, the aqueous solution of the metal salt and deionized water obtained in the step 2), wherein the feeding ratio of the polymer microsphere modified by the carbon quantum dots, the aqueous solution of the metal salt and the deionized water is 1g: 5-20 mL: 10-25 mL, and drying an impregnated sample after impregnating for 5-10 hours to obtain a catalyst precursor. Wherein the drying conditions are preferably: drying the dipped sample at 40-80 ℃ for 12-48 hours.
In the step 4) of the invention, the inert atmosphere is N2(ii) a And in the calcining process, the volume flow of the inert atmosphere is 10-80 ml/min.
The invention further provides application of the photo-thermal catalytic hydrogenation catalyst in a reaction of synthesizing 3, 4-dichloroaniline shown in a formula II by selective catalytic hydrogenation of 3, 4-dichloronitrobenzene shown in a formula I under the irradiation of 280-350 nm ultraviolet light.
Specifically, the application method of the catalyst comprises the following steps:
putting a photo-thermal catalytic hydrogenation catalyst and 3, 4-dichloronitrobenzene shown in formula I into a high-pressure hydrogenation reaction kettle with ultraviolet irradiation, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen at the pressure of 0.5-1.5MPa, opening a heating bond of the reaction kettle, heating to 30-120 ℃, opening a 280-350 nm ultraviolet lamp for irradiation after the temperature is stable, starting stirring to start the reaction, continuing stirring at constant temperature and constant pressure for a period of time when the pressure in the kettle does not decrease, stopping stirring and cooling to room temperature, opening the kettle, taking out a hydrogenation liquid, and separating and treating the hydrogenation liquid to obtain 3, 4-dichloroaniline shown in formula II;
Figure BDA0001707211990000041
further, in the application, the feeding mass ratio of the compound shown in the formula I to the photo-thermal catalytic hydrogenation catalyst is 100: 0.5-4, preferably 100: 1.0 to 2.0.
Furthermore, the compound shown in the formula I can also be subjected to hydrogenation reaction under the conditions of solvent and no solvent. When the solvent-free hydrogenation reaction is carried out, firstly, the raw material is preheated and melted to be in a liquid state, and then the temperature is raised to the reaction temperature for hydrogenation reaction; in the solvent hydrogenation reaction, the solvent is preferably methanol or ethanol, wherein the feeding ratio of the catalyst to the solvent is 1g to 10-30 ml.
Furthermore, the irradiation wavelength range of the ultraviolet lamp is 280-350 nm, the power is 200-250W, and the radiation intensity is 3660-3980 muW/cm2
Further, the method for separating and post-treating the hydrogenation liquid comprises the following steps: filtering the hydrogenation liquid to separate out the catalyst, and carrying out vacuum rectification on the filtrate to obtain a product; in the post-treatment process, the catalyst obtained by filtering the hydrogenation liquid can be returned to the reaction kettle for catalyst reuse.
Compared with the prior art, the invention has the beneficial effects that:
1) the mesoporous carbon microspheres are used as carriers of photo-thermal catalysts, groups are simple and controllable, the preparation repeatability is high, and the particle size of spheres is 50-100 nm, so that the influence of mass transfer can be eliminated; the pi-pi bonding bond formed between the carbon quantum dot and the mesoporous carbon microsphere can modulate the anchoring capability of the metal active component, so that the metal is better dispersed on the mesoporous carbon carrier and is not easy to agglomerate, and the metal utilization rate is improved; in addition, under the action of ultraviolet light of 280-350 nm and thermal coupling, excited photoelectrons of 4.5-6.5 nm carbon dots and 10-15 nm metal dots modulate the electronic characteristics of active sites, and a special size effect and quantum effect are presented.
2) The preparation of the carbon quantum dots can achieve more accurate and controllable particle size distribution range of the carbon quantum dots only by simply and conveniently regulating and controlling the microwave temperature and time. In addition, the organic matter based on the synthesized carbon quantum dots is orderly adsorbed on the surface of the polymer microsphere, and a microwave modulation polymerization process is applied to realize the generation and growth of the carbon quantum dots on the surface of the carbon sphere in one step in situ. Compared with the traditional hydrothermal and impregnation loading step-by-step operation, the method is simpler and more convenient.
3) The load type catalyst with 4.5-6.5 nm carbon points and 10-15 nm metal points modulates the electronic characteristic of an active site by excited photoelectrons under the action of 280-350 nm ultraviolet light and thermal coupling, and further modulates the adsorbed hydrogen, so that the load type catalyst is particularly suitable for the reaction of synthesizing 3, 4-dichloroaniline by selective hydrogenation of 3, 4-dichloronitrobenzene. The catalyst has the advantages of mild condition, good stability, low catalyst consumption, multiple times of application, long service life, high catalytic activity and selectivity, high hydrogenation reaction rate and 100 percent of selectivity of the 3, 4-dichloroaniline in the recycling process.
(IV) description of the drawings
FIG. 1 is a transmission electron micrograph of a catalyst prepared according to example 1, in which the spherical balls with the largest particle size are mesoporous carbon microspheres; the carbon quantum dots with the smallest particle size; darker colored are metal dots.
Fig. 2 is a graph showing dynamic light scattering of carbon quantum dots prepared in example 1.
(V) detailed description of the preferred embodiments
Example 1
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the mixture is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃ to obtain the polymer microspheres.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with palladium concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 5-6 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Example 2
Measuring 1ml of ammonia water with the mass concentration of 20%, 20ml of ethanol and 70ml of deionized water, mixing and fully stirring, then adding 2g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 2ml of formaldehyde solution with the mass concentration of 33%, stirring for 2 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 100 ℃, cooling to room temperature, and then putting the mixture into an oven to dry for 12 hours at 20 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
The particle size of the catalyst carrier is 50-65 nm, the particle size of the carbon dots is 5.5-6 nm, and the particle size of the metal is 12-13 nm through TEM test; by TG, ICP and material balance, the loading of carbon points is 19 percent, and the loading of metal is 1.8 percent.
Example 3
Measuring 1ml of ammonia water with the mass concentration of 25%, 60ml of ethanol and 100ml of deionized water, mixing and fully stirring, then adding 5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 8ml of formaldehyde solution with the mass concentration of 38%, stirring for 10h at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 48h at 300 ℃, cooling to room temperature, and then putting the mixture into an oven to be dried for 48h at 80 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 85-100 nm, the particle size of the carbon dots is 5.5-6 nm, and the particle size of the metal is 12-13 nm; by TG, ICP and material balance, the loading of carbon points is 17%, and the loading of metal is 2%.
Example 4
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 10ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 180 ℃ and the microwave reaction time at 20 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 20 ℃ for 12 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
The particle size of the catalyst carrier is 70-80 nm, the particle size of the carbon dots is 4.5-5 nm and the particle size of the metal is 11-12 nm through TEM test; by TG, ICP and material balance, the loading of carbon points is 10%, and the loading of metal is 2%.
Example 5
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in an atmosphere with the volume flow of an inert atmosphere of 50ml/min, keeping the temperature for 2 hours at 300 ℃ and keeping the temperature for 4 hours at 600 ℃ (wherein the temperature rise procedure is 1 ℃/min from room temperature to 300 ℃,300 ℃ to 600 ℃ at 5 ℃/min) to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 65-75 nm, the particle size of the carbon dots is 5.5-6 nm, and the particle size of the metal is 12-13 nm; by TG, ICP and material balance, the loading of carbon points is 21 percent, and the loading of metal is 1.7 percent.
Example 6
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 25ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 210 ℃ and the microwave reaction time at 30 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 80 ℃ for 48 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in an atmosphere with the volume flow of 50ml of inert atmosphere, keeping the temperature at 300 ℃ for 2 hours and keeping the temperature at 600 ℃ for 4 hours (wherein the temperature rising procedure is that the temperature is 1 ℃/minute from room temperature to 300 ℃ and 5 ℃/minute from 300 ℃ to 600 ℃) so as to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 6-6.5 nm, and the particle size of the metal is 11-13 nm; by TG, ICP and material balance, the loading of carbon points is 30%, and the loading of metal is 2%.
Example 7
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
And (3) mixing 1g of the quantum dot-loaded carbon microsphere solid powder prepared by the method with 10mL of deionized water, uniformly stirring, dripping 20mL of chloropalladate solution with the concentration of 0.001g/mL into the mixed solution, stirring for 5 hours, washing to be neutral, and drying in an oven at 40 ℃ for 12 hours.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
The particle size of the catalyst carrier is 70-80 nm, the particle size of the carbon dots is 5.5-5 nm, and the particle size of the metal is 10-11 nm through TEM test; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 1%.
Example 8
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 8 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-80 nm, the particle size of the carbon dots is 5.5-6.5 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Example 9
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
And (3) mixing 1g of the quantum dot-loaded carbon microsphere solid powder prepared by the method with 25mL of deionized water, uniformly stirring, dripping 4mL of chloropalladate solution with the concentration of 0.05g/mL into the mixed solution, stirring for 10 hours, washing to be neutral, and drying in an oven at 80 ℃ for 48 hours.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 4.5-5.5 nm, and the particle size of the metal is 13.5-15 nm; by TG, ICP and material balance, the loading of carbon points is 18 percent, and the loading of metal is 1.8 percent.
Example 10
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in atmosphere with volume flow of inert atmosphere of 10ml/min at 200 deg.C for 1 hr and at 400 deg.C for 3 hr (wherein the temperature rise procedure is 0.5 deg.C/min from room temperature to 200 deg.C and 3.5 deg.C from 200 deg.C to 400 deg.C)C/min) to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 65-75 nm, the particle size of the carbon dots is 5-5.5 nm, and the particle size of the metal is 11-13 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 1%.
Example 11
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept at 250 ℃ for 2 hours, and the temperature is kept at 500 ℃ for 5 hours, (wherein the temperature rise program is that the temperature is between room temperature and 250 ℃ for 1.5 ℃/minute, and between 250 ℃ and 500 ℃ for 5 ℃/minute), so as to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-80 nm, the particle size of the carbon dots is 5.5-6 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 1.8%.
Example 12
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 195 ℃ and the microwave reaction time at 25 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with the concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at the temperature of 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 80ml/min, the temperature rise process is that the temperature is kept for 4 hours at 300 ℃ and is kept for 6 hours at 600 ℃ (the temperature rise program is that the temperature is 3.5 ℃/min from room temperature to 300 ℃, and is 8.5 ℃/min from 300 ℃ to 600 ℃) so as to obtain the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-85 nm, the particle size of the carbon dots is 4.5-5.5 nm, and the particle size of the metal is 12-13 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Comparative example 1
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the aminophenol is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃.
And (3) mixing 1g of the carbon microsphere solid powder prepared by the method with 15mL of deionized water, uniformly stirring, dripping 10mL of chloropalladate solution with the concentration of 0.002g/mL into the mixed solution, stirring for 5 hours, washing to be neutral, and drying in an oven at 60 ℃ for 24 hours.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus the catalytic hydrogenation catalyst without quantum dot load is obtained.
The particle size of the catalyst carrier is 70-75 nm through TEM test, and the particle size of the metal is 11-12 nm; the metal loading was 2% by TG, ICP and mass balance.
Comparative example 2
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the mixture is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃ to obtain the polymer microspheres.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 165 ℃ and the microwave reaction time at 15 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with palladium concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at 60 ℃.
The solid obtained is then in N2Calcining in an atmosphere with an inert atmosphere volume flow of 50ml/min at 300 deg.C for 2 hr and 600 deg.C for 4 hr (wherein the temperature rise is from room temperature to 300 deg.C at 1 deg.C/min and from 300 deg.C to 600 deg.C at 5 deg.C/min)) Thereby obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 2-3 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Comparative example 3
Measuring 1ml of ammonia water with the mass concentration of 23%, 32ml of ethanol and 80ml of deionized water, mixing and fully stirring, then adding 3.5g of 3-aminophenol, stirring until the mixture is completely dissolved, then dripping 5ml of formaldehyde solution with the mass concentration of 35%, stirring for 4 hours at room temperature, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to the room temperature, and then putting the mixture into an oven to dry for 24 hours at 60 ℃ to obtain the polymer microspheres.
Weighing 1g of polymer microspheres and 15ml of deionized water, uniformly stirring, putting the prepared mixed slurry into a microwave digestion instrument, setting the temperature at 225 ℃ and the microwave reaction time at 35 minutes, carrying out microwave reaction, cooling, taking out the mixed slurry, putting the mixed slurry into a vacuum oven, and drying at 60 ℃ for 24 hours under the relative vacuum degree of-0.099-0.05 MPa to obtain solid powder.
1g of the quantum dot supported carbon microsphere solid powder prepared by the method is mixed with 15mL of deionized water and stirred uniformly, 10mL of chloropalladate solution with palladium concentration of 0.002g/mL is dripped into the mixed solution, the mixture is stirred for 5 hours and then washed to be neutral, and the mixture is put into an oven to be dried for 24 hours at 60 ℃.
The solid obtained is then in N2Calcining in the atmosphere, wherein the volume flow of the inert atmosphere is 50ml/min, the temperature rise process is that the temperature is kept for 2 hours at 300 ℃ and is kept for 4 hours at 600 ℃ (the temperature rise program is that the temperature is 1 ℃/minute from room temperature to 300 ℃, and 5 ℃/minute from 300 ℃ to 600 ℃), and thus obtaining the photo-thermal catalytic hydrogenation catalyst.
According to TEM test, the particle size of the catalyst carrier is 70-75 nm, the particle size of the carbon dots is 7.5-8.5 nm, and the particle size of the metal is 11-12 nm; by TG, ICP and material balance, the loading of carbon points is 20%, and the loading of metal is 2%.
Example 13
0.5g of the catalyst of example 1, 25 g of 3,4-Putting dichloronitrobenzene and 30mL methanol solvent into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, starting stirring, controlling the wavelength of ultraviolet light to be 350nm, the power to be 250W, and the radiation intensity to be 3980 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 120 ℃ and the hydrogen pressure is 1.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 99.94%, and the reaction time is 35 minutes.
Example 14
0.5g of the catalyst of example 3, 50 g of 3, 4-dichloronitrobenzene and 10mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 280nm, the power is 200W, and the radiation intensity is 3660 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 30 ℃ and the hydrogen pressure is 0.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 99.8 percent, the selectivity of the 3, 4-dichloroaniline is 99.2 percent, and the reaction time is 45 minutes.
Example 15
0.5g of the catalyst of example 1, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 325nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 100%, and the reaction time is 25 minutes.
Example 16
0.5g of the catalyst from example 5, 40 g of 3, 4-dichloronitrobenzene, and 15mL of methanol solvent were placed in a UV lampSealing the reaction kettle in a high-pressure hydrogenation reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, starting stirring, controlling ultraviolet wavelength at 325nm, power at 225W, and radiation intensity at 3820 μ W/cm2,The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 99.8 percent, the selectivity of the 3, 4-dichloroaniline is 99.94 percent, and the reaction time is 35 minutes.
Example 17
0.5g of the catalyst of example 6, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 99.96%, and the reaction time is 35 minutes.
Example 18
0.5g of the catalyst of example 10, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 99.94%, and the reaction time is 45 minutes.
Example 19
0.5g of the catalyst of example 1 and 25 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, and air is replaced by nitrogenReplacing nitrogen with hydrogen, stirring, controlling ultraviolet wavelength at 350nm, power at 250W, and radiation intensity at 3980 μ W/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 120 ℃ and the hydrogen pressure is 1.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3, 4-dichloroaniline is 99.96 percent, and the reaction time is 120 minutes.
Example 20
0.5g of the catalyst of example 8 and 50 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 280nm, the power is 200W, and the radiation intensity is 3660 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 0.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 99.8 percent, the selectivity of the 3, 4-dichloroaniline is 99.94 percent, and the reaction time is 120 minutes.
Example 21
0.5g of the catalyst of example 1 and 40 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 90 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3, 4-dichloroaniline is 99.96 percent, and the reaction time is 80 minutes.
Example 22
0.5g of the catalyst of example 7 and 40 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 350nm, the power is 250W,the radiation intensity is 3980 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 120 ℃ and the hydrogen pressure is 1.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 99.7 percent, the selectivity of the 3, 4-dichloroaniline is 99.94 percent, and the reaction time is 120 minutes.
Example 23
0.5g of the catalyst of example 8 and 25 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100 percent, the selectivity of the 3, 4-dichloroaniline is 99.95 percent, and the reaction time is 120 minutes.
Comparative example 4
0.5g of the catalyst of comparative example 1 and 25 g of 3, 4-dichloronitrobenzene are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 315nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 92%, the selectivity of 3, 4-dichloroaniline is 94%, and the reaction time is 250 minutes.
Comparative example 5
0.5g of the catalyst of comparative example 2, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 325nm, the power is 225W, and the radiation intensity is 3820 muW/cm2At a temperature of 80 ℃ and a hydrogen pressure of 1MPaHydrogenation reaction is carried out. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 100%, the selectivity of 3, 4-dichloroaniline is 95.6%, and the reaction time is 225 minutes.
Comparative example 6
0.5g of the catalyst of comparative example 3, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is closed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 325nm, the power is 225W, and the radiation intensity is 3820 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 97,9 percent, the selectivity of 3, 4-dichloroaniline is 93.7 percent, and the reaction time is 215 minutes.
Comparative example 7
0.5g of the catalyst of example 1, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 364nm, the power is 275W, and the radiation intensity is 4070 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 20 minutes at constant temperature and constant pressure, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and the analysis result is as follows: the reaction conversion rate is 98.7%, the selectivity of 3, 4-dichloroaniline is 94.9%, and the reaction time is 250 minutes.
Comparative example 8
0.5g of the catalyst of example 1, 40 g of 3, 4-dichloronitrobenzene and 15mL of methanol solvent are put into an ultraviolet irradiation high-pressure hydrogenation reaction kettle, the reaction kettle is sealed, air is replaced by nitrogen, then the nitrogen is replaced by hydrogen, stirring is started, the wavelength of ultraviolet light is controlled to be 240nm, the power is 175W, and the radiation intensity is 3480 muW/cm2The hydrogenation reaction is carried out under the conditions that the temperature is 80 ℃ and the hydrogen pressure is 1 MPa. When the pressure in the kettle is not lowerAnd (3) reducing, continuing stirring at constant temperature and constant pressure for 20 minutes, stopping the reaction, filtering and separating the hydrogenation liquid and the catalyst filter cake, and obtaining an analysis result as follows: the reaction conversion rate is 96.3 percent, the selectivity of the 3, 4-dichloroaniline is 92.8 percent, and the reaction time is 244 minutes.
Comparative examples 9 to 19
Comparative examples 9 to 19 show the results of the catalytic hydrogenation of 3, 4-dichloronitrobenzene using the catalyst of example 1 in the absence of light under the other reaction conditions described in examples 13 to 23, respectively, as shown in the following table.
Examples Conversion rate% Selectivity% Reaction time min
Comparative example 9 97.68 97.29 190
Comparative example 10 94.42 96.36 250
Comparative example 11 98.66 99.98 80
Comparative example12 97.25 97.25 210
Comparative example 13 97.45 97.34 210
Comparative example 14 96.12 96.58 200
Comparative example 15 97.23 95.85 400
Comparative example 16 90.21 92.47 400
Comparative example 17 94.82 95.15 200
Comparative example 18 96.52 94.47 350
Comparative example 19 93.44 95.13 350
Example 24
Example 24 is the results of using the catalyst of example 1 in the catalytic hydrogenation of 3, 4-dichloronitrobenzene in multiple applications under light conditions, reaction conditions referred to the reaction conditions of example 15, as shown in the following table.
Figure BDA0001707211990000161
Figure BDA0001707211990000171

Claims (9)

1. A preparation method of a photo-thermal catalytic hydrogenation catalyst comprises a mesoporous carbon microsphere carrier, and carbon quantum dots and metal quantum dots which are loaded on the surface of the carrier, wherein the size of the catalyst is 50-100 nm, the particle size range of the carbon quantum dots is 4.5-6.5 nm, the metal quantum dots are one or the combination of two of palladium quantum dots and platinum quantum dots, and the particle size range of the metal quantum dots is 10-15 nm; in the catalyst, the mass fractions of the carbon quantum dots and the metal quantum dots are respectively 10-30% and 1-2%;
the preparation method comprises the following steps:
1) carrying out polycondensation reaction in an alcohol-water solution system by using 3-aminophenol and formaldehyde as carbon source precursors and ammonia water as a catalyst to obtain polymer microspheres;
2) preparing mixed slurry from the polymer microspheres obtained in the step 1) and deionized water, placing the prepared mixed slurry into a microwave digestion instrument, carrying out microwave reaction for 20-30 minutes at 180-210 ℃, cooling, taking out the mixed slurry, and carrying out vacuum drying to obtain the polymer microspheres modified by the carbon quantum dots, wherein the carbon quantum dots are distributed on the surfaces of the polymer microspheres and have particle sizes ranging from 4.5 nm to 6.5 nm;
3) loading metal salt to the carbon quantum dot modified polymer microspheres obtained in the step 2) through wet impregnation, and drying to obtain a catalyst precursor;
4) calcining and cooling the catalyst precursor obtained in the step 3) in an inert atmosphere to obtain the photo-thermal catalytic hydrogenation catalyst, wherein the calcining process is a temperature programming process: raising the temperature from room temperature to 200-300 ℃ at a heating rate of 0.5-3.5 ℃/min, and keeping the temperature for 1-4 hours; raising the temperature from 200-300 ℃ to 400-600 ℃ at a heating rate of 3.5-8.5 ℃/min, and keeping the temperature for 3-6 hours.
2. The method of claim 1, wherein: step 1) was carried out as follows: preparing a mixed solution consisting of 20-25% by mass of ammonia water, alcohol, deionized water, 3-aminophenol and 33-38% by mass of formaldehyde aqueous solution, wherein the volume ratio of the ammonia water to the formaldehyde aqueous solution to the alcohol to the deionized water is 1: 2-8: 20-60: 70-100, and the molar ratio of the 3-aminophenol to the formaldehyde is 1: 2-5; stirring the prepared mixed solution at room temperature for 2-10 h, transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100-300 ℃ for 12-48 h, and drying to obtain the polymer microspheres.
3. The method of claim 1, wherein: in the step 2), the feeding ratio of the polymer microspheres to the deionized water is 1g: 10-25 ml; the vacuum drying conditions were: and drying the mixed slurry obtained by the microwave method for 12-48 hours at the temperature of 20-80 ℃ under the relative vacuum degree of-0.099-0.05 MPa.
4. The method of claim 1, wherein: in the step 3), the metal salt is one or more of the following combinations: palladium nitrate, chloropalladic acid, ethylenediamine palladium chloride, ammonium tetrachloropalladate, sodium chloropalladate, tetraamminepalladium nitrate, tetraamminepalladium bicarbonate, chloroplatinic acid, platinum nitrate, sodium chloroplatinate, tetraammineplatinum nitrate, dinitrosoplatinum, potassium trichloroammine platinate and sodium hexachloroplatinate; the step 3) is carried out as follows: preparing an aqueous solution of metal salt with the metal mass concentration of 0.001-0.05 g/mL, mixing the polymer microsphere modified by the carbon quantum dots, the aqueous solution of the metal salt and deionized water obtained in the step 2), wherein the feeding ratio of the polymer microsphere modified by the carbon quantum dots, the aqueous solution of the metal salt and the deionized water is 1g: 5-20 mL: 10-25 mL, and drying an impregnated sample after impregnating for 5-10 hours to obtain a catalyst precursor.
5. The photo-thermal catalytic hydrogenation catalyst prepared by the preparation method of claim 1 is applied to the reaction of synthesizing 3, 4-dichloroaniline shown in formula II by selective catalytic hydrogenation of 3, 4-dichloronitrobenzene shown in formula I under the irradiation of ultraviolet light of 280-350 nm;
Figure FDA0002956893690000021
6. the use of claim 5, wherein: the application method of the catalyst comprises the following steps:
the method comprises the steps of putting a photo-thermal catalytic hydrogenation catalyst and 3, 4-dichloronitrobenzene shown in a formula I into a high-pressure hydrogenation reaction kettle with ultraviolet irradiation, sealing the reaction kettle, replacing air with nitrogen, replacing nitrogen with hydrogen at the pressure of 0.5-1.5MPa, opening a heating bond of the reaction kettle, heating to 30-120 ℃, opening a 280-350 nm ultraviolet lamp for irradiation after the temperature is stable, starting stirring to start reaction, continuing stirring at constant temperature and constant pressure for a period of time when the pressure in the kettle does not decrease, stopping stirring, cooling to room temperature, opening the kettle, taking out hydrogenation liquid, and separating and treating the hydrogenation liquid to obtain the 3, 4-dichloroaniline shown in a formula II.
7. The use of claim 6, wherein: the feeding mass ratio of the compound shown in the formula I to the photo-thermal catalytic hydrogenation catalyst is 100: 0.5 to 4.
8. The use of claim 6, wherein: carrying out hydrogenation reaction on the compound shown in the formula I in the presence of a solvent or in the absence of the solvent; when the solvent-free hydrogenation reaction is carried out, firstly, the raw material is preheated and melted to be in a liquid state, and then the temperature is raised to the reaction temperature for hydrogenation reaction; when the hydrogenation reaction with the solvent is carried out, the solvent is methanol or ethanol.
9. The use of claim 6, wherein: the irradiation wavelength range of the ultraviolet lamp is 280-350 nm, the power is 200-250W, and the radiation intensity is 3660-3980 muW/cm2
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