CN109174175B - Composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots, and preparation and application thereof - Google Patents
Composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots, and preparation and application thereof Download PDFInfo
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- CN109174175B CN109174175B CN201810664880.0A CN201810664880A CN109174175B CN 109174175 B CN109174175 B CN 109174175B CN 201810664880 A CN201810664880 A CN 201810664880A CN 109174175 B CN109174175 B CN 109174175B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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Abstract
The invention discloses a mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dot composite catalyst, and a preparation method and application thereof, wherein the catalyst consists of a mesoporous carbon microsphere carrier, surface functionalized carbon quantum dots and metal palladium, wherein the surface functionalized carbon quantum dots and the metal palladium are supported on the carrier; the surface functionalized carbon quantum dots and the metal palladium form a snowflake dispersed in each piece on the surface of the carrier, the center of each snowflake is the surface functionalized carbon quantum dot which is directly loaded on the carrier and has the size of not more than 10nm, the metal palladium takes the surface functionalized carbon quantum dots as an anchoring position and grows around the surface functionalized carbon quantum dots in a flake form to form a snowflake shape, and the size of each snowflake is between 40nm and 100 nm; the surface functionalized carbon quantum dot is characterized in that an N-containing functional group is introduced to the surface of the carbon quantum dot, and the N-containing functional group is one or more of amino, pyridine nitrogen, pyrrole nitrogen and graphite nitrogen. The invention provides application of the catalyst in the reaction of synthesizing crotyl alcohol by selective catalytic hydrogenation of crotonaldehyde.
Description
(I) technical field
The invention relates to a mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dot composite catalyst, a preparation method thereof and application thereof in preparing crotyl alcohol through selective catalytic hydrogenation of crotonaldehyde.
(II) technical background
Crotonaldehyde is a representative α, β -unsaturated aldehyde, and a series of products such as butyraldehyde, crotyl alcohol, enol, butanol, etc. can be obtained by hydrogenating crotonaldehyde. The crotyl alcohol, which is a selective hydrogenation product of C ═ O, has wide application value and can be used in the synthesis of spices, medicines, fine chemicals and the like. Currently, the commonly used methods for preparing crotyl alcohol include lithium aluminum hydride reduction, sodium borohydride reduction, and metal catalytic hydrogenation. However, the former two methods have the disadvantages of high price, difficult product separation, high energy consumption, complex equipment and the like. Therefore, the metal catalytic hydrogenation method has wide development prospect due to the advantages of green safety, less side reaction, simple equipment and the like.
However, from the thermodynamic viewpoint, since the bond energy of C ═ O is 715.0kJ/mol, the bond energy of C ═ C is 615.0kJ/mol, and a conjugation effect exists between the two, selective hydrogenation of C ═ O is difficult. Therefore, in order to selectively produce crotonaldehyde into crotyl alcohol, which is a C ═ O hydrogenation product, higher requirements are placed on catalysts and equipment, and it is very important to research catalysts with high activity and high selectivity. Common alpha, beta-unsaturated aldehyde selective hydrogenation metal catalysts include Os, Rh, Pt, Co, Au and the like. Although their catalytic activity is relatively high, the selectivity is generally low. Researchers have generally solved the problem of not only adding promoters (Van Broekhoven E.H.PonecV.Surface chemistry of small particulate [ J ]. Surf.Sci.,1985,162(1-3):731-741), modifying catalyst Supports (Planex J M., Count N., Brotons V., Kumbrar P.S., Dutartre R., Genete P., Ajayan P.M.application Caron Nano particulate in heterogenous particulate catalysts [ J ], J.Am.Chem.Soc.,1994,116(17):7935-7936), modifying the spatial structure of metals (Richard D, Fouillux P., Galparticulate P.structural and chemical in purity) but also increasing the cost of these processes (plant C., filtration, plant C., origin) 1088. plant, C.1088. the cost of these processes is increased by adding promoters.
Carbon Quantum Dots (CQDs) are a novel carbon nano fluorescent material with a sphere-like structure and the size of the carbon nano fluorescent material is less than 10 nm. It has the advantages of stable chemical property, low cost, good water solubility, good fluorescence, low cytotoxicity, easy functionalization, etc. Among them, the high-efficiency electron storage and transfer capability of carbon dots makes it attract attention in the fields of catalysts, capacitor materials, and the like. The surface functionalization is carried out on the carbon quantum dots, namely various heteroatoms or groups are introduced to modify the surfaces of the carbon quantum dots. Various groups introduced by surface functionalization can interact with palladium, so that metal active components can be effectively dispersed, the interaction is enhanced, and the metal loss is reduced. The doping of heteroatoms such as N and S can enable the heteroatoms to contain a large number of basic groups (amino, pyridine nitrogen, pyrrole nitrogen, graphite nitrogen, S heterocyclic rings and the like) to modulate surface power supply centers. And junction boundaries and channels can be formed between the metal particles, electron transmission is accelerated, and the metal particles are greatly helped to control the size of the metal particles, so that the metal active component can be promoted to better play a role.
The invention introduces the surface functionalized carbon quantum dots into the catalyst system, can greatly improve the selectivity of the reaction, and simultaneously can improve the stability and the recycling performance of the Pd catalyst and obviously reduce the production cost.
Disclosure of the invention
The first purpose of the present invention is to provide a composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots, wherein the surface functionalized carbon quantum dots are introduced into the catalyst, and the surface functionalization of the carbon dots can not only promote the combination of the mesoporous carbon microsphere supported palladium and the mesoporous carbon microsphere, but also modulate the morphology and electronic characteristics of metal particles, accelerate electron transmission, and greatly help to control the size of the metal particles, thereby promoting the metal active components to better perform functions.
The second purpose of the invention is to provide a preparation method of the composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots, which has the advantages of high metal loading efficiency, uniform metal dispersion, uniform size, difficult metal loss and the like.
The third purpose of the invention is to provide the application of the mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dot composite catalyst in the reaction of synthesizing crotyl alcohol by selective catalytic hydrogenation of crotonaldehyde, wherein the composite catalyst has high catalytic activity, selectivity and reaction rate.
In order to achieve the purpose, the invention adopts the following scheme:
a composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots comprises a mesoporous carbon microsphere carrier, and surface functionalized carbon quantum dots and metal palladium which are supported on the carrier; the size of the mesoporous carbon catalyst is between 400nm and 1 mu m; the surface functionalized carbon quantum dots and the metal palladium form a snowflake dispersed in each piece on the surface of the carrier, the center of each snowflake is the surface functionalized carbon quantum dot which is directly loaded on the carrier and has the size of not more than 10nm, the metal palladium takes the surface functionalized carbon quantum dots as an anchoring position and grows around the surface functionalized carbon quantum dots in a flake form to form a snowflake shape, and the size of each snowflake is between 40nm and 100 nm; the surface functionalized carbon quantum dot is characterized in that an N-containing functional group is introduced to the surface of the carbon quantum dot, and the N-containing functional group is one or more of amino, pyridine nitrogen, pyrrole nitrogen and graphite nitrogen; in the catalyst, the mass fraction (load) of metal palladium is not higher than 10.0 wt%, and the mass fraction (load) of the surface functionalized carbon quantum dots is 2-35 wt%.
Further, the mass fraction of the carbon quantum dots is preferably 5% to 30%.
Further, the mass fraction of metallic palladium is preferably 0.5% to 5%.
The invention also provides a preparation method of the composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots, which comprises the following steps:
1) carrying out polycondensation reaction by taking 3-aminophenol and formaldehyde as carbon source precursors in an ethanol-water solution system by taking ammonia water as a catalyst and F127 as a template agent to obtain F127/3-aminophenol-formaldehyde polymer microspheres;
2) preparing a chloropalladate solution;
3) preparing a surface functionalized carbon quantum dot, wherein the surface functionalized carbon quantum dot is formed by introducing an N-containing functional group on the surface of the carbon quantum dot, and the N-containing functional group is one or the combination of any more of amino, pyridine nitrogen, pyrrole nitrogen and graphite nitrogen;
4) loading the surface functionalized carbon quantum dots in the step 2) on F127/3-aminophenol-formaldehyde polymer microspheres by adopting wet impregnation, then roasting at the temperature of 600 ℃ in a nitrogen atmosphere to obtain mesoporous carbon microspheres loaded with the surface functionalized carbon quantum dots, and then loading palladium in a chloropalladate solution on a mesoporous carbon microsphere carrier by adopting an ultraviolet light reduction method, thereby obtaining the mesoporous carbon microsphere-loaded palladium and surface functionalized carbon quantum dot composite catalyst.
The preparation of the F127/3-aminophenol-formaldehyde polymer microsphere belongs to the prior art, and the preparation is specifically recommended to be carried out according to the following steps: taking deionized water, ethanol, F127 and an ammonia water solution with the mass concentration of 25-28%, mixing and stirring for 0.5-2h until the F127 is completely dissolved; then adding 3-aminophenol, and continuing stirring for 0.5-2 hours until the 3-aminophenol is completely dissolved; slowly adding 37-40% formaldehyde solution, and stirring for 12-48 h; then stopping stirring, and carrying out hydrothermal treatment at the temperature of 80-200 ℃ for 12-48 h; then filtering and drying at 40-80 ℃ to obtain brick red polymer solid powder, namely the F127/3-aminophenol-formaldehyde polymer microspheres. Wherein the feed ratio is recommended as follows: water: ethanol: f127: ammonia water solution: 3-aminophenol: 60-80 ml of formaldehyde solution: 25-35 ml: 0.2-1.5 g: 0.5-2 ml: 2.5-3.5 g: 4-6 ml.
The surface functionalized carbon quantum dot can also be prepared by adopting a method reported in the literature, and the following preparation method is specifically recommended: 1-5 parts by mass: 10-25: 0.1-0.5, adding citric acid, deionized water and N-containing substances into a hydrothermal kettle, wherein the N-containing substances can be selected from one or more of the following combinations: ammonia water, ethylenediamine, urea, glycine, alanine, serine, lysine, glutamic acid, tryptophan, tyrosine, histidine, leucine and aspartic acid are subjected to hydrothermal reaction at 180-220 ℃ for 5-12h, then a hydrothermal sample is taken out and dissolved in water, then the water solution is filled into a dialysis bag with the cut-off molecular weight of 1000, 3500 or 7000 for dialysis until the solution outside the bag has no obvious color, and the solution outside the bag after dialysis is collected because the size of the carbon quantum dots outside the bag is more uniform, so that the water solution with the surface functionalized carbon quantum dots is obtained. The carbon quantum dots prepared by the method can emit blue and bluish-violet fluorescence under 365nm ultraviolet light. The concentration of the aqueous solution of the surface functionalized carbon quantum dots is preferably 0.14-1.20 wt%.
The chloropalladate solution is prepared by a conventional method, such as: weighing palladium chloride, adding a proper amount of water, placing the palladium chloride into a hot water bath at 70 ℃, placing a certain volume of hydrochloric acid solution into a beaker, stirring, pouring the dissolved part into a volumetric flask, continuously adding hydrochloric acid into the undissolved part for dissolving, and finally adding water into the solution in the volumetric flask for diluting to the required concentration to obtain the chloropalladate solution. The concentration of the chloropalladate solution is preferably 0.01-0.05 g/ml in terms of palladium mass concentration.
In the step 4), the surface functionalized carbon quantum dots in the step 2) are loaded on the F127/3-aminophenol-formaldehyde polymer microspheres by wet impregnation, wherein the mass ratio of the aqueous solution of the surface functionalized carbon quantum dots to the feeding of the F127/3-aminophenol-formaldehyde polymer microspheres is 20-100 ml: 0.5-4.5 g.
In step 4), the operation method of the ultraviolet reduction method is as follows: placing mesoporous carbon microspheres loaded with surface functionalized carbon quantum dots into a reaction container, adding deionized water and methanol into the reaction container, then adding a certain amount of palladium chloride palladium acid solution with the mass concentration of 0.01-0.05 g/ml, irradiating and stirring for 1-10h under an ultraviolet lamp of 100-500w, filtering, washing and vacuum drying; wherein the mesoporous carbon microsphere loaded with the surface functionalized carbon quantum dots comprises the following components: deionized water: methanol: chloropalladate solution 0.5-2 g: 40-160 mL: 10-40 mL: 0.1-4 mL.
The invention further provides application of the mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dot composite catalyst in the reaction of synthesizing crotyl alcohol by selective catalytic hydrogenation of crotonaldehyde.
Specifically, the application method of the catalyst comprises the following steps: putting crotonaldehyde and mesoporous carbon microsphere-supported palladium and surface functionalized carbon quantum dot composite catalyst into a high-pressure hydrogenation reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle (preferably for 10-15 times) with hydrogen, heating to 30-120 ℃, ensuring that materials in the kettle are in a molten or solution state, charging hydrogen until the pressure in the kettle is 0.2-2.5 MPa, starting stirring, starting the reaction, continuing stirring at constant temperature and constant pressure for a period of time when the pressure in the kettle does not decrease, then stopping stirring and cooling to room temperature, opening the kettle, and taking out the hydrogenation liquid.
Further, the reaction of the present invention may be carried out in the absence of a solvent or in the presence of a solvent. Suitable solvents are: one or more than two mixed solvents in any proportion of n-hexane, isopropanol, Tetrahydrofuran (THF), isobutanol, sec-butanol, methanol, ethanol, water, butane, n-propanol, ethylbenzene, tert-butanol, toluene, n-butanol, n-butane and Dimethylformamide (DMF).
Furthermore, the feeding ratio of the crotonaldehyde to the catalyst of the mesoporous carbon microsphere supported palladium and the surface functionalized carbon quantum dots is 100: 1-10.
In the present invention, "snowflakes" on the surface of the catalyst are visual depictions of a snowflake-like structure that looks like snowflakes, and do not mean that the topographical structure must also have the hexagonal structure that snowflakes typically have.
Compared with the prior art, the invention has the beneficial effects that:
1) the surface modified carbon quantum dots are introduced into the catalyst, and the surface modified carbon quantum dots and the metal palladium are compounded to form a snowflake-shaped appearance. The surface modification leads hetero atoms and groups to be introduced on the surfaces of the carbon points, so that the combination of the carbon points and a mesoporous carbon carrier can be promoted, the surface power supply center can be modulated, the electron transmission is accelerated, the active component palladium can be better exerted, the selectivity and the conversion rate of crotyl alcohol generated by selective hydrogenation of crotonaldehyde and the rate of selective hydrogenation reaction are improved, and the catalyst has good stability.
2) The loading metal adopts an ultraviolet reduction method, and the method has the advantages of high loading efficiency, uniform metal dispersion, uniform size, difficult metal loss and the like.
3) The catalyst synthesized by the method has good stability and mild conditions in the use process, and can be recycled for a plurality of times.
(IV) description of the drawings
Fig. 1 and 2 are a TEM image and a partial enlarged view of a TEM of the catalyst prepared in example 1, respectively.
(V) detailed description of the preferred embodiments
Example 1
Taking 65ml of deionized water, 25ml of ethanol, 0.2g F127 and 1ml of 25-28% ammonia water solution, mixing and stirring for 1 hour until F127 is completely dissolved. Then 3.2g of 3-aminophenol were added and stirring was continued for 0.5h until the 3-aminophenol was completely dissolved. 4ml of 37-40% formaldehyde solution is slowly added and stirred for 24 h. Then stirring is stopped, and the mixture is hydrothermal for 24 hours at the temperature of 100 ℃. Then filtering and drying at 60 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 1g of citric acid, 10ml of deionized water and 0.2g of ethylenediamine, putting the citric acid, the deionized water and the ethylenediamine into a hydrothermal kettle, carrying out hydrothermal treatment at 200 ℃ for 10 hours, taking out a sample after the hydrothermal treatment, and fixing the volume to a 100ml volumetric flask to obtain the surface functionalized carbon quantum dot aqueous solution. Then 50ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length is cut out firstly, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 50ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-5h, collecting the solution outside the bag each time, dialyzing for three days totally, and spin-steaming the collected solution outside the bag to about 50ml, wherein the mass fraction of CQDs is 1.20 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.1g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And heating the evaporated sample to 400 ℃ at a heating rate of 1 ℃/min, roasting at 400 ℃ for 6h in a nitrogen atmosphere, and thus obtaining the carbon spheres loaded with carbon dots.
0.5g of carbon-point-supported carbon spheres are placed in a beaker, 10ml of methanol, 40ml of deionized water and 1ml of chloropalladate solution with palladium concentration of 0.01g/ml are added, and the mixture is stirred for 2 hours under the irradiation of a 100w ultraviolet lamp. Then filtering, washing and vacuum drying for 3h at 100 ℃ to obtain the mesoporous carbon microsphere supported palladium and the surface functionalized CQDs catalyst. As shown in figure 1, each snow flake is distributed on the surface of the mesoporous carbon microsphere, each snow flake contains a carbon quantum dot, and the flaky metal palladium grows around the carbon quantum dot as an anchoring point to form a snowflake-shaped appearance.
TEM analysis shows that the catalyst size is 960-990nm, the carbon dot size is 2-4 nm, and the size of the snowflake is 41-45 nm; ICP analysis, palladium loading was 1.99 wt%; the carbon point loading was 34.63 wt% by TG analysis; the carbon dot surface contained pyridine nitrogen and amino groups by combined FTIR and XPS analysis.
Example 2
60ml of deionized water, 28ml of ethanol, 0.8g F127 and 0.8ml of 25-28% ammonia water solution are mixed and stirred for 0.5h until F127 is completely dissolved. Then 3.5g of 3-aminophenol was added and stirring was continued for 1h until the 3-aminophenol was completely dissolved. 6ml of 37-40% formaldehyde solution is slowly added and stirred for 12 h. Then stirring is stopped, and the mixture is hydrothermal for 24 hours at the temperature of 100 ℃. Then filtering and drying at 80 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 5g of citric acid, 15ml of deionized water, 0.05g of urea and 0.05g of ammonia water, putting the mixture into a hydrothermal kettle, carrying out hydrothermal treatment at 190 ℃ for 11h, taking out a sample after the hydrothermal treatment, and carrying out constant volume treatment in a volumetric flask of 250ml to obtain the surface functionalized carbon quantum dot aqueous solution. Then 50ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length and a molecular weight cutoff of 1000 is cut out, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 50ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. All collected solution outside the bag was then spin-evaporated to about 50ml more, at which point the mass fraction of CQDs was 0.48 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 0.5g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 600 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.2g of carbon-point-supported carbon spheres are placed in a beaker, 10ml of methanol, 40ml of deionized water and 0.5ml of 0.03 g/ml chloropalladate solution are added, and the mixture is stirred for 1 hour under the irradiation of a 300w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
TEM analysis shows that the catalyst has a size of 986-1000nm, the carbon dot size is 1-2 nm, and the size of the snowflake is 56-57 nm; ICP analysis, palladium loading was 7.42 wt%; the carbon point loading was 33.33 wt% by TG analysis; the carbon dot surface contained pyridine nitrogen graphite nitrogen by FTIR and XPS combined analysis.
Example 3
And (3) mixing and stirring 80ml of deionized water, 26ml of ethanol, 1.5g F127 and 0.5ml of 25-28% ammonia water solution for 2 hours until the F127 is completely dissolved. Thereafter, 2.8g of 3-aminophenol were added and stirring was continued for 2 hours until the 3-aminophenol was completely dissolved. Then 5ml of 37-40% formaldehyde solution is slowly added and stirred for 48 h. Then stirring is stopped, and the mixture is hydrothermal for 48 hours at 100 ℃. Then filtering and drying at 70 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 0.5g of citric acid, 12ml of deionized water and 0.3g of glycine, putting the mixture into a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 12 hours, taking out a sample after the hydrothermal treatment, and fixing the volume to a volumetric flask of 250ml to obtain the surface functionalized carbon quantum dot aqueous solution. Then 100ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length and a molecular weight cutoff of 7000 is cut out, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 100ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. All collected solution outside the bag was then spin-evaporated to about 50ml more, at which point the mass fraction of CQDs was 0.96 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 2.2g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 250 ℃ for 6h in a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon ball loaded with the carbon dots.
1g of carbon-point-supported carbon spheres are put into a beaker, 40ml of methanol, 160ml of deionized water and 0.1ml of 0.05g/ml chloropalladate solution are added, and the mixture is stirred for 4 hours under the irradiation of a 300w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
According to TEM analysis, the size of the catalyst is 402-416 nm, the size of the carbon dots is 3-5 nm, and the size of the snowflakes is 85-88 nm; ICP analysis, palladium loading was 0.5 wt%; the carbon point loading was 11.47 wt% by TG analysis; the carbon dot surface contained pyridine nitrogen and pyrrole nitrogen by XPS analysis.
Example 4
75ml of deionized water, 30ml of ethanol, 0.6g F127 and 1.2ml of 25-28% ammonia water solution are mixed and stirred for 1.5 hours until the F127 is completely dissolved. Thereafter, 2.9g of 3-aminophenol were added and stirring was continued for 1 hour until the 3-aminophenol was completely dissolved. 4.5ml of 37-40% formaldehyde solution is slowly added and stirred for 24 h. Then stirring is stopped, and the mixture is hydrothermal for 12 hours at 100 ℃. Then filtering and drying at 40 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 3g of citric acid, 11ml of deionized water, 0.1g of alanine and 0.1g of lysine, putting the citric acid, the deionized water, the alanine and the lysine into a hydrothermal kettle, carrying out hydrothermal treatment at 200 ℃ for 11 hours, taking out a hydrothermal sample, and carrying out constant volume treatment on the sample to a volumetric flask of 100ml to obtain the surface functionalized carbon quantum dot aqueous solution. Then taking out 20ml of carbon quantum dot aqueous solution for dialysis, firstly cutting a dialysis bag with a certain length and molecular weight cutoff of 1000, and boiling for 2h in boiling water. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 20ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added to the beaker to start dialysis and start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. All collected solution outside the bag was then spin-evaporated to about 50ml more, at which point the mass fraction of CQDs was 0.48 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.6g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 400 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.8g of carbon-point-supported carbon spheres are put into a beaker, 15ml of methanol, 60ml of deionized water and 4ml of 0.02g/ml chloropalladate solution are added, and the mixture is stirred for 4 hours under the irradiation of a 500w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
According to TEM analysis, the size of the catalyst is 589-603 nm, the size of the carbon dots is 4-5 nm, and the size of the snowflakes is 67-70 nm; ICP analysis, palladium loading was 10 wt%; the carbon point loading was 5.88 wt% by TG analysis; the carbon dot surface contained pyrrole nitrogen and amino groups as analyzed by XPS.
Example 5
Taking 68ml of deionized water, 35ml of ethanol, 1.5g F127 and 1.5ml of 25-28% ammonia water solution, mixing and stirring for 1 hour until F127 is completely dissolved. Thereafter, 2.6g of 3-aminophenol were added and stirring was continued for 2 hours until the 3-aminophenol was completely dissolved. Then 5ml of 37-40% formaldehyde solution is slowly added and stirred for 24 h. Then stirring is stopped, and hydrothermal treatment is carried out for 36h at 100 ℃. Then filtering and drying at 65 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 4g of citric acid, 20ml of deionized water and 0.4g of glutamic acid, putting the citric acid, the deionized water and the glutamic acid into a hydrothermal kettle, carrying out hydrothermal treatment at 215 ℃ for 6 hours, taking out a sample after the hydrothermal treatment, and fixing the volume to a 500ml volumetric flask to obtain the surface functionalized carbon quantum dot aqueous solution. Then 30ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length and a molecular weight cutoff of 7000 is cut out, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 30ml of carbon quantum dot solution is added into the dialysis bag, so that a gap between 1/3 and 1/2 is reserved on the dialysis bag, and the other end of the dialysis bag is clamped by another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. All collected solution outside the bag was then spin-evaporated to about 50ml more, at which point the mass fraction of CQDs was 0.14 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.3g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 450 ℃ for 6h in a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.6g of carbon sphere loaded with carbon dots is put into a beaker, 10ml of methanol, 40ml of deionized water and 0.2ml of 0.05g/ml chloropalladate solution are added, and the mixture is stirred for 10 hours under the irradiation of a 100w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
According to TEM analysis, the size of the catalyst is 400-409 nm, the size of carbon dots is 3-4 nm, and the size of snowflakes is 40-44 nm; ICP analysis, palladium loading was 1.66 wt%; the carbon point loading was 2 wt% by TG analysis; the carbon dot surface contained pyridine nitrogen, graphite nitrogen and pyrrole nitrogen by the combined analysis of FTIR and XPS.
Example 6
79ml of deionized water, 32ml of ethanol, 1g F127 and 1.1ml of ammonia water solution with the mass concentration of 25-28% are mixed and stirred for 2 hours until F127 is completely dissolved. Thereafter, 2.5g of 3-aminophenol were added and stirring was continued for 1 hour until the 3-aminophenol was completely dissolved. 4ml of 37-40% formaldehyde solution is slowly added and stirred for 20 h. Then stirring is stopped, and the mixture is hydrothermal for 28 hours at the temperature of 100 ℃. Then filtering and drying at 50 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 3g of citric acid, 10ml of deionized water, 0.2g of tryptophan, 0.2g of histidine and 0.1g of alanine, putting the citric acid, the deionized water, the tryptophan, the histidine and the alanine into a hydrothermal kettle, carrying out hydrothermal treatment at 220 ℃ for 5 hours, taking out a sample after the hydrothermal treatment, and fixing the volume to a 100ml volumetric flask to obtain the surface functionalized carbon quantum dot aqueous solution. Then taking out 40ml of carbon quantum dot aqueous solution for dialysis, firstly cutting out a dialysis bag with a certain length and molecular weight cutoff of 1000, and boiling for 2h in boiling water. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 40ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. All collected solution outside the bag was then spin-evaporated to about 50ml more, at which point the mass fraction of CQDs was 0.96 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.7g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 450 ℃ for 6h in a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.8g of carbon sphere loaded with carbon dots is placed in a beaker, 13ml of methanol, 52ml of deionized water and 0.3ml of 0.02g/ml chloropalladate solution are added, and the mixture is stirred for 7 hours under the irradiation of a 300w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
Through TEM analysis, the size of the catalyst is 678-680 nm, the size of the carbon dots is 8-9 nm, and the size of the snowflakes is 96-100 nm; ICP analysis, palladium loading was 0.75 wt%; the carbon point loading was 14.76 wt% by TG analysis; the carbon dot surface contained pyrrole nitrogen by a combined analysis of FTIR and XPS.
Example 7
88ml of deionized water, 27ml of ethanol, 1.2g F127 and 2.0ml of 25-28% ammonia water solution are mixed and stirred for 0.5h until F127 is completely dissolved. Then 3.1g of 3-aminophenol was added and stirring was continued for 1h until the 3-aminophenol was completely dissolved. Then 5.5ml of 37-40% formaldehyde solution is slowly added and stirred for 12 h. Then stirring is stopped, and the mixture is hydrothermal for 24 hours at the temperature of 100 ℃. Then filtering and drying at 80 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
2g of citric acid, 18ml of deionized water and 0.1g of tyrosine are taken to be put into a hydrothermal kettle, hydrothermal is carried out for 11 hours at 185 ℃, then a sample after hydrothermal is taken out and is subjected to constant volume to be put into a volumetric flask of 250ml, and the carbon quantum dot aqueous solution with functionalized surface is obtained. Then taking out 60ml of carbon quantum dot aqueous solution for dialysis, firstly cutting out a dialysis bag with a certain length and a molecular weight cutoff of 3500, and boiling for 2h in boiling water. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 60ml of carbon quantum dot solution is added into the dialysis bag, so that a gap between 1/3 and 1/2 is reserved on the dialysis bag, and the other end of the dialysis bag is clamped by another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. Then, all the collected solution outside the bag was spin-evaporated to about 50ml, at which time the mass fraction of CQDs was 0.58 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 0.9g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 350 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.4g of carbon sphere loaded with carbon dots is put into a beaker, 10ml of methanol, 40ml of deionized water and 0.1ml of chloropalladate solution with 0.04 g/ml are added, and the mixture is stirred for 5 hours under the irradiation of a 100w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
Through TEM analysis, the size of the catalyst is 692-715 nm, the size of the carbon dot is 6-9 nm, and the size of the snowflake is 88-90 nm; ICP analysis, palladium loading was 0.96 wt%; the carbon point loading was 18.42 wt% by TG analysis; the carbon dot surface contained amino, pyridine nitrogen and pyrrole nitrogen by combined FTIR and XPS analysis.
Comparative example 1
And (3) mixing and stirring 80ml of deionized water, 32ml of ethanol, 0.5g F127 and 1ml of 25-28% ammonia water solution until F127 is completely dissolved. Then 3.2g of 3-aminophenol were added and stirring was continued for 1h until the 3-aminophenol was completely dissolved. Then 5ml of 37-40% formaldehyde solution is slowly added and stirred for 20 h. Then stirring is stopped, and the mixture is hydrothermal for 28 hours at the temperature of 100 ℃. Then filtering and drying at 50 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
4.5g of polymer microspheres are roasted for 6h at 450 ℃, and the carbon spheres are obtained in nitrogen atmosphere at the heating rate of 1 ℃/min.
2g of carbon spheres are put into a beaker, 13ml of methanol, 52ml of deionized water and 0.2ml of 0.05g/ml chloropalladate solution are added, and the mixture is stirred for 4 hours under the irradiation of a 300w ultraviolet lamp. And then filtering, washing and drying in vacuum at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium catalyst.
According to TEM analysis, the size of the catalyst is 666-671 nm; the palladium loading was 0.50% by ICP analysis.
Comparative example 2
And (3) mixing and stirring 80ml of deionized water, 32ml of ethanol, 0.5g F127 and 1ml of 25-28% ammonia water solution until the F127 is completely dissolved. Then 3.2g of 3-aminophenol were added and stirring was continued for 1h until the 3-aminophenol was completely dissolved. Then 5ml of 37-40% formaldehyde solution is slowly added and stirred for 12 h. Then stirring is stopped, and the mixture is hydrothermal for 24 hours at the temperature of 100 ℃. Then filtering and drying at 80 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 2g of citric acid and 10ml of deionized water, putting the citric acid and the deionized water into a hydrothermal kettle, carrying out hydrothermal treatment at 190 ℃ for 8 hours, taking out a hydrothermal sample, and fixing the volume of the hydrothermal sample into a volumetric flask of 250ml to obtain a carbon quantum dot aqueous solution. Then taking out 60ml of carbon quantum dot aqueous solution for dialysis, firstly cutting out a dialysis bag with a certain length and a molecular weight cutoff of 3500, and boiling for 2h in boiling water. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, then one end of the dialysis bag is clamped by a clamp, 60ml of carbon quantum dot solution is added into the dialysis bag, a gap ranging from 1/3 to 1/2 is reserved in the dialysis bag, and the other end of the dialysis bag is clamped by another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. Then, all the collected solution outside the bag was spin-evaporated to about 50ml, at which time the mass fraction of CQDs was 0.58 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.5g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 350 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.5g of carbon-point-supported carbon spheres are placed in a beaker, 10ml of methanol, 40ml of deionized water and 0.1ml of 0.05g/ml chloropalladate solution are added, and the mixture is stirred for 3 hours under the irradiation of a 100w ultraviolet lamp. And then filtering, washing and drying in vacuum at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and CQDs composite catalyst.
According to TEM analysis, the size of the catalyst is 732-735 nm, and the size of the carbon dots is 3-5 nm; ICP analysis, palladium loading is 0.90%; the carbon point loading was 14.08 wt% by TG analysis; the carbon dots contain no nitrogen elements and no nitrogen-containing groups through the combined analysis of FTIR and XPS.
Comparative example 3
And (3) mixing and stirring 80ml of deionized water, 32ml of ethanol, 0.5g F127 and 1ml of 25-28% ammonia water solution until the F127 is completely dissolved. Then 3.2g of 3-aminophenol were added and stirring was continued for 1h until the 3-aminophenol was completely dissolved. Then 5ml of 37-40% formaldehyde solution is slowly added and stirred for 12 h. Then stirring is stopped, and the mixture is hydrothermal for 24 hours at the temperature of 100 ℃. Then filtering and drying at 80 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 2g of citric acid, 0.1g of serine and 10ml of deionized water, putting the citric acid, the serine and the deionized water into a hydrothermal kettle, carrying out hydrothermal reaction at 190 ℃ for 8 hours, taking out a sample after the hydrothermal reaction, and fixing the volume to a volumetric flask of 250ml to obtain the carbon quantum dot aqueous solution. Then taking out 60ml of carbon quantum dot aqueous solution for dialysis, firstly cutting out a dialysis bag with a certain length and molecular weight cutoff of 1000, and boiling for 2h in boiling water. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 60ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. Then, all the collected solution outside the bag was spin-evaporated to about 50ml, at which time the mass fraction of CQDs was 0.58 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.4g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 350 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.5g of carbon sphere loaded with carbon dots is put into a beaker, 10ml of methanol, 40ml of deionized water and 0.1ml of chloropalladate solution with 0.05g/ml are added, and the mixture is stirred for 3 hours. And then filtering, washing and drying in vacuum at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and CQDs composite catalyst.
According to TEM analysis, the size of the catalyst is 809-815 nm, and the size of the carbon dots is 7-9 nm; ICP analysis, palladium loading is 0%; the carbon point loading was 14.08 wt% by TG analysis; and through FTIR and XPS combined analysis, the carbon dots contain pyridine nitrogen, graphite nitrogen and pyrrole nitrogen.
Example 8
70ml of deionized water, 31ml of ethanol, 1.3g F127 and 0.6ml of 25-28% ammonia water solution are mixed and stirred for 1 hour until F127 is completely dissolved. Then 3g of 3-aminophenol was added and stirring was continued for 0.5h until the 3-aminophenol was completely dissolved. 6ml of 37-40% formaldehyde solution is slowly added and stirred for 36 h. Then stirring is stopped, and hydrothermal treatment is carried out for 36h at 100 ℃. Then filtering and drying at 60 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
2.5g of citric acid, 25ml of deionized water, 0.1g of serine, 0.1g of leucine and 0.2g of glutamic acid are put into a hydrothermal kettle, hydrothermal is carried out for 12 hours at 195 ℃, and then a sample after hydrothermal treatment is taken out and is subjected to constant volume treatment in a volumetric flask of 250ml, so as to obtain the surface functionalized carbon quantum dot aqueous solution. Then 70ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length and a cut-off molecular weight of 1000 is cut out, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 70ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. Thereafter, all of the collected solution outside the bag was spin-evaporated to about 50ml more, at which time the mass fraction of CQDs was 0.67 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.2g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 500 ℃ for 6h in a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.5g of carbon-point-supported carbon spheres are placed in a beaker, 10ml of methanol, 40ml of deionized water and 1ml of 0.02g/ml chloropalladate solution are added, and the mixture is stirred for 9 hours under the irradiation of a 500w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
According to TEM analysis, the size of the catalyst is 489-501 nm, the size of carbon dots is 7-8 nm, and the size of snowflakes is 47-51 nm; ICP analysis, palladium loading was 3.91 wt%; the carbon point loading was 16.39 wt% by TG analysis; the carbon dot surface contained pyrrole nitrogen, amino and graphite nitrogen by combined FTIR and XPS analysis.
Example 9
And (3) mixing and stirring 80ml of deionized water, 33ml of ethanol, 0.7g F127 and 0.7ml of 25-28% ammonia water solution until the F127 is completely dissolved. Thereafter, 2.7g of 3-aminophenol were added and stirring was continued for 1h until the 3-aminophenol was completely dissolved. 4.8ml of 37-40% formaldehyde solution is slowly added and stirred for 20 h. Then stirring is stopped, and the mixture is hydrothermal for 20 hours at the temperature of 100 ℃. Then filtering and drying at 50 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 2g of citric acid, 14ml of deionized water and 0.5g of aspartic acid, putting the citric acid, the deionized water and the aspartic acid into a hydrothermal kettle, carrying out hydrothermal reaction at 210 ℃ for 8 hours, taking out a sample after the hydrothermal reaction, and fixing the volume to a volumetric flask of 250ml to obtain the surface functionalized carbon quantum dot aqueous solution. Then 55ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length and a molecular weight cutoff of 3500 is cut out, and the dialysis bag is boiled in boiling water for 2 h. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 80ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. Thereafter, all of the collected solution outside the bag was spin-evaporated to about 50ml more, at which time the mass fraction of CQDs was 0.53 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 0.6g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the dried sample at 550 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.2g of carbon-point-supported carbon spheres are placed in a beaker, 10ml of methanol, 40ml of deionized water and 1ml of 0.01g/ml chloropalladate solution are added, and the mixture is stirred for 6 hours under the irradiation of a 300w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
According to TEM analysis, the size of the catalyst is 533-540 nm, the size of the carbon dots is 1-3 nm, and the size of the snowflakes is 58-60 nm; ICP analysis, palladium loading was 35 wt%; the carbon point loading was 12 wt% by TG analysis; the carbon dot surface contained amino groups as analyzed by a combination of FTIR and XPS.
Example 10
66ml of deionized water, 29ml of ethanol, 1.4g F127 and 1.3ml of 25-28% ammonia water solution are mixed and stirred for 1 hour until F127 is completely dissolved. Then 3.3g of 3-aminophenol was added and stirring was continued for 2h until the 3-aminophenol was completely dissolved. Then 5.4ml of 37-40% formaldehyde solution is slowly added and stirred for 25 h. Then stirring is stopped, and the mixture is hydrothermal for 24 hours at the temperature of 100 ℃. Then filtering and drying at 80 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
Taking 4.5g of citric acid, 16ml of deionized water and 0.2g of ammonia water, putting the mixture into a hydrothermal kettle, carrying out hydrothermal treatment at 180 ℃ for 7 hours, taking out a sample after the hydrothermal treatment, and fixing the volume to a 500ml volumetric flask to obtain the surface functionalized carbon quantum dot aqueous solution. Then, 45ml of carbon quantum dot aqueous solution is dialyzed, a dialysis bag with a certain length and a molecular weight cutoff of 7000 is cut out, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. To this was added 45ml of carbon quantum dot solution leaving a gap between 1/3 and 1/2 in the dialysis bag, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. Thereafter, all of the collected solution outside the bag was spin-evaporated to about 50ml more, at which time the mass fraction of CQDs was 0.22 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 0.7g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 420 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.3g of carbon-point-supported carbon spheres are placed in a beaker, 20ml of methanol, 80ml of deionized water and 0.2ml of 0.03 g/ml chloropalladate solution are added, and the mixture is stirred for 8 hours under the irradiation of a 300w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
Through TEM analysis, the size of the catalyst is 556-562 nm, the size of the carbon dots is 2-3 nm, and the size of the snowflakes is 62-65 nm; ICP analysis, palladium loading was 1.87 wt%; the carbon point loading was 8.36 wt% by TG analysis; the carbon dot surface contained pyrrole nitrogen, pyridine nitrogen, amino and graphite nitrogen by FTIR and XPS combined analysis.
Example 11
And (3) mixing and stirring 62ml of deionized water, 34ml of ethanol, 0.3g F127 and 1.4ml of 25-28% ammonia water solution until F127 is completely dissolved. Then 3.5g of 3-aminophenol was added and stirring was continued for 1h until the 3-aminophenol was completely dissolved. Then 5ml of 37-40% formaldehyde solution is slowly added and stirred for 12 h. Then stirring is stopped, and the mixture is hydrothermal for 24 hours at the temperature of 100 ℃. Then filtering and drying at 80 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
1.5g of citric acid, 13ml of deionized water and 0.3g of histidine are put into a hydrothermal kettle, hydrothermal is carried out for 9 hours at 205 ℃, then a sample after hydrothermal is taken out and is subjected to constant volume to a volumetric flask of 100ml, and the surface functionalized carbon quantum dot aqueous solution is obtained. Then 35ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length and a molecular weight cutoff of 7000 is cut out, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 90ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added to the beaker to start dialysis and start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. All collected solution outside the bag was then spin-evaporated to about 50ml more, at which point the mass fraction of CQDs was 0.84 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.3g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 380 ℃ for 6h in a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.5g of carbon-point-supported carbon spheres are placed in a beaker, 30ml of methanol, 120ml of deionized water and 0.3ml of 0.05g/ml chloropalladate solution are added, and the mixture is stirred for 7 hours under the irradiation of a 500w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
According to TEM analysis, the size of the catalyst is 899-907 nm, the size of the carbon dots is 5-7 nm, and the size of the snowflakes is 88-91 nm; ICP analysis, palladium loading was 3 wt%; the carbon point loading was 21.96 wt% by TG analysis; the carbon dot surface contained amino and pyrrole nitrogen by a combined FTIR and XPS analysis.
Example 12
And mixing and stirring 78ml of deionized water, 35ml of ethanol, 0.5g F127 and 1.8ml of 25-28% ammonia water solution until the F127 is completely dissolved. Then 3.4g of 3-aminophenol were added and stirring was continued for 1h until the 3-aminophenol was completely dissolved. 4.9ml of 37-40% formaldehyde solution is slowly added and stirred for 12 h. Then stirring is stopped, and the mixture is hydrothermal for 24 hours at the temperature of 100 ℃. Then filtering and drying at 80 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
And (3) putting 1.2g of citric acid, 18ml of deionized water, 0.2g of tryptophan and 0.1g of glutamic acid into a hydrothermal kettle, carrying out hydrothermal treatment at 208 ℃ for 12h, taking out a hydrothermal sample, and metering the volume of the hydrothermal sample into a volumetric flask of 250ml to obtain the surface functionalized carbon quantum dot aqueous solution. Then 50ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length and a molecular weight cutoff of 1000 is cut out, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 50ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added thereto to start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. All collected solution outside the bag was then spin-evaporated to about 50ml more, at which point the mass fraction of CQDs was 0.48 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 2.1g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 600 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.9g of carbon-point-supported carbon spheres are placed in a beaker, 10ml of methanol, 40ml of deionized water and 2.5ml of 0.03 g/ml chloropalladate solution are added, and the mixture is stirred for 2 hours under the irradiation of a 100w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
According to TEM analysis, the size of the catalyst is 753-760 nm, the size of the carbon dots is 6-8 nm, and the size of the snowflakes is 68-71 nm; ICP analysis, palladium loading was 6.06 wt%; the carbon point loading was 16 wt% by TG analysis; the carbon dot surface contained graphitic nitrogen by a combination of FTIR and XPS analysis.
Example 13
And mixing and stirring 72ml of deionized water, 25ml of ethanol, 0.9g F127 and 0.9ml of 25-28% ammonia water solution for 2 hours until the F127 is completely dissolved. Thereafter, 2.8g of 3-aminophenol were added and stirring was continued for 2 hours until the 3-aminophenol was completely dissolved. Then 5.2ml of 37-40% formaldehyde solution is slowly added and stirred for 30 h. Then stirring is stopped, and the mixture is hydrothermal for 30 hours at 100 ℃. Then filtering and drying at 65 ℃ to obtain brick red solid powder, namely: polymeric microspheres.
3.2g of citric acid, 21ml of deionized water and 0.4g of serine are taken and put into a hydrothermal kettle, hydrothermal is carried out for 10 hours at 200 ℃, then a sample after hydrothermal is taken out and is subjected to constant volume to be a volumetric flask of 500ml, and the carbon quantum dot aqueous solution with functionalized surface is obtained. Then 100ml of carbon quantum dot aqueous solution is taken out for dialysis, a dialysis bag with a certain length and a molecular weight cutoff of 3500 is cut out, and the dialysis bag is boiled in boiling water for 2 hours. Then, the dialysis bag is taken out, the inside and the outside of the dialysis bag are washed by deionized water, and then one end of the dialysis bag is clamped by a clamp. 100ml of carbon quantum dot solution was added to the bag leaving a gap between 1/3 and 1/2, and the other end of the bag was clamped with another clamp. The dialysis bag was slightly pressurized by hand to check for leakage. If no leakage occurs, the dialysis bag is put into a 1000ml large beaker, and an appropriate amount of water is added to the beaker to start dialysis and start dialysis. Changing water every 2-12h, collecting the solution outside the bag every time, and dialyzing for three days. All collected solution outside the bag was then spin-evaporated to about 50ml more, at which point the mass fraction of CQDs was 0.48 wt%. Transferring into a beaker, performing ultrasonic treatment for 15min, adding 1.9g of polymer microspheres, stirring for 5h, and then stirring and evaporating to dryness. And roasting the evaporated sample at 300 ℃ for 6h under a nitrogen atmosphere at a heating rate of 1 ℃/min to obtain the carbon sphere loaded with the carbon dots.
0.7g of carbon-point-supported carbon spheres are placed in a beaker, 10ml of methanol, 40ml of deionized water and 0.6ml of 0.04 g/ml chloropalladate solution are added, and the mixture is stirred for 4 hours under the irradiation of a 300w ultraviolet lamp. And then filtering, washing and vacuum drying at 100 ℃ for 3h to obtain the mesoporous carbon microsphere supported palladium and surface functionalized CQDs composite catalyst, wherein the morphology of the catalyst is similar to that of the catalyst in the embodiment 1.
Through TEM analysis, the size of the catalyst is 933-960 nm, the size of the carbon dots is 3-4 nm, and the size of the snowflakes is 77-80 nm; ICP analysis, palladium loading was 3.4 wt%; the carbon point loading was 7.93 wt% by TG analysis; the carbon dot surface contained amino groups and graphite nitrogen by combined FTIR and XPS analysis.
Example 14
0.01g of the catalyst of example 1, 1g of crotonaldehyde, 25ml of methanol and 29ml of an isopropanol solvent were put into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen 10 times, and hydrogenation was carried out under conditions of a temperature of 50 ℃ and a hydrogen pressure of 0.8 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 crotyl alcohol selectivity is 99.92%, and the reaction time is 36 minutes.
Example 15
0.05g of the catalyst of example 2, 2g of crotonaldehyde and 35ml of an aqueous solvent were put into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen 15 times, and hydrogenation was carried out under conditions of 80 ℃ and 1.5MPa of hydrogen pressure. When the pressure in the kettle does not decrease any more, continuously stirring for 10 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 crotyl alcohol selectivity is 99.88%, and the reaction time is 25 minutes.
Example 16
0.02g of the catalyst of example 3 and 1.5g of crotonaldehyde were charged into a high-pressure hydrogenation reactor, and the reactor was closed, and the air was replaced with hydrogen gas 12 times, and hydrogenation was carried out under conditions of a temperature of 120 ℃ and a hydrogen pressure of 1 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 15 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 crotyl alcohol selectivity is 100%, and the reaction time is 31 minutes.
Example 17
0.05g of the catalyst of example 4, 2.5g of crotonaldehyde, 15ml of n-butane and 11ml of n-hexane were charged as solvents into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen 11 times, and hydrogenation was carried out under conditions of 45 ℃ and 1.0MPa of hydrogen pressure. When the pressure in the kettle does not decrease any more, continuously stirring for 27 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 crotyl alcohol selectivity is 100%, and the reaction time is 28 minutes.
Example 18
0.15g of the catalyst of example 5, 1.5g of crotonaldehyde, and 15ml of dimethylformamide were placed as a solvent in a high-pressure hydrogenation reactor, the reactor was closed, and the air was replaced with hydrogen 10 times, and hydrogenation was carried out under conditions of 60 ℃ and 2MPa of hydrogen pressure. When the pressure in the kettle does not decrease any more, continuously stirring for 16 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 crotyl alcohol selectivity is 100%, and the reaction time is 33 minutes.
Example 19
0.09g of the catalyst of example 6, 3g of crotonaldehyde, 10ml of t-butanol, 10ml of 1 n-butanol and 10ml of isobutanol were charged as solvents into a high-pressure hydrogenation reactor, and the reactor was closed, and the air was replaced with hydrogen gas 13 times, and hydrogenation was carried out under conditions of a temperature of 100 ℃ and a hydrogen pressure of 2.5 MPa. When the pressure in the kettle does not decrease any more, stirring for 26 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 crotyl alcohol selectivity is 100%, and the reaction time is 25 minutes.
Example 20
0.08g of the catalyst of example 7, 2g of crotonaldehyde, and 40ml of tetrahydrofuran were charged into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen 14 times, and hydrogenation was carried out under conditions of a temperature of 90 ℃ and a hydrogen pressure of 0.5 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 18 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 crotyl alcohol selectivity is 100%, and the reaction time is 35 minutes.
Example 21
0.025g of the catalyst of example 8 and 1.8g of crotonaldehyde were charged into a high-pressure hydrogenation reactor, and the reactor was closed, and the air was replaced with hydrogen 15 times, and hydrogenation was carried out under conditions of a temperature of 70 ℃ and a hydrogen pressure of 1.4 MPa. When the pressure in the kettle does not decrease any more, stirring for 19 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 crotyl alcohol selectivity is 100%, and the reaction time is 38 minutes.
Example 22
0.018g of the catalyst of example 9, 1.2g of crotonaldehyde, 10ml of sec-butanol and 12ml of n-propanol were placed in a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen 12 times, and hydrogenation was carried out under conditions of a temperature of 85 ℃ and a hydrogen pressure of 0.2 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 21 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 crotyl alcohol selectivity is 100%, and the reaction time is 32 minutes.
Example 23
0.02g of the catalyst of example 10, 1.3g of crotonaldehyde, 14ml of ethylbenzene and 12ml of toluene were charged into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen 14 times, and hydrogenation was carried out under conditions of a temperature of 40 ℃ and a hydrogen pressure of 0.9 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 25 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 crotyl alcohol selectivity is 100%, and the reaction time is 27 minutes.
Example 24
0.02g of the catalyst of example 11, 1.9g of crotonaldehyde, and 20ml of ethanol were placed in a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen gas 13 times, and hydrogenation was carried out under conditions of a temperature of 85 ℃ and a hydrogen pressure of 1.8 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 14 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 crotyl alcohol selectivity is 100%, and the reaction time is 34 minutes.
Example 25
0.01g of the catalyst of example 12, 0.5g of crotonaldehyde, and 24ml of methanol were charged into a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen gas 15 times, and hydrogenation was carried out under conditions of a temperature of 110 ℃ and a hydrogen pressure of 2.3 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 24 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 crotyl alcohol selectivity is 100%, and the reaction time is 23 minutes.
Example 26
0.02g of the catalyst of example 13, 0.8g of crotonaldehyde, 11ml of tert-butanol and 16ml of sec-butanol were placed in a high-pressure hydrogenation reactor, the reactor was closed, air was replaced with hydrogen 14 times, and hydrogenation was carried out under conditions of a temperature of 105 ℃ and a hydrogen pressure of 1.6 MPa. When the pressure in the kettle does not decrease any more, continuously stirring for 17 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 crotyl alcohol selectivity is 100%, and the reaction time is 22 minutes.
Examples 24 to 36
Examples 24 to 38 are the results of using the catalysts of comparative example 1, comparative example 2 and comparative example 3 to perform catalytic hydrogenation of crotonaldehyde under the reaction conditions corresponding to examples 14 to 18, 19 to 23 and 24 to 26, respectively, as shown in Table 1.
TABLE 1 results of using catalysts of comparative example 1, comparative example 2 and comparative example 3 for catalyzing chloronitrobenzene
The results of the experiment for applying the catalyst of example 15 are shown in table 2.
Table 2 results of experiment for applying catalyst of example 15
| Number of times of application | Conversion rate% | Selectivity% | Reaction time min |
| 1 | 100 | 99.95 | 35 |
| 2 | 100 | 99.98 | 28 |
| 3 | 100 | 99.97 | 29 |
| 4 | 100 | 99.94 | 30 |
| 5 | 100 | 99.95 | 26 |
| 6 | 100 | 99.97 | 30 |
| 7 | 100 | 99.96 | 29 |
| 8 | 100 | 99.99 | 25 |
| 9 | 100 | 99.92 | 26 |
| 10 | 100 | 99.91 | 31 |
| 11 | 100 | 99.98 | 29 |
| 12 | 100 | 99.96 | 29 |
| 13 | 100 | 99.97 | 30 |
| 14 | 100 | 99.98 | 36 |
| 15 | 100 | 99.91 | 28 |
| 16 | 100 | 99.96 | 37 |
| 17 | 100 | 99.94 | 38 |
| 18 | 100 | 99.92 | 29 |
| 19 | 100 | 99.95 | 35 |
| 20 | 100 | 99.96 | 34 |
Claims (10)
1. A composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots comprises a mesoporous carbon microsphere carrier, and surface functionalized carbon quantum dots and metal palladium which are supported on the carrier; the size of the catalyst is between 400nm and 1 mu m; the surface functionalized carbon quantum dots and the metal palladium form a snowflake dispersed in each piece on the surface of the carrier, the center of each snowflake is the surface functionalized carbon quantum dot which is directly loaded on the carrier and has the size of not more than 10nm, the metal palladium takes the surface functionalized carbon quantum dots as an anchoring position and grows around the surface functionalized carbon quantum dots in a flake form to form a snowflake shape, and the size of each snowflake is between 40nm and 100 nm; the surface functionalized carbon quantum dot is characterized in that an N-containing functional group is introduced to the surface of the carbon quantum dot, and the N-containing functional group is one or more of amino, pyridine nitrogen, pyrrole nitrogen and graphite nitrogen; in the catalyst, the mass fraction of metal palladium is not higher than 10.0 wt%, and the mass fraction of the surface functionalized carbon quantum dots is 2-35 wt%.
2. The composite catalyst of claim 1, wherein: the mass fraction of the surface functionalized carbon quantum dots is 5-30 wt%.
3. The composite catalyst of claim 1, wherein: the mass fraction of the metal palladium is 0.5-5 wt%.
4. A preparation method of the composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots according to claim 1 comprises the following steps:
1) carrying out polycondensation reaction by taking 3-aminophenol and formaldehyde as carbon source precursors in an ethanol-water solution system by taking ammonia water as a catalyst and F127 as a template agent to obtain F127/3-aminophenol-formaldehyde polymer microspheres;
2) preparing a chloropalladate solution;
3) preparing a surface functionalized carbon quantum dot, wherein the surface of the surface functionalized carbon quantum dot is introduced with an N-containing functional group, and the N-containing functional group is one or the combination of any more of amino, pyridine nitrogen, pyrrole nitrogen and graphite nitrogen;
4) loading the surface functionalized carbon quantum dots in the step 3) on F127/3-aminophenol-formaldehyde polymer microspheres by adopting wet impregnation, then roasting at the temperature of 250-600 ℃ in a nitrogen atmosphere to obtain mesoporous carbon microspheres loaded with the surface functionalized carbon quantum dots, and then loading palladium in a chloropalladate solution on a mesoporous carbon microsphere carrier by adopting an ultraviolet light reduction method, thereby obtaining the mesoporous carbon microsphere-loaded palladium and surface functionalized carbon quantum dot composite catalyst.
5. The method of claim 4, wherein: the surface functionalized carbon quantum dot is prepared by the following method: 1-5 parts by mass: 10-25: 0.1-0.5, adding citric acid, deionized water and N-containing substances into a hydrothermal kettle, wherein the N-containing substances are selected from one or more of the following combinations: performing hydrothermal reaction on ammonia water, ethylenediamine, urea, glycine, alanine, serine, lysine, glutamic acid, tryptophan, tyrosine, histidine, leucine and aspartic acid at the temperature of 180-220 ℃ for 5-12h, taking out a hydrothermal sample, dissolving the hydrothermal sample in water, filling the water solution into a dialysis bag with the cut-off molecular weight of 1000, 3500 or 7000 for dialysis until the solution outside the bag has no obvious color, and collecting the solution outside the dialysis bag to obtain the water solution with the surface functionalized carbon quantum dots.
6. The method of claim 4, wherein: in the step 4), the operation method of the ultraviolet reduction method is as follows: placing mesoporous carbon microspheres loaded with surface functionalized carbon quantum dots into a reaction container, adding deionized water and methanol into the reaction container, then adding a certain amount of palladium chloride palladium acid solution with the mass concentration of 0.01-0.05 g/ml, irradiating and stirring for 1-10h under an ultraviolet lamp of 100-500w, filtering, washing and vacuum drying; wherein the mesoporous carbon microsphere loaded with the surface functionalized carbon quantum dots comprises the following components: deionized water: methanol: chloropalladate solution 0.5-2 g: 40-160 mL: 10-40 mL: 0.1-4 mL.
7. The use of the composite catalyst of mesoporous carbon microsphere supported palladium and surface functionalized carbon quantum dots according to claim 1 in the reaction of synthesizing crotyl alcohol by selective catalytic hydrogenation of crotonaldehyde.
8. The use of claim 7, wherein: the application method of the catalyst comprises the following steps: putting crotonaldehyde and mesoporous carbon microsphere supported palladium and a surface functionalized carbon quantum dot composite catalyst into a high-pressure hydrogenation reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle with hydrogen, heating to 30-120 ℃, ensuring that materials in the kettle are in a molten or solution state, filling hydrogen until the pressure in the kettle is 0.2-2.5 MPa, starting stirring, starting reaction, continuing stirring at constant temperature and constant pressure for a period of time when the pressure in the kettle does not decrease any more, stopping stirring, cooling to room temperature, opening the kettle, taking out a hydrogenation liquid, and performing post-treatment on the hydrogenation liquid to obtain crotyl alcohol.
9. The use of claim 8, wherein: the reaction is carried out under the condition of no solvent or under the condition of solvent, and the solvent is one or a mixed solvent of more than two of normal hexane, isopropanol, tetrahydrofuran, isobutanol, sec-butyl alcohol, methanol, ethanol, water, butane, normal propyl alcohol, ethylbenzene, tert-butyl alcohol, toluene, normal butanol, normal butane and dimethylformamide in any proportion.
10. The use of claim 9, wherein: the mass ratio of the charge materials of the composite catalyst of the crotonaldehyde, the mesoporous carbon microsphere supported palladium and the surface functionalized carbon quantum dots is 100: 1-10.
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| CN110627617A (en) * | 2019-08-27 | 2019-12-31 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in reaction of synthesizing crotyl alcohol by selective catalytic hydrogenation of crotonaldehyde |
| CN112371173B (en) * | 2020-11-27 | 2023-09-08 | 沈阳化工研究院有限公司 | Platinum-carbon catalyst applied to hydrogenation of m-nitrobenzenesulfonic acid and preparation method thereof |
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