CN111905726B - Preparation method of Au-C high-selectivity oxidation catalyst with controllable size - Google Patents

Preparation method of Au-C high-selectivity oxidation catalyst with controllable size Download PDF

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CN111905726B
CN111905726B CN202010765293.8A CN202010765293A CN111905726B CN 111905726 B CN111905726 B CN 111905726B CN 202010765293 A CN202010765293 A CN 202010765293A CN 111905726 B CN111905726 B CN 111905726B
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CN111905726A (en
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梁长海
单风祥
罗靖洁
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Dalian University of Technology
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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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    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group

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Abstract

The invention discloses a preparation method of an Au-C high-selectivity oxidation catalyst with controllable size. One or more than one of tannic acid, polyvinylpyrrolidone, polyvinyl alcohol, cetyl trimethyl ammonium bromide and polyethylene glycol are mixed as a protective agent, a gold precursor is reduced into uniform spherical particles with the size range of 2-20nm by a reducing agent, 0.5-5.0wt% of gold particles are anchored on the surface of a carbon material by immobilization, and the gold particles comprise one or more than one of activated carbon, carbon nano tubes, graphene oxide, carbon nano-fibers and the like. Under the condition of normal pressure and oxygen circulation at 40-90 ℃ or connection of an oxygen ball, the conversion rate of preparing benzaldehyde by oxidizing benzyl alcohol by adopting the Au-C catalyst can reach 87%, and the selectivity of benzaldehyde can reach more than 83%; the selectivity of the oxidation coupling of benzylamine for preparing imine is up to more than 99%.

Description

Preparation method of Au-C high-selectivity oxidation catalyst with controllable size
Technical Field
The invention relates to a method for preparing an Au-C catalyst with controllable particle size, which can be used for oxidation reactions (including benzaldehyde oxidation, benzylamine oxidation coupling reaction and the like) to generate corresponding oxidation or coupling products with high selectivity. Under the condition of a protective agent, reducing the gold precursor into uniform spherical particles with the size ranging from 2 nm to 20nm by using a reducing agent, and anchoring 0.5 wt% to 5.0wt% of gold particles on the surface of the carbon material through immobilization. Under the condition of normal pressure and oxygen circulation at 40-90 ℃ or connection of an oxygen ball, the conversion rate of preparing benzaldehyde by oxidizing benzyl alcohol by adopting the Au-C catalyst can reach 87%, and the selectivity of benzaldehyde can reach more than 83%; the selectivity of the oxidation coupling of benzylamine to imine is up to more than 99%.
Background
Gold nanocatalysts are widely noticed by researchers due to their excellent activity and selectivity in heterogeneous catalysis. However, the application of the related catalyst in industrialization is still to be further expanded due to the cost of the gold catalyst and the thermal stability in the reaction. As is well known, the nano-gold catalyst has size effect for the reaction, including structure-sensitive CO oxidation reaction, WGSR reaction, nitrobenzene hydrogenation reaction, etc., therefore, the means for developing the nano-gold catalyst with stable performance and controllable size has certain necessity. Meanwhile, the carbon material has rich reserves in the crust of the earth, and can effectively improve the physical properties of the catalyst, such as conductivity, corrosion resistance, hardness and the like, when being used as a carrier of the nano-gold catalyst. The adsorption effect of the large pi bond strengthens the binding force between the carbon nano tube and a noble metal matrix comprising Pt, ru and the like, can highly disperse noble metal nano particles on the outer surface of the carbon nano tube, and avoids the increase of the agglomeration size of the nano particles, thereby further leading to excellent catalytic activity of the noble metal catalyst. In addition, the carbon carrier can be removed by a post-combustion treatment method to recover the noble metal, so that the repeated utilization rate of the noble metal is greatly improved. However, the successful anchoring and surface stabilization of carbon material-supported gold nanoparticles has been very challenging in the case of the gold nanoparticle catalysts using a nanocarbon material as a carrier so far due to the weak interaction between Au-C and the relatively low isoelectric point of the C material.
In any case, for catalytic oxidation processes, such as oxidation removal of trace CO in a fuel cell and reactions of producing acid or aldehyde by selective oxidation of alcohols, the nano-gold catalyst shows more excellent product conversion rate and activity than noble metals such as Pt, pd and Ru. At present, researchers develop design and research aiming at the stability of a nanogold catalyst and a heterogeneous liquid phase catalytic oxidation reaction under a mild condition and single selectivity of a target product.
Patent CN110075830A introduces a method for preparing benzaldehyde by catalyzing benzyl alcohol oxidation reaction with a nano carbon sphere supported palladium catalyst, wherein the nano carbon sphere supported palladium catalyst is prepared by a batch wetting impregnation method, and is stirred and reacted for 6 hours at 80 ℃ to finally prepare a product benzaldehyde, and the conversion rate of the reactant benzyl alcohol reaches 90%. However, the size of the metal nanoparticles of the catalyst prepared by the method is not easy to control, the batch impregnation process is complicated, and the catalyst is used in the benzyl alcohol oxidation reaction and has long reaction time.
Patent CN104069857A discloses a preparation method of a nano Au/MgO catalyst, wherein an MgO carrier is obtained by calcining magnesium hydroxide powder at 450-500 ℃, then the MgO carrier and a methanol solution of chloroauric acid are mixed and added into anhydrous methanol, and the anhydrous ethanol is used as a solvent and a reducing agent to prepare the nano Au/MgO catalyst at room temperature. The catalyst is used for the oxidation reaction of the benzyl alcohol, and the reaction lasts for 3 hours at the temperature of 110 ℃, and the conversion rate of the benzyl alcohol reaches more than 95 percent. However, in the oxidation reaction of benzyl alcohol, the reaction temperature of the catalytic process is relatively high (110 ℃).
In summary, in view of the limitations of stability and product selectivity of the current supported gold nano-catalyst in liquid phase catalytic reaction, it is important to develop a high-efficiency and high-selectivity carbon-based material supported nano-gold catalyst to realize a high-selectivity catalytic process involving molecular oxygen at normal pressure and low temperature.
Disclosure of Invention
The invention relates to a method for preparing an Au-C catalyst with controllable particle size. Under the condition of a protective agent, reducing the gold precursor into uniform spherical particles with the size ranging from 2 nm to 20nm by using a reducing agent, and anchoring 0.5 wt% to 5.0wt% of gold particles on the surface of the carbon material through immobilization. Under the condition of normal pressure and oxygen circulation at 40-90 ℃ or connection of an oxygen ball, the conversion rate of preparing benzaldehyde by oxidizing benzyl alcohol by adopting the Au-C catalyst can reach 87%, and the selectivity of benzaldehyde can reach more than 83%; the selectivity of the oxidation coupling of benzylamine for preparing imine is up to more than 99%.
The technical scheme of the invention is as follows:
a preparation method of a Au-C high-selectivity oxidation catalyst with controllable size comprises the following steps:
the molar concentration is 10 -4 -10 -2 Uniformly mixing a chloroauric acid aqueous solution of mol/L and a protective agent solution of 0.5-4.5mol/L to obtain a mixed solution; adding reducing agent into the mixed solution, controlling the stirring speed at 500-1200r/min, and stirring for 1Forming stable gold sol solution with size range of 2-20nm and homogeneous spherical particles in 0-60 min; in the solid loading process, adding one or more than two of active carbon, carbon nano tubes, graphene oxide and carbon nano-fibers into the stable gold sol solution to be mixed as a carrier, wherein the metal loading is 0.5-5.0wt%, and continuously stirring for 1-16 hours at the temperature of 20-90 ℃ until the color of the supernatant turns transparent and colorless; the sample was washed and filtered with distilled water until pH =7, dried overnight at 60 ℃, ground to a powder; and finally calcining the powder at 250-500 ℃ for 3 hours in an oxygen atmosphere to obtain the Au-C high-selectivity oxidation catalyst.
The protective agent is one or more of tannic acid, polyvinylpyrrolidone, polyvinyl alcohol, cetyl trimethyl ammonium bromide and polyethylene glycol.
One or more than two of sodium borohydride, sodium citrate and ethylene oxide are mixed.
The mass ratio of the protective agent to Au is controlled to be 0.5-10.
An Au-C catalyst powder for high-selectivity catalytic oxidation reaction comprises the following steps:
mixing Au-C high-selectivity oxidation catalyst, benzyl alcohol, sodium hydroxide and p-xylene, controlling the temperature to be 40-90 ℃ under the condition of oxygen circulation or oxygen ball connection, and reacting for 1-10 hours under normal pressure; the mass ratio of the Au-C high-selectivity oxidation catalyst to the benzyl alcohol to the p-xylene to the sodium hydroxide is 0.001-0.05: 0.01 to 0.6:1 to 20:0.01 to 0.2.
Mixing an Au-C catalyst with benzylamine, adding no other reagent, controlling the temperature to be 40-90 ℃ under the condition of oxygen circulation or oxygen ball connection, and reacting for 1-10 hours at normal pressure; the mass ratio of the catalyst to the benzylamine is 0.001-0.05.
The invention has the beneficial effects that: under the conditions of normal pressure and oxygen circulation at 40-90 ℃ or connection of oxygen spheres, the conversion rate of benzaldehyde prepared by oxidizing benzyl alcohol can reach 87%, and the selectivity of benzaldehyde can reach more than 83%; the selectivity of the oxidation coupling of benzylamine for preparing imine is up to more than 99%.
Drawings
FIG. 1 is an X-ray diffraction pattern of an Au-C-1 catalyst with polyvinyl alcohol as a protecting agent.
FIG. 2 is a scanning transmission electron microscope image of Au-C-1 catalyst with polyvinyl alcohol as a protecting agent.
FIG. 3 is an X-ray diffraction pattern of Au-C-2 catalyst with tannic acid as protecting agent.
FIG. 4 is N of Au-C-2 catalyst with tannic acid as protectant 2 Adsorption and desorption isotherm graphs.
FIG. 5 is an X-ray diffraction pattern of an Au-C-3 catalyst with tannic acid as the protecting agent.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the scope of the invention.
EXAMPLE 1Au-C-1 catalyst prepared with PVA as a protectant
0.3mL of the solution was added at a concentration of 5.0X 10 -2 The aqueous chloroauric acid solution in mol/L and 1.5mL of PVA solution with a mass concentration of 1wt% were added to a beaker, and stirred for 20 minutes at room temperature using a magnetic stirrer. 0.76mL of a 0.1mol/L sodium borohydride solution was added, after formation of the wine red gold sol, 5g of carbon nanotubes were added, stirring was continued for 16 hours at normal temperature, and then, the sample was washed and filtered with distilled water to pH =7, dried in air at 60 ℃, and ground to a powder of 60-80 mesh. The powder sample was finally calcined in synthetic air at 300 ℃ for 3 hours to obtain a catalyst Au-C-1 having a gold particle size of 3 to 5nm, and the X-ray diffraction image thereof is shown in FIG. 1 and the scanning transmission electron microscope image thereof is shown in FIG. 2.
EXAMPLE 2 Au-C-2 catalyst with tannic acid as protection and preparation
0.3mL of an aqueous solution of chloroauric acid (5.08X 10) -2 mol/L) was added to a three-necked flask under the protection of 1.3mL of tannin solution (1 wt%), 30mL of deionized water was added, and then placed on a magnetic stirrer and stirred at 80 ℃ for 10 minutes, and 1.37mL of sodium citrate solution (1 wt%)) Reduction was carried out, stirring was continued for 15 minutes while maintaining the temperature until the solution turned wine red and a gold sol was formed, a mass of carbon nanotubes (metal loading 1.5 wt%) was added to the gold sol, stirring was continued for 16 hours at normal temperature, and subsequently, the sample was washed and filtered with distilled water to pH =7, dried in air at 60 ℃, and then ground into a fine powder. The powder sample was finally calcined at 300 ℃ for 3 hours in an oxygen atmosphere to obtain a catalyst Au-C-2 having a gold particle size of 6 to 10nm, the X-ray diffraction pattern of which is shown in FIG. 3, N 2 The adsorption and desorption isotherms are shown in FIG. 4.
EXAMPLE 3 Au-C-3 catalyst with tannic acid as protection and preparation
0.3mL of an aqueous solution of chloroauric acid (5.08X 10) -2 mol/L) was added to a three-necked flask under the protection of 0.5mL of tannin solution (1 wt%), 30mL of deionized water was added, then placed on a magnetic stirrer and stirred at 80 ℃ for 10 minutes, then 1.37mL of sodium citrate solution (1 wt%) was added thereto to perform reduction, the temperature was kept continuously stirred for 15 minutes until the solution became wine red and gold sol was formed, a certain mass of carbon nanotubes (metal loading 1.5 wt%) was added to the gold sol, stirring was continued at normal temperature for 16 hours, and then, the sample was washed and filtered with distilled water to pH =7, dried in air at 60 ℃, and then ground into fine powder. The powder sample was finally calcined at 300 ℃ for 3 hours in an oxygen atmosphere to obtain a catalyst Au-C-3 having a gold particle size of 9 to 13nm, and its X-ray diffraction pattern is shown in FIG. 5.
EXAMPLE 4 Au-C-4 catalyst prepared with polyvinylpyrrolidone (PVP) as a protectant
0.3mL of an aqueous solution of chloroauric acid (5.08X 10) -2 mol/L) is added into a beaker under the protection of PVP solution (1 wt percent), 30mL of deionized water is added, then the beaker is placed on a magnetic stirrer to be stirred for 20 minutes at normal temperature, and a certain amount of sodium borohydride (NaBH) is added into the beaker 4 ) The solution (0.1 mol/L) was reduced, the solution turned to wine red, a gold sol was formed, a certain mass of carbon nanotubes (metal loading 1.5 wt%) was added to the gold sol, stirring was continued for 16 hours at normal temperature, and then, the sample was washed and filtered with distilled water to have pH =7, dried in the air at 60 ℃, and then, driedGrinding into fine powder. And finally calcining the powder sample at 300 ℃ for 3 hours in an oxygen atmosphere to obtain the catalyst Au-C-4 with the gold particle size of 13-20nm.
EXAMPLE 5 Au-C-5 catalyst prepared with PVA as protectant
0.3mL of the solution was added at a concentration of 5.0X 10 -2 The aqueous chloroauric acid solution in mol/L and 1.5mL of PVA solution with a mass concentration of 1wt% were added to a beaker, and stirred for 20 minutes at room temperature using a magnetic stirrer. 0.76mL of a 0.1mol/L sodium borohydride solution was added, after formation of a wine red gold sol, 5g of activated carbon was added, the pH was adjusted to 1.0 with 1.0mol/L HCl solution, stirring was continued for 16 hours at normal temperature, and subsequently, the sample was washed and filtered with distilled water to pH =7, dried in air at 60 ℃, and ground to a powder of 60-80 mesh. The powder sample was finally calcined in synthetic air at 300 ℃ for 3 hours to obtain the catalyst Au-C-5 with gold particle size of 2-4 nm.
EXAMPLE 6Au-C-1 catalyst for the preparation of benzaldehyde by the Oxidation of benzyl alcohol
0.01g of Au-C-1 catalyst, 0.054g of benzyl alcohol, 5.5g of p-xylene and 0.0084g of sodium hydroxide are mixed and added into a three-neck flask, the three-neck flask is placed in an oil bath kettle at the temperature of 80 ℃, oxygen is continuously introduced into the three-neck flask for continuous reaction, the flow rate of the oxygen is controlled to be 40mL/min, and the reaction time is 3 hours. The product was separated and the reaction was analyzed by gas chromatography to yield a benzyl alcohol conversion of 87% with a benzaldehyde selectivity of 71%.
EXAMPLE 7Au-C-2 for the preparation of benzaldehyde by the Oxidation of benzyl alcohol
0.01g of Au-C-2 catalyst, 0.054g of benzyl alcohol, 5.5g of p-xylene and 0.0084g of sodium hydroxide are mixed and added into a three-neck flask, the three-neck flask is placed in an oil bath kettle at the temperature of 80 ℃, oxygen is continuously introduced into the three-neck flask for continuous reaction, the flow rate of the oxygen is controlled to be 40mL/min, the reaction time is 3 hours, the product is separated, and the reactants are analyzed by gas chromatography, so that the conversion rate of the benzyl alcohol is 76 percent, and the selectivity of benzaldehyde is 72 percent.
EXAMPLE 8Au-C-3 preparation of benzaldehyde by Oxidation of benzyl alcohol
0.01g of Au-C-3 catalyst, 0.054g of benzyl alcohol, 5.5g of p-xylene and 0.0084g of sodium hydroxide are mixed and added into a three-neck flask, the three-neck flask is placed in an oil bath kettle at the temperature of 80 ℃, oxygen is continuously introduced into the three-neck flask for continuous reaction, the flow rate of the oxygen is controlled to be 40mL/min, the reaction time is 3 hours, products are separated, reactants are analyzed by adopting gas chromatography, the conversion rate of the benzyl alcohol is 45 percent, and the selectivity of benzaldehyde is 83 percent.
EXAMPLE 9Au-C-4 preparation of benzaldehyde by Oxidation of benzyl alcohol
0.01g of Au-C-4 catalyst, 0.054g of benzyl alcohol, 5.5g of p-xylene and 0.0084g of sodium hydroxide are mixed and added into a three-neck flask, the three-neck flask is placed in an oil bath kettle at the temperature of 80 ℃, oxygen is continuously introduced into the three-neck flask for continuous reaction, the flow rate of the oxygen is controlled to be 40mL/min, the reaction time is 3 hours, products are separated, reactants are analyzed by adopting gas chromatography, the conversion rate of the benzyl alcohol is 28 percent, and the selectivity of benzaldehyde is 70 percent.
EXAMPLE 10 use of Au-C-1 catalyst for oxidative coupling of benzylamine to imine
0.02g of Au-C-1 catalyst and 7.5mmol of imine were added to a three-necked flask and mixed uniformly, vacuum-pumping was performed and oxygen gas was introduced to replace pure oxygen gas three times, the three-necked flask was sealed with a rubber stopper, and molecular oxygen was supplied by connecting an oxygen balloon. The reaction mixture is heated to 100 ℃ and reacted for 10h without other alkaline substances or solutions. Separating the product, and analyzing the reactant by gas chromatography to obtain benzylamine with conversion rate of 19% and imine selectivity of 99%.
EXAMPLE 11 use of Au-C-1 catalyst for oxidative coupling of benzylamine to imine
0.02g of Au-C-1 catalyst and 7.5mmol of imine were added to a three-necked flask and mixed uniformly, vacuum-pumping was performed and oxygen gas was introduced to replace pure oxygen gas three times, the three-necked flask was sealed with a rubber stopper, and molecular oxygen was supplied by connecting an oxygen balloon. The reaction mixture was warmed to 100 ℃ and reacted for 10h without other alkaline substances or solutions. And separating the product, and analyzing the reactant by adopting gas chromatography to obtain the benzylamine with the conversion rate of 56% and the imine selectivity of more than 99%.

Claims (4)

1. A preparation method of a Au-C high-selectivity oxidation catalyst with controllable size is characterized by comprising the following steps:
the molar concentration is 10 -4 -10 -2 Uniformly mixing a chloroauric acid aqueous solution of mol/L and a protective agent solution of 0.5-4.5mol/L to obtain a mixed solution; adding a reducing agent into the mixed solution, controlling the stirring speed to be 500-1200r/min, and stirring for 10-60 min to form a stable gold sol solution consisting of uniform spherical particles with the size range of 2-20 nm; in the solid loading process, adding one or more than two of activated carbon, carbon nano tubes, graphene oxide and carbon nano fibers into the stable gold sol solution to be mixed as a carrier, wherein the metal loading is 0.5-5.0wt%, and continuously stirring for 1-16 hours at the temperature of 20-90 ℃ until the color of the supernatant turns transparent and colorless; the sample was washed and filtered with distilled water until pH =7, dried overnight at 60 ℃, ground to a powder; calcining the powder in an oxygen atmosphere at 250-500 ℃ for 3 hours to obtain an Au-C high-selectivity oxidation catalyst;
the protective agent is tannic acid, polyvinylpyrrolidone or polyethylene glycol;
the reducing agent is sodium borohydride or sodium citrate;
when the protective agent is tannic acid, the reducing agent is sodium citrate;
when the protective agent is polyvinylpyrrolidone or polyethylene glycol, the reducing agent is sodium borohydride.
2. The preparation method according to claim 1, wherein the mass ratio of the protecting agent to Au is 0.5 to 1-10, and the molar ratio of the reducing agent to the Au precursor is 0.5 to 1-10.
3. The use of a highly selective Au-C catalyst powder in catalytic oxidation reactions, said Au-C catalyst powder being obtained by the process according to claim 1, characterized by the following steps:
mixing Au-C high-selectivity oxidation catalyst, benzyl alcohol, sodium hydroxide and p-xylene, controlling the temperature to be 40-90 ℃ under the condition of oxygen circulation or oxygen ball connection, and reacting for 1-10 hours under normal pressure; the mass ratio of the Au-C high-selectivity oxidation catalyst to the benzyl alcohol to the p-xylene to the sodium hydroxide is 0.001 to 0.05:0.01 to 0.6:1 to 20:0.01 to 0.2.
4. The use of a highly selective Au-C catalyst powder in catalytic oxidation reactions, said Au-C catalyst powder being obtained by the process according to claim 1, characterized by the following steps:
mixing Au-C catalyst with benzylamine, without adding other reagents, controlling the temperature to 40-90 ℃ under the condition of oxygen circulation or oxygen ball connection, and reacting for 1-10 hours under normal pressure; the mass ratio of the catalyst to benzylamine is 0.001 to 0.05.
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CN107597109A (en) * 2017-08-09 2018-01-19 华东师范大学 Load type gold catalyst of nano-metal-oxide doping and preparation method and application
CN108160094A (en) * 2016-12-07 2018-06-15 中国科学院大连化学物理研究所 A kind of N doping Carbon Materials support noble metal catalyst and preparation and application
CN109731573A (en) * 2018-12-24 2019-05-10 大连理工大学 A kind of preparation method and application of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst

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Publication number Priority date Publication date Assignee Title
CN105618038A (en) * 2014-10-28 2016-06-01 中国石油化工股份有限公司 Supported gold catalyst, preparation method thereof, and p-aminophenol preparation method
CN108160094A (en) * 2016-12-07 2018-06-15 中国科学院大连化学物理研究所 A kind of N doping Carbon Materials support noble metal catalyst and preparation and application
CN107597109A (en) * 2017-08-09 2018-01-19 华东师范大学 Load type gold catalyst of nano-metal-oxide doping and preparation method and application
CN109731573A (en) * 2018-12-24 2019-05-10 大连理工大学 A kind of preparation method and application of benzyl alcohol oxidation producing benzaldehyde high activity Au/ nanocarbon catalyst

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