CN115672321B - Pt 3 Preparation method of Mn/CNTs catalyst and application of catalyst - Google Patents
Pt 3 Preparation method of Mn/CNTs catalyst and application of catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000000243 solution Substances 0.000 claims abstract description 45
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
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- 239000011572 manganese Substances 0.000 claims description 46
- MSTNYGQPCMXVAQ-KIYNQFGBSA-N 5,6,7,8-tetrahydrofolic acid Chemical compound N1C=2C(=O)NC(N)=NC=2NCC1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 MSTNYGQPCMXVAQ-KIYNQFGBSA-N 0.000 claims description 28
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- 229960000304 folic acid Drugs 0.000 claims description 26
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- 239000001257 hydrogen Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- MSTNYGQPCMXVAQ-RYUDHWBXSA-N (6S)-5,6,7,8-tetrahydrofolic acid Chemical compound C([C@H]1CNC=2N=C(NC(=O)C=2N1)N)NC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 MSTNYGQPCMXVAQ-RYUDHWBXSA-N 0.000 claims description 9
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 30
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
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- 239000006171 Britton–Robinson buffer Substances 0.000 description 1
- 229910002837 PtCo Inorganic materials 0.000 description 1
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- HDFXRQJQZBPDLF-UHFFFAOYSA-L disodium hydrogen carbonate Chemical compound [Na+].[Na+].OC([O-])=O.OC([O-])=O HDFXRQJQZBPDLF-UHFFFAOYSA-L 0.000 description 1
- CBMPTFJVXNIWHP-UHFFFAOYSA-L disodium;hydrogen phosphate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].OP([O-])([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CBMPTFJVXNIWHP-UHFFFAOYSA-L 0.000 description 1
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- 150000004687 hexahydrates Chemical class 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- BUCIWTBCUUHRHZ-UHFFFAOYSA-K potassium;disodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[K+].OP(O)([O-])=O.OP([O-])([O-])=O BUCIWTBCUUHRHZ-UHFFFAOYSA-K 0.000 description 1
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Abstract
The present invention relates to Pt 3 The preparation method of Mn/CNTs catalyst and the application of the catalyst at least comprise the following steps: s1, respectively preparing a carbon nano tube solution and a precursor metal salt solution; s2, uniformly mixing the carbon nanotube solution and the precursor metal salt solution to obtain a first mixed solution; s3, freeze-drying the first mixed solution, and performing thermal shock to obtain Pt 3 Mn/CNTs catalyst. The invention prepares Pt by using a thermal shock method 3 Mn/CNTs catalyst. The preparation method is simple, and meanwhile, pt 3 Mn can be uniformly loaded on the carbon nano tube, so that the problem of agglomeration of platinum-based bimetallic intermetallic compound particles is solved.
Description
Technical Field
The invention relates to the field of intermetallic compound synthesis, in particular to Pt 3 Preparation method of Mn/CNTs catalyst and application of the catalyst.
Background
Intermetallic compounds are materials composed of two or more elements located in the periodic table, whose particular combination of crystal and electronic structure results in their unique adsorption and catalytic properties. Heterogeneous catalysis of intermetallic compounds has been considered as a rapidly evolving field.
Unlike the crystal structure of the constituent elements, the intermetallic compound crystal structure is completely or at least partially ordered. The degree of ordering of intermetallic structures is mainly determined by the annealing temperature, and is therefore usually made into an ordered structure by a high-temperature annealing method. However, high temperature heat treatment can lead to agglomeration of nanoparticles, resulting in a reduction in surface area. Thus, one of the major challenges in current intermetallic catalyst research is how to obtain ordered intermetallic structures without serious nanoparticle agglomeration.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Pt 3 Mn catalyst preparation method and application of Mn catalyst, pt is prepared by using thermal shock method 3 Mn/CNTs catalyst. The preparation method is simple, and meanwhile, pt 3 Mn can be uniformly loaded on the carbon nano tube, so that the problem of agglomeration of platinum-based bimetallic intermetallic compound particles is solved.
To solve the technical problems, the invention provides Pt 3 The preparation method of the Mn/CNTs catalyst at least comprises the following steps:
s1, respectively preparing a carbon nano tube solution and a precursor metal salt solution;
s2, uniformly mixing the carbon nanotube solution and the precursor metal salt solution to obtain a first mixed solution;
s3, freeze-drying the first mixed solution, and performing thermal shock to obtain Pt 3 Mn/CNTs catalyst.
Further, the precursor metal salt solution comprises chloroplatinic acid aqueous solution and manganese salt aqueous solution, and the concentrations of the chloroplatinic acid aqueous solution and the manganese salt aqueous solution are respectively 0.01-0.2mol/L.
Further, the concentration of the carbon nanotube solution is 5-25mg/mL.
And further, the freeze drying step is that the first mixed solution is placed in a freeze dryer, frozen for 3-24 hours, and then dried in vacuum for 12-48 hours, so that the sample to be subjected to thermal shock is obtained.
Further, the thermal shock step is that a sample to be thermal shock is evenly paved on the carbon cloth, the impact voltage is 20V, the impact current is 9+2 (n-1) A, and n is the impact times; the impact current is impacted for 10s each time, and the intermittent time between two adjacent impacts is 5s, until the surface temperature of the sample to be impacted reaches 800 ℃, and the impact is stopped.
Through the technical scheme, in the thermal shock process, one current corresponds to one temperature, the sample to be thermally shocked is impacted for 10S from 9A, and the temperature of the surface of the sample is detected. The impact is then stopped and the sample surface undergoes a cooling process. 11A impacted the sample and the surface of the sample began to warm again, held for 10S, and then underwent a cool down process. And so on until the sample surface reached 800 ℃. Therefore, the surface of the sample is subjected to a temperature raising and reducing process each time the sample is impacted, the annealing temperature is accurately controlled, and the ordering degree of the intermetallic compound structure can be promoted.
The second invention provides Pt obtained by the preparation method 3 Mn/CNTs catalyst.
The third invention provides a Pt film comprising the above Pt 3 Mn/CNTs catalyst in synthesizing tetrahydrofolic acid.
Further, pt is 3 Adding Mn/CNTs catalyst and folic acid solution into a reaction kettle, filling hydrogen into the reaction kettle, and carrying out hydrogenation reaction on folic acid and hydrogen under the conditions that the internal pressure of the reaction kettle is 20-80bar and the internal temperature is 40-90 ℃, thus obtaining tetrahydrofolic acid after the reaction is finished.
Further, the folic acid and the Pt 3 The mass ratio of Mn/CNTs catalyst is 100 (0.1-20).
Further, the reaction time of the folic acid and the hydrogen for hydrogenation reaction is 6-24h.
Through the technical scheme, carbon-nitrogen double bonds in the folic acid are reduced by hydrogen, and particularly, the hydrogen is adsorbed on Pt 3 MnOn the surface of the CNTs catalyst, folic acid coordinates with the catalyst, and hydrogen molecules of hydrogen gas are Pt 3 The Mn/CNTs catalyst is catalyzed to break bonds to form active hydrogen atoms, the hydrogen atoms of the hydrogen atoms are combined with carbon-nitrogen double bonds of folic acid, and carbon-nitrogen single bonds are formed by reduction to generate tetrahydrofolic acid.
Wherein Pt is 3 Mn/CNTs catalyst refers to a catalyst in which intermetallic particles are uniformly supported on carbon nanotubes.
Further, filling hydrogen into the reaction kettle until the reaction kettle does not contain gas except hydrogen;
in the process of Pt 3 Before Mn/CNTs catalyst and folic acid solution are added into a reaction kettle, nitrogen or inert gas is filled into the reaction kettle so as to form an anaerobic environment in the reaction kettle.
Further, after the hydrogenation reaction is finished, the step of obtaining the tetrahydrofolic acid comprises the following steps:
after the reaction is finished, a solution containing the tetrahydrofolic acid is obtained, the pH value of the tetrahydrofolic acid-containing sediment is regulated to 3-3.5 by an acid solution, the solution containing the tetrahydrofolic acid-containing sediment is obtained, the solution containing the tetrahydrofolic acid-containing sediment is filtered, the tetrahydrofolic acid-containing sediment is collected, and the tetrahydrofolic acid-containing sediment is dried, so that the tetrahydrofolic acid is obtained.
Through the technical scheme, after the reaction is finished, the whole system is homogeneous, the tetrahydrofolic acid can be separated out under the acidic condition, and the pH value is 3-3.5 when the tetrahydrofolic acid separation yield is highest;
tetrahydrofolate is sensitive to oxygen and is easily oxidized into dihydrofolate, so that the whole reaction process needs an anaerobic environment;
further, the drying mode comprises freeze drying, vacuum drying and the like, and the drying is carried out under the anaerobic condition to prevent the tetrahydrofolic acid from being oxidized;
filtering under nitrogen or inert gas to avoid oxidation of tetrahydrofolic acid.
Further, the pH of the folic acid solution is 6-7, and the preparation of the folic acid solution comprises the following steps:
adding solid folic acid into a flask, filling nitrogen or inert gas into the flask to form an anaerobic environment, adding buffer solution with pH of 4-7 into the flask, stirring uniformly to obtain a mixed solution, and regulating the pH of the mixed solution to 6-7 by using alkali solution to obtain folic acid solution.
Further, folic acid solution is prepared under room temperature environment, namely 25-35 ℃.
Further, buffer solution is added to control the pH of the solution, so as to avoid titration jump;
further, folic acid is dissolved in an alkaline solution, and when the folic acid solution is adjusted to ph=7 by alkali, the folic acid reaction produces the highest yield of tetrahydrofolic acid.
Further, the buffer solution includes any one of disodium hydrogen phosphate-citric acid buffer solution, sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution, disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution, barbital sodium-hydrochloric acid buffer solution, tris-hydrochloric acid buffer solution, boric acid-borax buffer solution, glycine-sodium hydroxide buffer solution, borax-sodium hydroxide buffer solution, sodium carbonate-sodium bicarbonate buffer solution, britton-Robinson buffer solution and Tris buffer salt solution.
Further, the alkali solution includes any one of NaOH solution and KOH solution.
Further, the amount of buffer is 10-15ml/1g solid folic acid.
In summary, the invention has the following beneficial effects:
1. preparation of Pt according to the invention 3 The Mn/CNTs catalyst has low material cost, greatly reduces the use amount of Pt, and simultaneously has simple preparation method, thereby being suitable for mass production.
2. Pt prepared by the invention 3 Mn intermetallic compound has good dispersibility, pt 3 Mn intermetallic compound particles can be uniformly distributed on the carbon nano tube, so that the problem of nanoparticle agglomeration is effectively solved.
3. Compared with the traditional calcination process, the thermal shock can obtain a sample in a short time; and because the thermal shock can realize the heating and cooling process in a short time, fine and uniform intermetallic compound particles can be prepared. And calcination requires a long time of temperature rise and fall, which results in difficulty in controlling the particle size and agglomeration state of the catalyst.
4. The invention is realized by putting folic acid in Pt 3 The tetrahydrofolic acid is prepared by reduction under the catalysis of Mn/CNTs catalyst, and the yield of the tetrahydrofolic acid is up to 96 percent, thus Pt 3 The Mn/CNTs catalyst has high catalytic efficiency and can be recycled, and the problems of large catalyst dosage and low yield in the prior art are overcome.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows carbon nanotubes and Pt 3 Scanning electron microscope image of Mn catalyst.
FIG. 2 shows the nuclear magnetic resonance hydrogen spectrum of tetrahydrofolate.
FIG. 3 is a nuclear magnetic resonance carbon spectrum of tetrahydrofolate.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The quantitative tests in the following examples were all set up with three replicates, and the data are the mean or mean ± standard deviation of the three replicates.
In addition, "and/or" throughout this document includes three schemes, taking a and/or B as an example, including a technical scheme, a technical scheme B, and a technical scheme that both a and B satisfy; in addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the technical solutions, when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and the combination is not within the scope of protection claimed by the present invention.
Preparation of Pt 3 Mn/CNTs catalyst
Example 1
S1, preparing a carbon nano tube solution: weighing 100mg of industrial porous Carbon Nanotubes (CNTs), placing into a beaker, adding 10mL of deionized water, and uniformly mixing, wherein a carbon nanotube scanning electron microscope chart is shown in figure 1; preparing a precursor metal salt solution: respectively taking chloroplatinic acid hexahydrate and manganese acetate tetrahydrate to prepare an aqueous solution of chloroplatinic acid with the concentration of 0.1mol/L and an aqueous solution of manganese acetate with the concentration of 0.1 mol/L;
s2, mixing 330 mu L of chloroplatinic acid aqueous solution and 110 mu L of manganese acetate aqueous solution with 10mL of CNTs solution, and continuously carrying out ultrasonic treatment for 2 hours to form uniform H 2 PtCl 6 Mn(Ac) 2 CNTs solution;
s3, H obtained in the step S2 2 PtCl 6 Mn(Ac) 2 Placing the CNTs solution in a freeze dryer, freezing for 5 hr, vacuum drying for 12 hr to obtain dried H 2 PtCl 6 Mn(Ac) 2 CNTs sample;
will H 2 PtCl 6 Mn(Ac) 2 Uniformly paving CNTs samples on the carbon cloth, wherein the impulse voltage is 20V, the initial impulse current is 9A,9A impulse is 10S, and stopping for 5S; then increasing the impact current in sequence, namely 11A impacts 10S, and stopping for 5S;13A strike 10S, stop 5S;15A strike 10S, stop 5S; and so on until H 2 PtCl 6 Mn(Ac) 2 The impact was stopped when the CNTs sample temperature reached 800 ℃. After the thermal shock is finished, pt is obtained 3 Mn/CNTs catalyst.
Pt 3 The scanning electron microscope of Mn/CNTs catalyst is shown in figure 1, and it can be seen from the figure that Pt and Mn form ordered intermetallic compound particles, pt 3 Mn is uniformly distributed on the carbon nanotubes.
Example 2 differs from example 1 in the concentration and amount of carbon nanotube solution and precursor metal salt solution.
Mixing 660 μl of chloroplatinic acid aqueous solution (0.1 mol/L), 220 μl of manganese acetate aqueous solution (0.1 mol/L) and 4.0mL of carbon nanotube solution (16 mg/mL), and continuously performing ultrasonic treatment for 2 hr to obtain uniform H 2 PtCl 6 Mn(Ac) 2 CNTs solution.
Synthesis of tetrahydrofolic acid
Application example 1
100mg of solid folic acid was added to a 100mL three-necked flask at 25℃and the flask was replaced with nitrogen 3 times, and 5mL of 0.2mol/L NaH having a pH of 7 was added to the flask 2 PO 4 -Na 2 HPO 4 Stirring the buffer solution to be uniform to obtain a mixed solution, and regulating the pH value of the mixed solution to 7 by using a 20% NaOH solution to obtain a folic acid solution;
10mg of Pt prepared in example 2 was added to a reaction vessel 3 The Mn/CNTs catalyst is prepared by replacing a reaction kettle with nitrogen for 3 times, adding folic acid solution with pH of 7 into the reaction kettle, replacing the reaction kettle with hydrogen for 5 times, filling hydrogen into the reaction kettle, regulating the pressure of the reaction kettle to 50bar, placing the reaction kettle in an environment of 60 ℃ for hydrogenation reaction, and reacting for 15 hours to obtain solution containing tetrahydrofolate;
adjusting the pH of the solution containing the tetrahydrofolic acid to 3 by using 1mol/L hydrochloric acid solution, precipitating tetrahydrofolic acid precipitate, filtering the precipitate, and drying the precipitate for 8 hours by using a vacuum drying oven to obtain the tetrahydrofolic acid.
FIG. 2 shows the nuclear magnetic resonance hydrogen spectrum of tetrahydrofolate, the results are as follows:
1 H NMR(400MHz,Deuterium Oxide)δ/ppm 7.66(d,J＝8.6Hz,1H),6.76(d,J＝8.6Hz,1H),4.43(dd,J＝9.0,4.8Hz,1H),3.89–3.81(m,1H),3.68(dd,J＝13.9,3.3Hz,1H),3.57(d,J＝6.5Hz,1H),3.45(dd,J＝13.9,6.5Hz,1H),2.47(t,J＝7.6Hz,1H),2.33–1.95(m,1H).
FIG. 3 shows nuclear magnetic resonance spectra of tetrahydrofolate, which is the following:
13 C NMR(101MHz,DMSO-d6)δ/ppm 174.12,174.02,166.53,155.87,151.57,149.34,129.09,120.56,110.84,99.12,51.86,48.06,45.29,44.17,30.57,26.13.
from the above, pt 3 Mn/CNTs catalyst can promote folic acid to react with hydrogen to generate tetrahydrofolic acid.
The procedure of application examples 2 and 3 was the same as that of application example 1, except that the reaction parameters were different, and the specific reaction parameters are shown in Table 1.
TABLE 1 parameters of reaction conditions in the examples of application
Application comparative example 1 differs from application example 1 in that the catalyst was PtCo-IMC.
Application comparative example 2 differs from application example 1 in that the catalyst was PtMn-IMC.
Application comparative example 3 differs from application example 1 in that the catalyst is a PtCo alloy.
Application comparative example 4 differs from application example 1 in that the catalyst was Fe/Ni-N-C.
The tetrahydrofolic acid was assayed using mesitylene as an internal standard, and the yields of the tetrahydrofolic acid obtained by using examples 1 to 3 and comparative examples 1 to 4 are shown in Table 2.
TABLE 2 yield of tetrahydrofolic acid (%)
| Application example 1 | 96 | Comparative example 1 was used | 5 |
| Application example 2 | 85 | Comparative example 2 was used | 40 |
| Application example 3 | 88 | Comparative example 3 was used | 4 |
| Comparative example 4 was used | 0 |
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be regarded as the scope of the present specification.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1.Pt 3 The preparation method of the Mn/CNTs catalyst is characterized by at least comprising the following steps:
s1, respectively preparing a carbon nano tube solution and a precursor metal salt solution;
s2, uniformly mixing the carbon nanotube solution and the precursor metal salt solution to obtain a first mixed solution;
s3, freeze-drying the first mixed solution, and performing thermal shock to obtain Pt 3 Mn/CNTs catalyst.
2. Pt according to claim 1 3 The preparation method of the Mn/CNTs catalyst is characterized by comprising the following steps: the precursor metal salt solution comprises chloroplatinic acid aqueous solution and manganese salt aqueous solution, and the concentrations of the chloroplatinic acid aqueous solution and the manganese salt aqueous solution are respectively 0.01-0.2mol/L.
3. Pt according to claim 1 3 The preparation method of the Mn/CNTs catalyst is characterized by comprising the following steps: the concentration of the carbon nanotube solution is 5-25mg/mL.
4. Pt according to claim 1 3 The preparation method of the Mn/CNTs catalyst is characterized by comprising the following steps: and the freeze drying step is that the first mixed solution is placed in a freeze dryer, frozen for 3-24 hours, and then dried in vacuum for 12-48 hours, so as to obtain the sample to be subjected to thermal shock.
5. The Pt as claimed in claim 4 3 The preparation method of the Mn/CNTs catalyst is characterized by comprising the following steps: the thermal shock step is that a sample to be thermal shock is evenly laid on the carbon cloth, the impact voltage is 20V, the impact current is 9+2 (n-1) A, and n is the impact times; the impulse current is 10s each time of impulse, and the intermittent time between two adjacent impulses is 5s, until the surface temperature of the sample to be shocked reaches 800℃, the sample is stoppedImpact.
6.Pt 3 Mn/CNTs catalyst characterized by being composed of Pt as claimed in any one of claims 1 to 5 3 Mn/CNTs catalyst is prepared by a preparation method.
7. The Pt as claimed in claim 6 3 Mn/CNTs catalyst in synthesizing tetrahydrofolic acid.
8. The Pt as recited in claim 7 3 The application of Mn/CNTs catalyst in synthesizing tetrahydrofolate is characterized in that: pt is combined with 3 Adding Mn/CNTs catalyst and folic acid solution into a reaction kettle, filling hydrogen into the reaction kettle, and carrying out hydrogenation reaction on folic acid and hydrogen under the conditions that the internal pressure of the reaction kettle is 20-80bar and the internal temperature is 40-90 ℃, thus obtaining tetrahydrofolic acid after the reaction is finished.
9. Pt according to claim 8 3 The application of Mn/CNTs catalyst in synthesizing tetrahydrofolate is characterized in that: the folic acid and the Pt 3 The mass ratio of Mn/CNTs catalyst is 100 (0.1-20).
10. Pt according to claim 8 3 The application of Mn/CNTs catalyst in synthesizing tetrahydrofolate is characterized in that: the reaction time of the folic acid and the hydrogen for hydrogenation reaction is 6-24h.
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