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CN113877574B - Preparation method and application of zirconium dioxide nanotube array immobilized monoatomic catalyst - Google Patents

Preparation method and application of zirconium dioxide nanotube array immobilized monoatomic catalyst Download PDF

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CN113877574B
CN113877574B CN202111332005.0A CN202111332005A CN113877574B CN 113877574 B CN113877574 B CN 113877574B CN 202111332005 A CN202111332005 A CN 202111332005A CN 113877574 B CN113877574 B CN 113877574B
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catalyst
nanotube array
zirconium dioxide
dioxide nanotube
zirconium
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CN113877574A (en
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王延吉
郭力铭
丁晓墅
赵新强
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Hebei University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a preparation method and application of a zirconium dioxide nanotube array immobilized monoatomic catalyst. The method adopts an anodic oxidation method to generate a zirconia nanotube array on the surface of zirconium metal, and successfully carries monoatomic platinum by an extremely low concentration solution adsorption method, thereby improving the utilization rate of platinum and greatly reducing the cost of the catalyst; the single atom, namely the active component, is Pt, and the carrier of the catalyst is a zirconium piece of a zirconium dioxide nanotube array prepared by an anodic oxidation method. The catalyst prepared by the invention is used for 2, 4-dinitrotoluene or nitrotoluene, and the yield is over 90 percent.

Description

Preparation method and application of zirconium dioxide nanotube array immobilized monoatomic catalyst
Technical Field
The invention belongs to the field of combination of electrochemistry and green catalytic chemistry, and particularly relates to a preparation method and application of a zirconium dioxide nanotube array immobilized monoatomic catalyst.
Background
Aromatic amine and its derivative are widely used in chemical industry, dye, medicine and surfactant to prepare medicine intermediate, fluorescent brightening agent, etc. and are important organic intermediate. In practice, there are many methods for producing aromatic amines, such as addition of unsaturated bonds, substitution of amino groups with negative ion groups, reduction of N-containing organic substances, etc., but most of aromatic amines are produced by reduction of aromatic nitro compounds in practical use. With the rapid development of the chemical industry in China, the reduction methods of aromatic nitro compounds are numerous, and the reduction methods mainly comprise an iron powder reduction method, an alkali sulfide reduction method, a catalytic hydrogenation reduction method and the like. The iron powder reduction method has the defects of poor product quality, waste water discharge and the like, and the method has the advantages of higher raw material cost and lower yield of the reduction of the sodium sulfide, and cannot be widely applied. In order to solve the problems of energy shortage, serious environmental pollution and the like in the world, the use and development of clean energy are urgent, hydrogen is taken as a novel clean energy, the importance of the hydrogen is increasingly highlighted, and the research on the catalytic hydrogenation reaction of aromatic nitro compounds has become a hot spot and mainstream. The catalyst is a major factor affecting the hydrogenation of aromatic nitro compounds. The types of catalysts used for hydrogenation of aromatic nitro compounds are numerous, noble metals mainly comprise platinum and palladium, but the noble metals are expensive, and if the use amount of the noble metals can be reduced, the cost can be greatly saved.
The Wang Yanji subject group of Hebei university researches stainless steel-based supported monoatomic Pt for catalyzing nitrobenzene hydrogenation reaction, has high catalytic activity and is not deactivated after repeated use for 30 times, and meanwhile, the subject group researches powdery monoatomic Pt for catalyzing hydrogenation reaction of nitro compounds, has high catalytic activity and 100 percent of yield, but has the problem of loss in the recovery process.
Disclosure of Invention
The invention aims to provide a preparation method and application of a zirconium dioxide nanotube array immobilized monoatomic catalyst aiming at the problems of low atom utilization rate, high catalyst use cost, low catalyst efficiency and the like in the catalytic hydrogenation reaction of an aromatic nitro compound. The method adopts an anodic oxidation method to generate a zirconia nanotube array on the surface of zirconium metal, and successfully carries monoatomic platinum by an extremely low concentration solution adsorption method, thereby improving the utilization rate of platinum and greatly reducing the cost of the catalyst; the catalyst prepared by the invention is used for 2, 4-dinitrotoluene or nitrotoluene, and the yield is over 90 percent.
The technical scheme of the invention is as follows:
a preparation method of a zirconium dioxide nanotube array immobilized monoatomic catalyst, wherein the monoatomic catalyst is Pt as an active component, and the carrier of the catalyst is an anodic zirconium dioxide nanotube.
(1) Cleaning the polished Zr slice, inserting the Zr slice into the mixed solution, taking the Zr slice as an anode, taking the Pt slice as a cathode, carrying out anodic oxidation for 2-4 hours under the conditions of 20-50 ℃ and 20-50V voltage, and after the reaction, washing and drying to obtain the metallic zirconium slice with the surface generating the zirconium dioxide nanotube array;
wherein, the solute of the mixed solution is ammonium fluoride, and the concentration of the ammonium fluoride is 0.3 to 1 percent of the ammonium fluoride by mass percent; the solvent is a mixture of an organic solvent and water, and the volume of the water is 5% -10% of the total volume of the solvent; the organic solvent is glycerin and formamide, and the volume ratio of the glycerin to the formamide is 1:1;
(2) Immersing a metal zirconium sheet with a zirconium dioxide nanotube array generated on the surface into a reaction kettle filled with 0.8 ppm-45 ppm Pt chloroplatinic acid aqueous solution, heating the reaction kettle to 120-155 ℃, sealing, introducing 0.35-1 MPa hydrogen, and stirring for 1-3 h;
then opening the reaction kettle, replacing a new chloroplatinic acid aqueous solution with the concentration of 0.8ppm to 45ppm Pt, repeating the above-mentioned process of immersing, heating, ventilating and stirring for 4 to 10 times, cleaning and airing to obtain the catalyst of the zirconium dioxide nanotube array immobilized with the monoatomic Pt, namely Pt modified ZrO 2 -NTs。
The application of the zirconium dioxide nanotube array immobilized monoatomic catalyst prepared by the method is used for preparing aromatic amine by hydrogenation reaction of nitroaromatic hydrocarbon;
the method specifically comprises the following steps:
putting a zirconium dioxide nanotube array immobilized monoatomic catalyst, nitroarene and ethanol into a high-pressure reaction kettle, filling hydrogen with the pressure of 1-2 MPa after inert gas replaces air in the kettle, and reacting for 8-10 hours at the temperature of 80-120 ℃ under stirring to obtain aromatic amine;
adding 0.1-50 square cm of catalyst into each gram of nitroarene; the area of the catalyst is calculated as the area of one side of the zirconium support sheet.
The catalyst is preferably supported in a frame.
The nitroarene is preferably 2, 4-dinitrotoluene or nitrotoluene.
The invention has the substantial characteristics that:
in the prior art, platinum is immobilized with TiO 2 Nanotubes, al 2 O 3 Nanotubes, etc., but platinum exists in the form of nanoclusters, no report has been found that the active metal component is immobilized on ZrO in the form of a single atom 2 Report of catalysts for nanotubes.
It should be noted that the basic units of nanomaterials can be divided into three classes by dimension: (1) zero dimension: such as nanoscale particles, clusters of atoms, etc.; (2) one-dimensional: such as nanowires, nanorods, nanotubes, etc.; (3) two-dimensional: such as ultrathin films, multilayer films, superlattices, etc. The seemingly similar nanomaterials are quite different. The invention takes zirconium metal as a substrate, forms a zirconium dioxide nanotube array which is a one-dimensional nanotube through anodic oxidation, increases ZrO 2 And improves the immobilization efficiency of single atoms, so that the activity is greatly improved. Compared with the traditional powder catalyst, the preparation method has the advantages of short preparation period, simple operation and better economic benefit.
The invention has the beneficial effects that:
the invention discloses a preparation method and application of a single-atom platinum modified zirconium dioxide nanotube array immobilized catalyst. Compared with the existing nitroarene selective hydrogenation catalyst, the catalyst has remarkable advantages, and is specifically characterized in that:
(1) Firstly, a zirconium dioxide nanotube array is obtained by a simple anodic oxidation method, and a solution adsorption method with simple operation is used for preparing the catalyst, so that the catalyst is simple in preparation method, no cocatalyst is adopted, raw material Zr sheets are easy to obtain, the price of Pt is relatively high, but the used chloroplatinic acid solution exists in a very dilute solution form, noble metal Pt is dispersed in an atomic level, the metal utilization rate is high, and therefore, the use cost is greatly reduced, and the use cost is about 40-50%. The catalyst has low equipment requirement, safe operation and easy realization. The catalyst is used for catalyzing the hydrogenation reaction of 2, 4-dinitrotoluene, and the yield is 90%; the hydrogenation reaction of nitrobenzene is catalyzed, and the yield is 94 percent.
(2) The traditional powder catalyst, the product and the catalyst can be subjected to centrifugal separation or filtration separation, the catalyst can be lost in the operation process, and when the catalyst is subjected to stability evaluation, the catalyst can not be collected in a hundred percent, and the loss of the catalyst can be greatly reduced by the catalyst which is now made into a metal substrate. Compared with the traditional powder catalyst, the Zr piece prepared by anodic oxidation has the advantages that the surface area is increased by 70 to 80 percent, so that the atomic-level Pt is better and uniformly dispersed in the ZrO 2 Is a kind of medium. The prepared catalyst has good reaction activity and stability, is repeatedly used for about 20 times, has unchanged yield, and has strong directional hydrogenation capability on nitro groups in the use process, and the activity of other functional groups is inhibited without adding any organic reagent. The catalyst has better substrate adaptability for the selective hydrogenation of nitrobenzene or nitroaromatic hydrocarbon containing multiple functional groups.
Drawings
FIG. 1 shows ZrO as prepared in example 1 of the present invention 2 SEM photograph of nanotubes.
Detailed description of the preferred embodiments
The following is a further explanation of the embodiments of the present invention and the accompanying drawings. The following examples are only illustrative of the present invention and are not intended to limit the scope of the invention.
Example 1:
anodic oxidation of ZrO 2 And (3) preparation of a nanotube array.
Zr flakes were cut (10 mm x 20mm x 0.1 mm) and ultrasonically cleaned with absolute ethanol, acetone to remove oil stains from the Zr flakes surface. Preparing a mixed solution by 0.6g of ammonium fluoride, 5ml of distilled water, 30ml of glycerol and 30ml of formamide, inserting 10mm of lower end of a zirconium sheet into the mixed solution, taking the Zr sheet as an anode and the Pt sheet as a cathode, carrying out anodic oxidation for 3 hours under the condition of 30 ℃ and 50V voltage, washing and drying after the reaction is finished, and obtaining the metallic zirconium sheet with the surface of which the zirconium dioxide nanotube array is generated.
FIG. 1 shows ZrO as prepared in example 1 2 SEM photograph of nanotubes, by which we can see clearly visible ZrO 2 A nanotube.
Example 2:
monoatomic Pt immobilized ZrO 2 And (3) preparation of a nanotube array catalyst.
10 sheets were loaded with ZrO 2 Zr sheets (example 1) of the nanotube array are placed in a screen frame on a stirring paddle, an extremely dilute chloroplatinic acid aqueous solution of 15ppm Pt is added, then the reaction kettle is heated to 125 ℃, 1MPa hydrogen is introduced for treatment for 1h, and the treatment liquid is continuously stirred by the stirring paddle in the treatment process so as to be fully contacted with the metal carrier.
Repeating the above process for 4 times, washing the test piece with deionized water, and naturally drying at room temperature to obtain catalyst with Pt-modified ZrO 2 -NTs。
Example 3:
the application of the zirconium dioxide nanotube array immobilized monoatomic catalyst in the selective hydrogenation of nitroaromatics.
The hydrogenation of 2, 4-dinitrotoluene was carried out by subjecting 10 sheets of Pt-modified ZrO 2 NTs (example 2) were placed in a designed catalyst screen frame, 2g of 2, 4-dinitrotoluene and 100ml of ethanol were placed in an autoclave and then N was used 2 To replace the air in the autoclave, then the autoclave was punched to 2MPa with high-pressure hydrogen, the reaction temperature was raised to 100 ℃, reacted for 8 hours, cooled to room temperature, and the product was taken out of the autoclave and analyzed by gas chromatography. 2, 4-diaminotoluene was obtained in a yield of 90%.
Example 4:
the concentration of the aqueous solution of chloroplatinic acid was 5ppm, and the other conditions were the same as in examples 1, 2 and 3. The yield thereof was found to be 82%.
Example 5.
The concentration of the aqueous solution of chloroplatinic acid was 10ppm, and the other conditions were the same as in examples 1, 2 and 3. The yield thereof was found to be 84%.
Example 6:
the concentration of the aqueous solution of chloroplatinic acid was 20ppm, and the other conditions were the same as in examples 1, 2 and 3. The yield thereof was found to be 87%.
Example 7:
the concentration of the aqueous solution of chloroplatinic acid was 25ppm, and the other conditions were the same as in examples 1, 2 and 3. The yield thereof was found to be 85%.
Example 8:
the number of Zr flakes was 5, and the other conditions were the same as in examples 1, 2 and 3. The yield thereof was found to be 75%.
Example 9:
the number of Zr flakes was 20, and the other conditions were the same as in examples 1, 2 and 3. The yield thereof was found to be 95%.
Example 10:
the other conditions were the same as in examples 1, 2 and 3 except that nitrobenzene was used as a substrate. The aniline was obtained in 94% yield. After the reaction was completed, the product was taken out of the autoclave and analyzed by gas chromatography. In the examples, the conversion and yield were calculated from the following formulas, respectively:
conversion of nitroaromatics = (raw material-product)/raw material = 100%
Aromatic amine yield = product/(raw material-product) ×100%
Wherein, the qualitative and quantitative of the catalytic reaction is completed on Agilent gas chromatograph, and the FID detector is used for analysis.
The invention is not a matter of the known technology.

Claims (6)

1. The preparation method of the zirconium dioxide nanotube array immobilized monoatomic catalyst is characterized by comprising the following steps of:
(1) Cleaning the polished Zr slice, inserting the Zr slice into the mixed solution, taking the Zr slice as an anode, taking the Pt slice as a cathode, carrying out anodic oxidation for 2-4 hours under the conditions of 20-50 ℃ and 20-50V voltage, and after the reaction, washing and drying to obtain the metallic zirconium slice with the surface generating the zirconium dioxide nanotube array;
wherein, the solute of the mixed solution is ammonium fluoride, and the concentration of the ammonium fluoride is 0.3-1 percent by mass; the solvent is a mixture of an organic solvent and water, and the volume of the water is 5% -10% of the total volume of the solvent; the organic solvent is glycerin and formamide, and the volume ratio of the glycerin to the formamide is 1:1;
(2) Immersing a metal zirconium sheet with a zirconium dioxide nanotube array generated on the surface into a reaction kettle filled with 0.8 ppm-45 ppm Pt chloroplatinic acid aqueous solution, heating the reaction kettle to 120-155 ℃, sealing, introducing 0.35-1 MPa hydrogen, and stirring for 1-3 h;
then opening the reaction kettle, replacing a new chloroplatinic acid aqueous solution with the concentration of 0.8ppm to 45ppm Pt, repeating the above-mentioned process of immersing, heating, ventilating and stirring for 4 to 10 times, cleaning and airing to obtain the catalyst of the zirconium dioxide nanotube array with single atom Pt, namely Pt modified ZrO 2 -NTs；
The monoatomic active component is Pt, and the carrier of the catalyst is an anodic zirconia nanotube.
2. The application of the zirconium dioxide nanotube array immobilized monoatomic catalyst prepared by the method of claim 1, which is characterized in that the catalyst is used for preparing aromatic amine by hydrogenation of nitroaromatic hydrocarbon.
3. The use according to claim 2, characterized by the steps of:
putting a zirconium dioxide nanotube array immobilized monoatomic catalyst, nitroarene and ethanol into a high-pressure reaction kettle, filling hydrogen with the pressure of 1-2 MPa after inert gas replaces air in the kettle, and reacting for 8-10 h at 80-120 ℃ under stirring to obtain the aromatic amine.
4. Use according to claim 3, wherein the catalyst is preferably supported in a frame.
5. The process according to claim 3, wherein 0.1 to 50 square cm of catalyst is added per gram of nitroaromatic hydrocarbon; the area of the catalyst is the area of the carrier zirconium piece.
6. The method of claim 3, wherein the nitroarene is 2, 4-dinitrotoluene or nitrotoluene.
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