CN113813978A - Nitrogen-doped carbon-coated multi-center synergistic nano-reactor catalyst and preparation method thereof - Google Patents

Nitrogen-doped carbon-coated multi-center synergistic nano-reactor catalyst and preparation method thereof Download PDF

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CN113813978A
CN113813978A CN202111094405.2A CN202111094405A CN113813978A CN 113813978 A CN113813978 A CN 113813978A CN 202111094405 A CN202111094405 A CN 202111094405A CN 113813978 A CN113813978 A CN 113813978A
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李海涛
班丽君
张因
赵永祥
王浩
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Shanxi University
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Abstract

The invention relates to a nitrogen-doped carbon-coated multi-center synergetic nanoreactor catalyst, which has a Cu structure2C2−ZnO−Bi2O3@ CN, where CN is nitrogen dopedThe size of the carbon doped layer and the nano-reactor catalyst is 205 nm-293 nm, the nitrogen-doped carbon layer is of a hollow structure with the thickness of 5 nm-9 nm, and the Cu layer is2C2ZnO and Bi2O3The particles are embedded on the inner surface of the nitrogen-doped carbon layer; the mass ratio of Zn, Bi and Cu atoms is (0.23-0.91): 0.02-0.09): 1. The nano reactor catalyst provided by the invention is used for the reaction of synthesizing 1, 4-butynediol by reacting formaldehyde and acetylene, can increase the contact rate of gas, reaction substrates and the catalyst, and improves the utilization efficiency of active components, thereby improving the reaction performance.

Description

Nitrogen-doped carbon-coated multi-center synergistic nano-reactor catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis of 1, 4-butynediol, and particularly relates to a novel ethynylation catalyst for synthesizing 1, 4-butynediol and a preparation method thereof.
Background
The 1, 4-butynediol molecule contains-C ≡ C-with stronger electron fluidity and hydrophilic terminal-OH, and the structure ensures that the 1, 4-butynediol molecule has many excellent performances such as surface activity, dispersibility, defoaming property, corrosion inhibition and the like and is widely applied to the fields of electroplating liquid, artificial leather, medicines, pesticides and the like.
At present, acetylene and formaldehyde are used as raw materials in the industrial production of 1, 4-butynediol by a Reppe method using a copper-based catalyst. Copper species are easily lost due to limited dispersion of the active ingredient and weak interaction between the carrier and the active ingredient. For this reason, US patent publication No. US3920759 (a) uses magnesium silicate as a carrier, which effectively avoids loss of copper species during the preparation of the catalyst, while certain chemical action may keep the catalyst at a higher stability. The patent document with publication number US4002694 (A) aims at solving the problems that a silicon-magnesium carrier is unstable in an alkynylation reaction, silicon and magnesium are lost to cause product pollution, the product and a catalyst are difficult to separate and the like, and transition state Al is used2O3As a carrier of the copper bismuth catalyst. While the patent document with publication number US3954669 is to directly prepare a catalyst of copper-containing brucite layered structure, showing higher activity and stability. However, in the industry, the catalyst is operated for a long time, the reaction activity is in an acidic environment, the catalyst carrier is acidified to aggravate side reactions, and the loss of silicon and magnesium is serious.
Disclosure of Invention
The invention aims to overcome the defects of the existing 1, 4-butynediol synthesis process, and provides a nitrogen-doped carbon-coated multi-center synergistic nano-reactor catalyst from the perspective of catalyst structure design, so that the contact rate of gas, reaction substrates and catalyst contact is increased, the utilization efficiency of active components is improved, and the reaction performance is improved.
To achieve the above object, according to one aspect of the present invention, there is provided a nitrogen-doped carbon-coated multi-center cooperative nanoreactor catalyst, characterized in that: the structure of the nano reactor catalyst is Cu2C2−ZnO−Bi2O3@ CN, wherein CN is a nitrogen-doped carbon layer, the size of the nano reactor catalyst is 205 nm-293 nm, the nitrogen-doped carbon layer is a hollow structure with the thickness of 5 nm-9 nm, and Cu is added2C2ZnO and Bi2O3The particles are embedded on the inner surface of the nitrogen-doped carbon layer; the mass ratio of Zn, Bi and Cu atoms is (0.23-0.91): 0.02-0.09): 1.
According to another aspect of the present invention, there is provided the above-mentioned nitrogen-doped carbon-coated multi-center cooperative nanoreactor catalyst, comprising:
the method comprises the following steps: preparation of CuO-ZnO-Bi by coprecipitation method2O3A catalyst precursor; dissolving copper salt, zinc salt and bismuth salt in deionized water to prepare a copper salt mixed solution, sequentially adding urea and polyethylene glycol-400, heating to 60-70 ℃, dropwise adding a NaOH solution under the stirring condition, and standing and aging for 2-5 h after dropwise adding; respectively centrifugally washing the precipitate for 3-5 times by using deionized water and ethanol, and drying the precipitate for 3-18 h in a drying oven at the temperature of 80-150 ℃; placing the dried sample in a muffle furnace, roasting at 350-450 ℃ for 2-8 h to obtain CuO-ZnO-Bi2O3A catalyst precursor;
step two, adopting a solid phase grinding method to grind the CuO-ZnO-Bi prepared in the step one2O3Uniformly mixing a catalyst precursor, 2-ethylimidazole, an auxiliary carbon source and a surfactant, transferring a sample to a hydrothermal kettle with a polytetrafluoroethylene lining after grinding, adding ethanol, sealing the hydrothermal kettle, and then placing the hydrothermal kettle into a constant temperature cabinet at 120-180 ℃ for 6-12 hours; to be combinedAfter the completion of the formation reaction, cooling the hydrothermal kettle to room temperature, washing and drying to obtain CuO-ZnO-Bi2O3@ MAF-5 precursor.
Step three: the CuO-ZnO-Bi prepared in the second step2O3Charging the @ MAF-5 precursor into a tubular furnace, and heating to 350-450 ℃ at a heating rate of 3-5 ℃/min for 2-5 h in an inert atmosphere; then cooling to 250-300 ℃, and introducing O23 to 20 volume percent of O2-N2Keeping the mixed gas for 30-40 h, and cooling to room temperature to obtain the CuO-ZnO-Bi2O3@CN；
Step four: adding the sample obtained in the step three into a formaldehyde aqueous solution containing a cosolvent, heating to 80-95 ℃ under a nitrogen atmosphere, introducing acetylene gas, treating for 5-20 h, centrifugally separating out the treated catalyst, and drying in vacuum at 25-30 ℃ for 12-24 h to obtain the required catalyst Cu2C2−ZnO−Bi2O3@CN。
Further, in the step one, the copper salt, the zinc salt and the bismuth salt are respectively selected from Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O and Bi (NO)3)3·5H2O; the mass concentration of Cu in the copper salt mixed solution is 8.28-15.51 g/L, the mass concentration of Zn is 3.63-7.58 g/L, and the mass concentration of Bi is 0.36-0.74 g/L. The preferable mass concentration of Cu in the copper salt mixed solution is 8.28-12.62 g/L, the mass concentration of Zn is 4.95-7.58 g/L, and the mass concentration of Bi is 0.48-0.74 g/L;
in the first step, the adding amount of the urea is calculated by adding 60-75 g of urea to 1L of copper salt mixed solution, and preferably 60-70 g; the adding amount of the polyethylene glycol-400 is calculated by adding 50 g-75 g of polyethylene glycol-400 into 1L of copper salt mixed solution, and preferably 55 g-75 g.
In the first step, the mass concentration of the NaOH solution is 40-50 g/L; the adding amount of the sodium hydroxide is calculated by adding 12 mL-18 mL of NaOH solution into each 1L of the copper salt mixed solution.
In the first step, the preferable drying condition is that the drying oven is dried for 3 to 6 hours at the temperature of 100 to 120 ℃.
In the first step, the preferable roasting condition is that roasting is carried out in a muffle furnace for 3-5 h at 400-450 ℃.
Further, in the second step, the auxiliary carbon source is one of glucose, sucrose and citric acid, preferably citric acid; mass of auxiliary carbon source and CuO-ZnO-Bi2O3The mass ratio of the catalyst precursor is (0.1: 1-0.2): 1, preferably (0.1: 1-0.18): 1.
In the second step, the surfactant is polyethylene glycol-2000; mass of surfactant and CuO-ZnO-Bi2O3The mass ratio of the catalyst precursor is 0.01: 1-0.02: 1.
In the second step, the mass of the 2-ethylimidazole and CuO-ZnO-Bi2O3The mass ratio of the catalyst precursor is 0.05:1 to 0.26:1, preferably 0.05:1 to 0.21: 1.
In the second step, the amount of ethanol added is calculated according to the weight of CuO-ZnO-Bi per gram2O3Adding 30-50 mL of ethanol into the catalyst precursor for calculation;
in the second step, the washing condition is that the ethanol is centrifugally washed for 3 to 5 times;
in the second step, the drying condition is 60-70 ℃ and 8-12 h.
In the third step, the inert atmosphere is nitrogen or argon; the inert atmosphere and O2-N2The space velocity of the mixed gas is 300/h-1800/h, and the preferable space velocity is 500/h-1000/h.
Further, in the fourth step, the cosolvent is one of gamma-butyrolactone and toluene; the dosage of the cosolvent is calculated by taking 50 mL-300 mL of formaldehyde water solution per liter, and preferably 50 mL-200 mL.
In the fourth step, the dosage of the sample obtained in the third step is calculated according to 20 g-80 g of formaldehyde water solution per liter, and preferably 20 g-50 g.
In the fourth step, the mass concentration of formaldehyde in the formaldehyde aqueous solution is 150 g/L-300 g/L.
The catalyst of the invention selects CuO-ZnO-Bi2O3Basis of kernelIntroducing an organic ligand 2-ethylimidazole, an auxiliary carbon source and a surfactant to prepare CuO-ZnO-Bi with a coating structure2O3@ MAF-5. In the synthesis process, ZnO is etched by 2-ethylimidazole to generate Zn2+Then coordinating with N atom in 2-ethylimidazole to form MAF-5, and adding CuO and Bi2O3Encapsulated with the remaining small amount of ZnO in a special structure of MAF-5. Through the carbonization and controllable oxidation process in the third step, 2-ethylimidazole, an auxiliary carbon source and a surfactant in the coated MAF-5 layer are pyrolyzed and converted into an N-doped C layer, and the N-doped C layer presents an outwardly extending pore channel structure due to the guiding effect of the surfactant on the structure; under the catalytic action of CuO, the formed C layer can be partially oxidized in the low-temperature heat treatment process, so that the internal space of the N-doped C layer is increased, and a hollow structure is formed; on the other hand, the pore structure of the N-doped C layer extending outwards is increased, and the pore diameter is increased.
In the activation process of the further step four, formaldehyde and acetylene diffuse to CuO-ZnO-Bi through the outward extending pore channel structure of the N-doped C layer2O3Core, converting CuO to Cu2C2An active species. In the course of ethynylation reaction of formaldehyde, directly expose the active species of catalyst and catalyst promoter in the traditional catalytic process to the reaction environment, on one hand because of ion loss, on the other hand catalyst pulverization under the condition of stirring, this leads to catalyst life unsatisfactory. The catalyst provided by the invention constructs a micro-reactor, reactants of formaldehyde and acetylene molecules enter a microenvironment of an internal cavity through a shell pore passage of the nano-reactor to perform condensation reaction, and reaction molecules are influenced by a nano effect and are enriched in a micro-chamber environment, so that the contact rate of gas, reaction substrates and the catalyst is greatly increased, the utilization efficiency of active components is improved, and the reaction performance is greatly improved. Meanwhile, the N-doped C layer prevents the loss of ions on one hand, and on the other hand, the N-doped C layer serving as a protective layer inhibits the pulverization of the catalyst caused by stirring, so that the service life of the catalyst is prolonged.
The catalyst core adopts Cu2C2−ZnO−Bi2O3In which Cu2C2Is an active component, plays a role in adsorbing and activating formaldehyde and acetylene molecules, and promotes the formaldehyde and acetylene molecules to generate a target product 1, 4-butynediol through nucleophilic addition. ZnO acts as a catalytic reaction auxiliary agent, can play a role in adsorbing and activating formaldehyde molecules, and reacts with Cu2C2The activity of catalytic reaction is improved by synergistic effect; bi2O3As an electronic assistant, the Cu is stabilized+Can make Cu act+Under the reducing atmosphere of long-time formaldehyde ethynylation reaction, the valence state is maintained, and excessive reduction to metallic Cu is inhibited0Resulting in deactivation of the catalyst by carbon deposition.
The hollow nano reactor catalyst prepared by the invention is used for synthesizing 1, 4-butynediol by reacting formaldehyde and acetylene, the dosage of the catalyst is 40-50 g of N per liter of formaldehyde2Heating to 85-90 ℃ in the atmosphere, introducing acetylene gas for reacting for 18-20 h, and analyzing the composition of the sample by using a gas chromatography. The formaldehyde conversion rate is 92.4-100%, and the 1, 4-butynediol yield is 92.4-98%.
Drawings
FIG. 1 is a typical TEM image of a catalyst;
FIG. 2 is Cu2C2−ZnO−Bi2O3@ CN Mapping diagram;
FIG. 3 shows Cu2C2−ZnO−Bi2O3@ CN XRD pattern;
figure 4 stability of different catalysts.
Detailed Description
The claimed solution is further illustrated by the following examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
31.5 g of Cu (NO)3)2·3H2O、34.5 g Zn(NO3)2·6H2O、1.725 g Bi(NO3)3·5H2Dissolving O in deionized water to obtain 1LSequentially adding 65 g of urea and 75 g of polyethylene glycol-400 into a Cu salt mixed solution with the mass concentration of Cu of 8.28 g/L, the mass concentration of Zn of 7.58 g/L and the mass concentration of Bi of 0.74 g/L, putting the mixed solution into a water bath kettle at 60 ℃, dropwise adding 12 mL of NaOH solution with the mass concentration of 40 g/L at a constant speed, standing and aging for 2 h after dropwise adding, centrifugally separating out precipitate, washing for 3 times with deionized water, washing for 3 times with ethanol to remove impurities, drying for 5 h at 80 ℃ in a drying box, and roasting the dried sample in a muffle furnace for 2 h at 350 ℃ to obtain CuO-ZnO-Bi2O3A catalyst precursor.
5g of the CuO-ZnO-Bi prepared above was taken2O3Grinding a solid phase of the catalyst precursor, 0.25 g of 2-ethylimidazole, 0.5 g of glucose and 0.08 g of polyethylene glycol-2000 for 1.5 h, transferring the solid phase to a hydrothermal kettle, adding 200 mL of ethanol, sealing the hydrothermal kettle, keeping the temperature at 150 ℃ for 6 h, cooling to room temperature, carrying out centrifugal separation to obtain a catalyst, washing the catalyst with ethanol for 3 times to remove impurities, and drying the catalyst in a drying box at 60 ℃ for 12 h to obtain CuO-ZnO-Bi2O3@ MAF-5 precursor.
3g of the CuO-ZnO-Bi prepared above was taken2O3@ MAF-5 precursor, N2Roasting at 450 ℃ for 5 h at the speed of 3 ℃/min under the condition of the space velocity of 500/h. Cooling to 250 deg.C, introducing O2Volume fraction of 3% of O2-N2The air speed of the mixed gas is 500/h, the mixed gas is kept for 32 h, and the mixed gas is cooled to room temperature to obtain CuO-ZnO-Bi2O3@CN。
100 mL of an aqueous formaldehyde solution having a mass concentration of 200 g/L was taken, and 5 mL of gamma-butyrolactone, and 2g of the CuO-ZnO-Bi prepared above were added2O3@ CN, firstly introducing nitrogen, heating to 90 ℃, and then switching to acetylene gas treatment for 5 h. The mixed solution is cooled to room temperature, the treated catalyst is separated out by centrifugation and dried in vacuum for 24 hours at 25 ℃ to obtain the catalyst No. 1.
Example 2
42 g of Cu (NO) was taken3)2·3H2O、26 g Zn(NO3)2·6H2O、1.3 g Bi(NO3)3·5H2Dissolving O in deionized water to prepare 1L Cu with mass concentration of 11.04 g/L,sequentially adding 70 g of urea and 55 g of polyethylene glycol-400 into a Cu salt mixed solution with the Zn mass concentration of 5.72g/L and the Bi mass concentration of 0.56 g/L, putting the mixed solution into a water bath kettle at 65 ℃, dropwise adding 18 mL of NaOH solution with the NaOH mass concentration of 45 g/L at a constant speed, standing and aging for 3 h after dropwise adding, centrifugally separating out a precipitate, washing for 4 times by deionized water, washing for 4 times by ethanol to remove impurities, drying for 3 h in a drying box at 100 ℃, roasting the dried sample for 3 h in a muffle furnace at 430 ℃ to obtain CuO-ZnO-Bi2O3A catalyst precursor.
5g of the CuO-ZnO-Bi prepared above was taken2O3Grinding a solid phase of the catalyst precursor, 0.78 g of 2-ethylimidazole, 0.75 g of citric acid and 0.05 g of polyethylene glycol-2000 for 1 h, transferring the solid phase to a hydrothermal kettle, adding 150 mL of ethanol, sealing the hydrothermal kettle, keeping the temperature at 160 ℃ for 10 h, cooling to room temperature, carrying out centrifugal separation to obtain a catalyst, washing with ethanol for 3 times to remove impurities, and drying in a drying oven at 65 ℃ for 12 h to obtain CuO-ZnO-Bi2O3@ MAF-5 precursor.
3g of the CuO-ZnO-Bi prepared above was taken2O3@ MAF-5 precursor, N2Roasting at 400 ℃ for 2 h at the speed of 4 ℃/min under the condition of the space velocity of 300/h. Cooling to 250 deg.C, introducing O2Volume fraction of 15% of O2-N2The air speed of the mixed gas is 800/h, the mixed gas is kept for 36 h, and the mixed gas is cooled to room temperature to obtain CuO-ZnO-Bi2O3@CN。
100 mL of a 150 g/L formaldehyde aqueous solution was taken, 10 mL of toluene and 8 g of the above-prepared CuO-ZnO-Bi were added2O3@ CN, firstly introducing nitrogen, heating to 85 ℃, and then switching to acetylene gas treatment for 10 h. The mixed solution is cooled to room temperature, the treated catalyst is separated out by centrifugation and dried in vacuum for 20 h at 30 ℃ to obtain the catalyst No. 2.
Example 3
59 g of Cu (NO) was taken3)2·3H2O、16.5 g Zn(NO3)2·6H2O、0.825 g Bi(NO3)3·5H2Dissolving O in deionized water to obtain 1L of Cu with mass concentration of 15.51 g/L and Zn with mass concentration of 3.63gAdding 75 g of urea and 50 g of polyethylene glycol-400 into a Cu salt mixed solution with the mass concentration of Bi of 0.36 g/L in sequence, putting the mixed solution into a 65-DEG C water bath, dropwise adding 14 mL of NaOH solution with the mass concentration of 40 g/L at a constant speed, standing and aging for 5 h after dropwise adding, centrifugally separating out precipitate, washing for 3 times by deionized water, washing for 3 times by ethanol to remove impurities, drying for 10 h at 120 ℃ in a drying box, putting the dried sample into a muffle furnace, and roasting for 8 h at 400 ℃ to obtain CuO-ZnO-Bi2O3A catalyst precursor.
5g of the CuO-ZnO-Bi prepared above was taken2O3Grinding a solid phase for 2 hours, transferring the solid phase to a hydrothermal kettle, adding 180 mL of ethanol, sealing the hydrothermal kettle, keeping the temperature at 180 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation to obtain a catalyst, washing with ethanol for 3 times to remove impurities, and drying in a drying box at 70 ℃ for 12 hours to obtain CuO-ZnO-Bi2O3@ MAF-5 precursor.
3g of the CuO-ZnO-Bi prepared above was taken2O3@ MAF-5 precursor, Ar space velocity is 1000/h, roasting at 350 deg.C for 3 h at 4 deg.C/min. Cooling to 300 deg.C, introducing O 218% by volume of O2-N2The air speed of the mixed gas is 300/h, the mixed gas is kept for 40 h, and the mixed gas is cooled to room temperature to obtain CuO-ZnO-Bi2O3@CN。
100 mL of an aqueous formaldehyde solution having a mass concentration of 200 g/L was taken, and 20 mL of gamma-butyrolactone, and 5g of the above-prepared CuO-ZnO-Bi were added2O3@ CN, firstly introducing nitrogen, heating to 80 ℃, and then switching to acetylene gas treatment for 15 h. The mixed solution is cooled to room temperature, the treated catalyst is separated out by centrifugation and dried for 18 hours in vacuum at 25 ℃ to obtain the catalyst No. 3.
Example 4
48 g of Cu (NO)3)2·3H2O、22.5 g Zn(NO3)2·6H2O、1.125 g Bi(NO3)3·5H2O is dissolved in deionized water to prepare 1L of Cu with the mass concentration of 12.62 g/L, Zn with the mass concentration of 4.95g/L and Bi with the mass concentration of 0.48 g/LAdding 65 g of urea and 60 g of polyethylene glycol-400 into the Cu salt mixed solution in sequence, putting the mixed solution into a water bath kettle at 70 ℃, dropwise adding 16 mL of NaOH solution with the NaOH mass concentration of 50 g/L at a constant speed, standing and aging for 4 h after dropwise adding, centrifugally separating out precipitate, washing the precipitate with deionized water for 5 times, washing the precipitate with ethanol for 5 times to remove impurities, drying the precipitate in a drying box at 120 ℃ for 6 h, putting the dried sample into a muffle furnace, and roasting the dried sample at 450 ℃ for 5 h to obtain CuO-ZnO-Bi2O3A catalyst precursor.
5g of the CuO-ZnO-Bi prepared above was taken2O3Grinding a solid phase of the catalyst precursor, 1.05 g of 2-ethylimidazole, 0.9 g of citric acid and 0.06 g of polyethylene glycol-2000 for 1.5 h, transferring the solid phase to a hydrothermal kettle, adding 220 mL of ethanol, sealing the hydrothermal kettle, keeping the temperature at 150 ℃ for 10 h, cooling to room temperature, carrying out centrifugal separation to obtain a catalyst, washing the catalyst with ethanol for 5 times to remove impurities, and drying the catalyst in a drying box at 70 ℃ for 10 h to obtain CuO-ZnO-Bi2O3@ MAF-5 precursor.
3g of the CuO-ZnO-Bi prepared above was taken2O3@ MAF-5 precursor, Ar space velocity is 1800/h, roasting at 400 ℃ for 4 h at the speed of 3 ℃/min. Cooling to 280 deg.C, introducing O 210% by volume of O2-N2The air speed of the mixed gas is 1000/h, the mixed gas is kept for 40 h, and the mixed gas is cooled to room temperature to obtain CuO-ZnO-Bi2O3@CN。
100 mL of 250 g/L aqueous formaldehyde solution was taken, and 25 mL of toluene and 4 g of the above-prepared CuO-ZnO-Bi were added2O3@ CN, firstly introducing nitrogen, heating to 85 ℃, and then switching to acetylene gas treatment for 18 h. The mixed solution is cooled to room temperature, the treated catalyst is separated out by centrifugation and dried for 16 h under vacuum at 30 ℃ to obtain the catalyst No. 4.
Example 5
37.5 g of Cu (NO) was taken3)2·3H2O、24.5 g Zn(NO3)2·6H2O、1.125 g Bi(NO3)3·5H2Dissolving O in deionized water to obtain 1L Cu salt mixed solution with Cu mass concentration of 9.86 g/L, Zn mass concentration of 5.39 g/L and Bi mass concentration of 0.48 g/LAdding 60 g of urea and 75 g of polyethylene glycol-400, putting the mixture into a 65 ℃ water bath kettle, dropwise adding 14 mL of NaOH solution with the NaOH mass concentration of 40 g/L at a constant speed, standing and aging for 2 h after dropwise adding, centrifugally separating out precipitate, washing the precipitate for 3 times with deionized water, washing the precipitate for 3 times with ethanol to remove impurities, drying the precipitate in a drying oven for 18 h at 150 ℃, putting the dried sample into a muffle furnace, and roasting the sample for 4 h at 430 ℃ to obtain CuO-ZnO-Bi2O3A catalyst precursor.
5g of the CuO-ZnO-Bi prepared above was taken2O3Grinding a solid phase for 2 hours, transferring the solid phase to a hydrothermal kettle, adding 250 mL of ethanol, sealing the hydrothermal kettle, keeping the temperature at 120 ℃ for 12 hours, cooling to room temperature, carrying out centrifugal separation to obtain a catalyst, washing with ethanol for 5 times to remove impurities, and drying in a drying box at 70 ℃ for 8 hours to obtain CuO-ZnO-Bi2O3@ MAF-5 precursor.
3g of the CuO-ZnO-Bi prepared above was taken2O3@ MAF-5 precursor, N2Roasting at 450 ℃ for 4 h at the speed of 5 ℃/min under the condition of the space velocity of 1500/h. Cooling to 250 deg.C, introducing O 220% by volume of O2-N2The air speed of the mixed gas is 1800/h, the mixed gas is kept for 30 h, and the mixed gas is cooled to room temperature to obtain CuO-ZnO-Bi2O3@CN。
100 mL of aqueous formaldehyde solution with the mass concentration of 300 g/L is taken, 30 mL of gamma-butyrolactone and 6 g of the prepared CuO-ZnO-Bi are added2O3@ CN, firstly introducing nitrogen, heating to 95 ℃, and then switching to acetylene gas treatment for 20 h. The mixed solution is cooled to room temperature, the treated catalyst is separated out by centrifugation and dried in vacuum for 12 hours at 25 ℃ to obtain the catalyst No. 5.
Example 6
The morphology of the catalyst prepared in examples 1-5 was characterized by a JEM-2100 type high resolution transmission electron microscope. Cu as shown in a typical TEM image of the catalyst of FIG. 12C2−ZnO−Bi2O3@ CN presents a hollow nanoreactor structure. Due to the particularity of MAF-5 that a hollow structure is formed during oxidation,the light part of the upper figure is an internal cavity, the light part of the outermost layer is a carbon-nitrogen layer formed by organic decomposition of MAF-5 in the carbonization process, and the darker part is Cu2C2−ZnO−Bi2O3Composite oxide of, Cu2C2ZnO and Bi2O3The particles are embedded on the inner surface of the carbon-nitrogen layer.
The size of the hollow nano-reactor and the thickness of the carbon-nitrogen shell layer were calculated from the TEM photograph, the mass ratio of Zn to Bi to Cu atoms in each prepared catalyst was determined by the ICP-AES technique, and the content of N element in the catalyst was determined by elemental analysis, with the results shown in table 1. As shown in Table 1, the size of the hollow nano reactor is 205 nm-293 nm, the thickness of the carbon nitrogen layer is about 5 nm-9 nm, wherein Cu2C2ZnO and Bi2O3The particles are embedded on the inner surface of the carbon-nitrogen layer, the mass ratio of Zn to Bi to Cu atoms is 0.23-0.91: 0.02-0.09: 1, and the content of N element is 3% -6.7%.
TABLE 1 size, thickness of carbon-nitrogen shell and atomic mass ratio of hollow nano-reactor
Catalyst and process for preparing same Nanoreactor size (nm) Thickness of carbon and nitrogen shell (nm) Mass ratio of Zn to Bi to Cu atoms Content of N element/%)
Number 1 205 5 0.91:0.09:1 3.4
Number 2 257 6.4 0.51:0.05:1 3
No. 3 270 7.5 0.23:0.02:1 5.2
Number 4 293 9 0.39:0.04:1 6.7
Number 5 235 5.5 0.55:0.05:1 4.2
Example 7
The catalyst No. 1-5 is used for synthesizing 1, 4-butynediol by reacting formaldehyde and acetylene, and the specific method comprises the following steps:
sequentially adding 40 g-50 g of catalyst, 1L of 35% formaldehyde aqueous solution and N into a 2.5L round-bottom two-mouth flask with a condensation pipe2Heating to 85-90 ℃ in the atmosphere, and then introducing 20-30 mL/min C2H2The reaction is carried out. The reaction is carried out for 18-20 h, the gas chromatography is adopted for analyzing the composition of the sample, and the results are shown in Table 2.
For comparison, Cu of non-hollow nanoreactor structure was prepared under the conditions of example 52C2−ZnO−Bi2O3Catalyst: 37.5 g of Cu (NO) was taken3)2·3H2O、24.5 g Zn(NO3)2·6H2O、1.125 g Bi(NO3)3·5H2Dissolving O in deionized water to prepare 1L of Cu salt mixed solution with the mass concentration of 9.86 g/L, the mass concentration of Zn of 5.35 g/L and the mass concentration of Bi of 0.48 g/L, sequentially adding 60 g of urea and 75 g of polyethylene glycol-400, putting the mixed solution into a water bath kettle at 65 ℃, dropwise adding 14 mL of NaOH solution with the mass concentration of 40 g/L at a constant speed, standing and aging for 2 h after dropwise adding, centrifugally separating out precipitate, washing 3 times with deionized water, washing 3 times with ethanol to remove impurities, drying in a drying box at 150 ℃ for 18 h, putting the dried sample into a muffle furnace, and roasting at 430 ℃ for 4 h to obtain CuO-ZnO-Bi2O3A catalyst precursor. 100 mL of aqueous formaldehyde solution with the mass concentration of 300 g/L is taken, 30 mL of gamma-butyrolactone and 6 g of the prepared CuO-ZnO-Bi are added2O3Firstly introducing nitrogen, heating to 95 ℃, and then switching to acetylene gas for treatment for 20 h. Cooling the mixed solution to room temperature, centrifugally separating the treated catalyst, and vacuum-drying at 25 ℃ for 12 h to obtain the catalyst Cu2C2−ZnO−Bi2O3。Cu2C2−ZnO−Bi2O3The evaluation conditions and results are also shown in Table 2.
As can be seen from Table 2, under the selected reaction conditions, the conversion of formaldehyde on the hollow nanoreactor catalyst is 92.4% to 100%, the yield of 1, 4-butynediol is 92.4% to 98%, which is significantly higher than Cu2C2−ZnO−Bi2O379.6% and 78.2%.
TABLE 2 evaluation conditions and evaluation results of hollow nano-reactors
Catalyst and process for preparing same Catalyst dosage per gram Reaction temperature/. degree.C C2H2Flow rate mL/min Reaction time/h Formaldehyde conversion (%) 1, 4-butynediol yield/%)
Cu2C2−ZnO−Bi2O3 50 87 20 20 79.6 78.2
Number 1 50 85 30 18 92.4 90.8
Number 2 40 89 25 19 93.3 91.7
No. 3 45 90 28 20 96.9 95.2
Number 4 48 90 30 20 100 98
Number 5 43 85 23 20 92.7 91.1
The evaluation conditions listed in Table 2 were used for the No. 5 hollow nanoreactor structured catalyst and the Cu having the same preparation conditions but without the hollow nanoreactor structure2C2−ZnO−Bi2O3The catalyst was subjected to 30 cycle stability tests. Along with the increase of the reaction cycle times, the yield change of the 1, 4-butynediol is shown in figure 4, and the evaluation result shows that the conversion rate of the catalyst without the shell layer is the lowest under the same reaction condition, the cavity generated by the catalyst with the shell layer is favorable for the enrichment of reaction substrates, the contact rate of the reaction substrates to the catalyst is increased, and the formaldehyde conversion rate is higher than that of the catalyst without the shell layerThe catalyst has obviously better stability than the catalyst without shell layer.

Claims (10)

1. A nitrogen-doped carbon-coated multi-center synergistic nanoreactor catalyst, characterized in that: the structure of the nano reactor catalyst is Cu2C2−ZnO−Bi2O3@ CN, wherein CN is a nitrogen-doped carbon layer, the size of the nano reactor catalyst is 205 nm-293 nm, the nitrogen-doped carbon layer is a hollow structure with the thickness of 5 nm-9 nm, and Cu is added2C2ZnO and Bi2O3The particles are embedded on the inner surface of the nitrogen-doped carbon layer; the mass ratio of Zn, Bi and Cu atoms is (0.23-0.91): 0.02-0.09): 1.
2. The method of preparing a nitrogen-doped carbon-coated multi-center-coordinated nanoreactor catalyst of claim 1, comprising:
the method comprises the following steps: preparation of CuO-ZnO-Bi by coprecipitation method2O3A catalyst precursor; dissolving copper salt, zinc salt and bismuth salt in deionized water to prepare a copper salt mixed solution, sequentially adding urea and polyethylene glycol-400, heating to 60-70 ℃, dropwise adding a NaOH solution under the stirring condition, and standing and aging for 2-5 h after dropwise adding; respectively centrifugally washing the precipitate for 3-5 times by using deionized water and ethanol, and drying the precipitate for 3-18 h in a drying oven at the temperature of 80-150 ℃; placing the dried sample in a muffle furnace, roasting at 350-450 ℃ for 2-8 h to obtain CuO-ZnO-Bi2O3A catalyst precursor;
step two, adopting a solid phase grinding method to grind the CuO-ZnO-Bi prepared in the step one2O3Uniformly mixing a catalyst precursor, 2-ethylimidazole, an auxiliary carbon source and a surfactant, transferring a sample to a hydrothermal kettle with a polytetrafluoroethylene lining after grinding, adding ethanol, sealing the hydrothermal kettle, and then placing the hydrothermal kettle into a constant temperature cabinet at 120-180 ℃ for 6-12 hours; after the synthesis reaction is finished, cooling the hydrothermal kettle to room temperature, washing and drying to obtain CuO-ZnO-Bi2O3@ MAF-5 precursor;
step three: the CuO-prepared in the step twoZnO−Bi2O3Charging the @ MAF-5 precursor into a tubular furnace, and heating to 350-450 ℃ at a heating rate of 3-5 ℃/min for 2-5 h in an inert atmosphere; then cooling to 250-300 ℃, and introducing O23 to 20 volume percent of O2-N2Keeping the mixed gas for 30-40 h, and cooling to room temperature to obtain the CuO-ZnO-Bi2O3@CN；
Step four: adding the sample obtained in the step three into a formaldehyde aqueous solution containing a cosolvent, heating to 80-95 ℃ under a nitrogen atmosphere, introducing acetylene gas, treating for 5-20 h, centrifugally separating out the treated catalyst, and drying in vacuum at 25-30 ℃ for 12-24 h to obtain the required catalyst Cu2C2−ZnO−Bi2O3@CN。
3. The method of claim 2, wherein: in the first step, the copper salt, the zinc salt and the bismuth salt are respectively selected from Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O and Bi (NO)3)3·5H2O; the mass concentration of Cu in the copper salt mixed solution is 8.28-15.51 g/L, the mass concentration of Zn is 3.63-7.58 g/L, and the mass concentration of Bi is 0.36-0.74 g/L.
4. The method of claim 2, wherein: in the first step, the adding amount of the urea is calculated by adding 60-75 g of urea into every 1L of copper salt mixed solution; the adding amount of the polyethylene glycol-400 is calculated by adding 50 g-75 g of polyethylene glycol-400 into 1L of copper salt mixed solution.
5. The method of claim 2, wherein: in the first step, the mass concentration of the NaOH solution is 40-50 g/L; the adding amount of the sodium hydroxide is calculated by adding 12 mL-18 mL of NaOH solution into each 1L of the copper salt mixed solution.
6. The method of claim 2, wherein: step twoThe auxiliary carbon source is one of glucose, sucrose and citric acid, preferably citric acid; mass of auxiliary carbon source and CuO-ZnO-Bi2O3The mass ratio of the catalyst precursor is 0.1: 1-0.2: 1.
7. The method of claim 2, wherein: in the second step, the surfactant is polyethylene glycol-2000; mass of surfactant and CuO-ZnO-Bi2O3The mass ratio of the catalyst precursor is 0.01: 1-0.02: 1.
8. The method of claim 2, wherein: in the second step, the mass of the 2-ethylimidazole and CuO-ZnO-Bi2O3The mass ratio of the catalyst precursor is 0.05:1 to 0.26:1, preferably 0.05:1 to 0.21: 1.
9. The method of claim 2, wherein: in the fourth step, the cosolvent is one of gamma-butyrolactone and toluene; the dosage of the cosolvent is calculated according to 50 mL-300 mL of formaldehyde aqueous solution per liter.
10. The use of the nitrogen-doped carbon-coated multi-center-coordinated nanoreactor catalyst of claim 1 for the reaction of formaldehyde with acetylene to synthesize 1, 4-butynediol.
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