CN109894135B - Nitrogen-doped carbon black supported palladium-bismuth alloy catalyst, preparation method and application thereof - Google Patents
Nitrogen-doped carbon black supported palladium-bismuth alloy catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped carbon black loaded palladium-bismuth alloy catalyst and a preparation method and application thereof. The catalyst is prepared from PdxBiyAlloy and nitrogen-doped carbon black, wherein the Pd isxBiyThe mass fraction of the alloy is 10-30%, wherein x and y are the atomic ratio of palladium and bismuth, and the ratio of x to y is 9: 1-5: 5; the catalyst can realize the high-efficiency selective oxidative esterification of alcohol under mild reaction conditions to obtain the corresponding ester compound. The palladium-bismuth alloy catalyst has the advantages of simple synthesis method, loose synthesis conditions and easy recovery and reuse, and the synergistic effect of the carrier and the metal can greatly improve the activity of the catalyst; the alloy catalyst is used for catalyzing alcohol oxidation esterification reaction, and has the advantages of high efficiency, environmental protection and mild reaction conditionsAnd the method has the advantages of simple operation, good selectivity of products, high yield, easy separation and the like.
Description
Technical Field
The invention belongs to the field of material preparation, relates to a supported palladium-bismuth alloy catalyst, and particularly relates to a nitrogen-doped carbon black supported palladium-bismuth alloy catalyst for alcohol oxidation esterification reaction, and a preparation method and application thereof.
Background
The organic carboxylic ester is an important chemical intermediate raw material, and the ester structure widely exists in medicines, pesticides and perfume products, and plays an indispensable important role in organic chemical production. The traditional synthesis method of organic carboxylic ester is that carboxylic acid or its derivative and alcohol are esterified under the catalysis of Lewis acid. In addition, concentrated sulfuric acid is often used as a catalyst in industry, so that the problems of equipment corrosion, more side reactions, difficulty in treatment of reaction waste liquid and the like exist. With the development of novel heteropoly acid, solid super acid and ionic liquid in recent years, acid-alcohol esterification is further developed, and the reaction esterification efficiency is obviously improved. However, these methods have disadvantages of environmental hazard, high cost, complicated post-treatment, harsh reaction conditions, and long reaction time, respectively. In contrast, the one-step reaction of alcohols to esters is considered the most direct, economical, efficient and greener synthetic route.
Pd is widely used for alcohol oxidation esterification research. Matthias Beller et al uses Pd (OAc)2Catalyst, methanol or toluene as solvent, under the action of ligand, AgPF6Or AgBF4The oxidative esterification of alcohols is carried out for additives, but the reaction temperature is high and the reaction takes a long time [ Gowrisankar S, Neumann H, Beller M.general and selective palladium-catalyzed oxidative esterification of alcohols [ J].Angewandte Chemie International Edition,2011,50(22):5139-5143.]. Xuliwen et al used Pd (OAc)2With BiCl3To be in commonThe catalyst catalyzes alcohol oxidation esterification reaction, and 2 mol equivalents of alkali and polymethylhydrosiloxane are added as additives during the reaction. BiCl in the catalytic system3The addition of (A) can greatly accelerate the reaction and reduce the reaction temperature, however, the adoption of a homogeneous catalysis system still has the problems of difficult catalyst recovery, difficult separation, complex treatment after the reaction and the like [ Bai X F, Ye F, Zheng L S, et al].Chemical Communications,2012,48(68):8592-8594.]。
Therefore, the development of supported transition metal catalysts for alcohol oxidation esterification reactions meets the demand of the development of the times. The transition metal is loaded on a specific carrier to form the catalyst, and the use of the carrier can reduce the using amount of the transition metal, particularly noble metal, and can effectively reduce the cost of the catalyst. Meanwhile, the synergistic effect between the carrier and the catalyst particles has obvious effect on improving the catalytic activity and stability of the catalyst. In 2017, nano Co is loaded on a nitrogen-doped carbon material by aging and the like to form an alcohol oxidation esterification catalyst, a heterogeneous catalyst system is adopted, which is beneficial to recycling of the catalyst, but the defects of long reaction time consumption and the like exist [ Su H, Zhang K X, Zhang B, et al].Journal of the American Chemical Society,2017,139(2):811-818.]. Shannon S.Stahl et al used Pd/Char catalyst in Bi (NO)3)3The one-step ester generation from alcohol is realized under the coordination with Te, but the catalytic system is more complex and the reaction time is relatively long, and a pure oxygen reaction atmosphere is required [ Powell AB, Stahl S].Organic letters,2013,15(19):5072-5075.]。
Disclosure of Invention
In order to overcome the defects and shortcomings of the traditional homogeneous catalyst, the preparation of the supported heterogeneous catalyst which is high in activity, easy to separate and reusable and is used for the alcohol oxidation esterification reaction is significant. The invention aims to provide a preparation method and application of a nitrogen-doped carbon black loaded palladium-bismuth alloy catalyst.
The purpose of the invention is realized by the following technical scheme:
a nitrogen-doped carbon black-loaded palladium-bismuth alloy catalyst for alcohol oxidation esterification reaction is prepared from PdxBiyAlloy and nitrogen-doped carbon black (NCB), wherein the Pd isxBiyThe mass fraction of the alloy is 10-30%, wherein x and y are atomic ratios of palladium and bismuth, and the ratio of x to y is 9: 1-5: 5.
Furthermore, the carbon black is XC-72 carbon black, and the doping amount of nitrogen in the nitrogen-doped carbon black is 2-5% (atom percentage content).
The preparation method of the nitrogen-doped carbon black supported palladium-bismuth alloy catalyst comprises the following specific steps:
(1) dispersing nitrogen-doped carbon black in ethylene glycol, and weighing corresponding K according to the atomic ratio of palladium to bismuth of 9: 1-5: 52PdCl4And Bi (NO)3)3·5H2Dissolving O in ethylene glycol, uniformly mixing, dropwise adding the mixture into ethylene glycol dispersion liquid of the nitrogen-doped carbon black, and uniformly stirring;
(2) reacting NaBH4Dropwise adding the aqueous solution into the solution obtained in the step (1), stirring and reacting at 20-30 ℃, filtering, washing, and freeze-drying to obtain PdxBiya/NCB catalyst.
Preferably, in the step (1), the stirring time is not less than 30 min.
Preferably, in the step (2), the reduction time is not less than 2 h.
The application of the nitrogen-doped carbon black loaded palladium-bismuth alloy catalyst in alcohol oxidation esterification reaction.
Preferably, the alcohols are primary aromatic alcohols and primary aliphatic alcohols.
Preferably, the reaction temperature is 60 ℃, the reaction pressure is normal pressure (1atm), the reaction atmosphere is air, and the stirring time is 2-3 h.
Preferably, the catalyst to alcohol ratio is 20 mg/mmol.
Compared with the prior art, the invention has the following remarkable advantages: (1) the preparation method of the catalyst is simple; (2) the catalyst consumption in the catalytic reaction is greatly reduced, the reaction time is shortened, and the catalytic efficiency is improved; (3) the catalyst is easy to separate, can be repeatedly used and has low cost.
Drawings
FIG. 1 shows Pd5Bi5Transmission electron microscopy for/NCB (a) and high resolution transmission electron microscopy (b).
FIG. 2 shows different ratios PdxBiyX-ray diffraction pattern of/NCB catalyst.
FIG. 3 is Pd5Bi5BET curve and pore size distribution of the/NCB catalyst (inset).
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
The catalyst is prepared by using NCB as a carrier and using XC-72 carbon black as the NCB through acidification and then nitrogen doping modification. PdBi alloy consisting of K2PdCl4And Bi (NO)3)3·5H2O is metal precursor treated by NaBH4Is prepared by one-step reduction. The carrier NCB selected by the invention has the following advantages:
(1) the NCB has rich oxygen-containing functional groups on the surface, is favorable for the adsorption of metal ions and the compounding of nano particles, has large specific surface area, and is favorable for the dispersion of catalyst particles and the adsorption of organic reactant molecules.
(2) The surface characteristics of the carbon black can be regulated and controlled by the nitrogen doping modification, so that the generation and the loading of small-particle nano particles are facilitated, and the agglomeration is prevented.
The NCB used according to the invention can be prepared as in example 1:
example 1
Firstly, weighing 18gXC-72 model carbon black, putting into a 1000mL round bottom flask, adding 600mL 65% -68% concentrated nitric acid, and performing ultrasonic dispersion for 20 min.
And secondly, placing the round-bottom flask in an oil bath at 100 ℃, carrying out condensation reflux for 12 hours while stirring, adding 1200mL of deionized water for dilution after the reaction is finished, removing supernatant after sedimentation, carrying out suction filtration and washing on solid residues until the solid residues are neutral, and carrying out freeze drying to obtain the acidified modified carbon black CB.
Thirdly, weighing 1.2gCB in 600mL of urea aqueous solution (1g of urea/mL of water), ultrasonically dispersing for 20min, transferring to a 1000mL hydrothermal reaction kettle, and reacting for 24h at 180 ℃. After cooling to room temperature, the solid residue was filtered with suction and washed until neutral, and lyophilized to give NCB.
The Pd for alcohol oxidative esterification of the inventionxBiythe/NCB catalyst can be prepared as in examples 2 to 6:
example 2
Firstly, 100mgNCB (obtained by acidifying XC-72 carbon black and then carrying out nitrogen doping modification on NCB) is weighed and dispersed in 100mL of glycol by ultrasound, the mass of metal accounts for 20 percent of the total mass of the catalyst, the atomic ratio of Pd to Bi is 9:1, and corresponding K is weighed2PdCl4And Bi (NO)3)3·5H2O is dissolved in 50mL of ethylene glycol, stirred uniformly and then added dropwise to the NCB dispersion, stirred for 30min, and the temperature is controlled at 25 ℃.
Second, 0.2g NaBH is weighed4Dissolving in 50mL of water, dropwise adding into the reaction solution in the first step, stirring at 25 deg.C for 2h, washing the solid residue with water and ethanol for several times, and drying to obtain Pd9Bi1a/NCB catalyst.
FIG. 2 is an XRD pattern of the catalyst prepared in this example, illustrating that the catalyst prepared by this method is Pd9Bi1a/NCB catalyst.
Example 3
Firstly, 100mgNCB (obtained by acidifying XC-72 carbon black and then carrying out nitrogen doping modification on NCB) is weighed and dispersed in 100mL of glycol by ultrasound, the mass of metal accounts for 20 percent of the total mass of the catalyst, the atomic ratio of Pd to Bi is 7:3, and corresponding K is weighed2PdCl4And Bi (NO)3)3·5H2O is dissolved in 50mL of ethylene glycol, stirred uniformly and then added dropwise to the NCB dispersion, stirred for 30min, and the temperature is controlled at 25 ℃.
Second, 0.2g NaBH is weighed4Dissolving in 50mL of water, dropwise adding into the reaction solution in the first step, stirring at 25 deg.C for 2h, washing the solid residue with water and ethanol for several times, and drying to obtain Pd7Bi3a/NCB catalyst.
FIG. 2 is an XRD pattern of the catalyst prepared in this example, illustrating that the catalyst prepared by this method is Pd7Bi3a/NCB catalyst.
Example 4
Firstly, 100mgNCB (obtained by acidifying XC-72 carbon black and then carrying out nitrogen doping modification on NCB) is weighed and dispersed in 100mL of glycol by ultrasound, the mass of metal accounts for 20 percent of the total mass of the catalyst, the atomic ratio of Pd to Bi is 5:5, and corresponding K is weighed2PdCl4And Bi (NO)3)3·5H2O is dissolved in 50mL of ethylene glycol, stirred uniformly and then added dropwise to the NCB dispersion, stirred for 30min, and the temperature is controlled at 25 ℃.
Second, 0.2g NaBH is weighed4Dissolving in 50mL of water, dropwise adding into the reaction solution in the first step, stirring at 25 deg.C for 2h, washing the solid residue with water and ethanol for several times, and drying to obtain Pd5Bi5a/NCB catalyst.
FIG. 1 is a projection electron micrograph (a) and a high-resolution projection electron micrograph (b) of the catalyst prepared in this example.
FIG. 2 is an XRD pattern of the catalyst prepared in this example, illustrating that the catalyst prepared by this method is Pd5Bi5a/NCB catalyst.
FIG. 3 is a BET curve and a pore size distribution (inset) of the catalyst prepared in this example, which illustrate the large specific surface area and the suitable pore structure of the catalyst prepared by the method, which facilitates the catalytic reaction.
Example 5
Firstly, 100mgNCB (obtained by acidifying XC-72 carbon black and then carrying out nitrogen doping modification on NCB) is weighed and dispersed in 100mL of glycol by ultrasound, the mass of metal accounts for 10 percent of the total mass of the catalyst, the atomic ratio of Pd to Bi is 5:5, and corresponding K is weighed2PdCl4And Bi (NO)3)3·5H2O is dissolved in 50mL of ethylene glycol, stirred uniformly and then added dropwise to the NCB dispersion, stirred for 30min, and the temperature is controlled at 25 ℃.
Second, 0.2g NaBH is weighed4Dissolving in 50mL of water, dropwise adding into the reaction solution in the first step, stirring at 25 deg.C for 2 hr, and washing the solid residue with water and ethanolThen, the Pd with the alloy mass fraction of 10 percent is obtained by drying5Bi5a/NCB catalyst.
Example 6
Firstly, 100mgNCB (obtained by acidifying XC-72 carbon black and then carrying out nitrogen doping modification on NCB) is weighed and dispersed in 100mL of glycol by ultrasound, the mass of metal accounts for 30 percent of the total mass of the catalyst, the atomic ratio of Pd to Bi is 5:5, and corresponding K is weighed2PdCl4And Bi (NO)3)3·5H2O is dissolved in 50mL of ethylene glycol, stirred uniformly and then added dropwise to the NCB dispersion, stirred for 1h, and the temperature is controlled at 25 ℃.
Second, 0.2g NaBH is weighed4Dissolving in 50mL of water, dropwise adding into the reaction solution in the first step, stirring at 25 ℃ for reaction for 3h, washing the solid residue with water and ethanol for several times, and drying to obtain Pd with the alloy mass fraction of 30%5Bi5a/NCB catalyst.
The application of the catalyst for the alcohol oxidation esterification nitrogen-doped carbon black loaded palladium-bismuth alloy can be implemented according to the embodiment 7-9:
example 7
The catalyst in the embodiment 2-5 is adopted to catalyze the reaction of the benzyl alcohol and the methanol to generate the methyl benzoate in one step. The specific reaction conditions are as follows: benzyl alcohol 0.5mmol, methanol 2mL, K2CO30.25mmol, 10mg of catalyst, 60 ℃ of reaction temperature, air atmosphere of reaction atmosphere, normal pressure (1atm) of reaction pressure and 2 hours of reaction time; after the reaction, the reaction mixture was naturally cooled, the catalyst was filtered, and the reaction product was separated by column to obtain the product, the results of which are shown in table 1.
TABLE 1 yield of methyl benzoate from catalytic oxidation of benzyl alcohol and methanol with catalysts of different metal ratios
Mixing all the materialsThe catalyst of example 4 was recovered, washed several times with water and ethanol, and dried at 60 ℃; the dried catalyst was repeated. The Pd5Bi5The cycle performance of the/NCB catalyst is shown in Table 2, the yield is still above 90% after five times of cycles, and the catalyst has good cycle stability.
TABLE 2 Pd5Bi5Determination result of cycle performance of methyl benzoate generated by catalyzing and oxidizing benzyl alcohol and methanol by NCB catalyst
Example 8
The catalyst in example 4 was used to catalyze the alcohol oxidation esterification reaction with the reactants shown in table 3 as raw materials and the fatty alcohol as solvent. The specific reaction conditions are as follows: 0.5mmol of reactant, 2mL of solvent, K2CO30.25mmol, 10mg of catalyst, 60 ℃ of reaction temperature, air atmosphere of reaction atmosphere, normal pressure (1atm) of reaction pressure and 2 hours of reaction time; after the reaction, the reaction mixture was naturally cooled, the catalyst was filtered, and the reaction product was separated by column to obtain a product, the results of which are shown in Table 3.
TABLE 3 Pd5Bi5Reaction result of alcohol oxidation esterification catalyzed by NCB catalyst
Example 9
The catalyst in the embodiment 4 is used for catalyzing the reaction of the benzyl alcohol and the methanol to generate the methyl benzoate in one step. The specific reaction conditions are as follows: benzyl alcohol 0.5mmol, methanol 2mL, K2CO30.25mmol, 10mg of catalyst, reaction temperature of 60 ℃, reaction atmosphere of air atmosphere and reaction pressure of normal pressure (1atm)) The reaction time is 3 hours; after the reaction is finished, the reaction product is naturally cooled, the catalyst is filtered out, and the reaction product is separated by a column to obtain a product, wherein the yield is 99%.
Claims (7)
1. The nitrogen-doped carbon black loaded palladium-bismuth alloy catalyst for alcohol oxidation esterification reaction is characterized in that the catalyst is prepared from PdxBiyAlloy and nitrogen-doped carbon black, wherein the Pd isxBiyThe mass of the alloy accounts for 10-30% of the total mass of the catalyst, wherein x and y are the atomic ratio of palladium and bismuth, and the ratio of x to y is 9: 1-5: 5;
the preparation method comprises the following steps:
(1) dispersing nitrogen-doped carbon black in ethylene glycol, and weighing corresponding K according to the atomic ratio of palladium to bismuth2PdCl4And Bi (NO)3)3·5H2Dissolving O in ethylene glycol, uniformly mixing, dropwise adding the mixture into ethylene glycol dispersion liquid of the nitrogen-doped carbon black, and uniformly stirring;
(2) reacting NaBH4Dropwise adding the aqueous solution into the solution obtained in the step (1), stirring and reacting at 20-30 ℃, filtering, washing, and freeze-drying to obtain PdxBiya/NCB catalyst;
wherein, the nitrogen-doped carbon black is prepared by the following steps:
firstly, weighing 18gXC-72 model carbon black, putting the carbon black into a 1000mL round bottom flask, adding 600mL of 65-68% concentrated nitric acid, and performing ultrasonic dispersion for 20 min;
secondly, placing the round-bottom flask in an oil bath at 100 ℃, stirring and condensing and refluxing for 12 hours, adding 1200mL of deionized water for dilution after the reaction is finished, removing supernatant after sedimentation, carrying out suction filtration and washing on solid residues until the solid residues are neutral, and carrying out freeze drying to obtain acidified modified carbon black CB;
and thirdly, weighing 1.2gCB in 600mL of 1g/mL urea aqueous solution, carrying out ultrasonic dispersion for 20min, transferring the solution into a 1000mL hydrothermal reaction kettle, reacting for 24h at 180 ℃, cooling to room temperature, carrying out suction filtration on solid residues, washing until the solid residues are neutral, and carrying out freeze drying to obtain the nitrogen-doped carbon black NCB.
2. The preparation method of the nitrogen-doped carbon black supported palladium-bismuth alloy catalyst as claimed in claim 1, which is characterized by comprising the following steps:
(1) dispersing nitrogen-doped carbon black in ethylene glycol, and weighing corresponding K according to the atomic ratio of palladium to bismuth2PdCl4And Bi (NO)3)3·5H2Dissolving O in ethylene glycol, uniformly mixing, dropwise adding the mixture into ethylene glycol dispersion liquid of the nitrogen-doped carbon black, and uniformly stirring;
(2) reacting NaBH4Dropwise adding the aqueous solution into the solution obtained in the step (1), stirring and reacting at 20-30 ℃, filtering, washing, and freeze-drying to obtain PdxBiya/NCB catalyst;
wherein, the nitrogen-doped carbon black is prepared by the following steps:
firstly, weighing 18gXC-72 model carbon black, putting the carbon black into a 1000mL round bottom flask, adding 600mL of 65-68% concentrated nitric acid, and performing ultrasonic dispersion for 20 min;
secondly, placing the round-bottom flask in an oil bath at 100 ℃, stirring and condensing and refluxing for 12 hours, adding 1200mL of deionized water for dilution after the reaction is finished, removing supernatant after sedimentation, carrying out suction filtration and washing on solid residues until the solid residues are neutral, and carrying out freeze drying to obtain acidified modified carbon black CB;
and thirdly, weighing 1.2gCB in 600mL of 1g/mL urea aqueous solution, carrying out ultrasonic dispersion for 20min, transferring the solution into a 1000mL hydrothermal reaction kettle, reacting for 24h at 180 ℃, cooling to room temperature, carrying out suction filtration on solid residues, washing until the solid residues are neutral, and carrying out freeze drying to obtain the nitrogen-doped carbon black NCB.
3. The process according to claim 2, wherein in the step (1), the stirring time is not less than 30 min.
4. The method according to claim 2, wherein in the step (2), the reduction time is not less than 2 hours.
5. The application of the nitrogen-doped carbon black supported palladium-bismuth alloy catalyst in alcohol oxidation esterification reaction according to claim 1, wherein the alcohol is aromatic primary alcohol and aliphatic alcohol.
6. The method as claimed in claim 5, wherein the reaction temperature is 60 ℃, the reaction pressure is normal pressure, the reaction atmosphere is air, and the stirring time is 2-3 h.
7. Use according to claim 5, wherein the catalyst to alcohol ratio is 20 mg/mmol.
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