CN115672321A - 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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Abstract
The present invention relates to Pt 3 The preparation method of the Mn/CNTs catalyst and the application of the catalyst at least comprise the following steps: s1, respectively preparing a carbon nanotube 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, carrying out thermal shock after freeze drying the first mixed solution 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 at the same time, pt 3 Mn can be uniformly loaded on the carbon nano tube, and 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 A preparation method of an Mn/CNTs catalyst and application of the catalyst.
Background
Intermetallic compounds are materials composed of two or more elements in the periodic table, the specific combination of their crystalline and electronic structures leading to their unique adsorption and catalytic properties. Heterogeneous catalysis of intermetallic compounds has been identified as a rapidly growing field.
Unlike the crystal structure of the constituent elements, the intermetallic crystal structure is completely or at least partially ordered. The degree of order of the intermetallic structure is mainly determined by the annealing temperature, and thus it is usually made into an ordered structure by a high-temperature annealing method. However, high temperature heat treatment can cause agglomeration of the nanoparticles, resulting in a reduction in surface area. Therefore, one of the major challenges in the current intermetallic catalyst research is how to obtain an ordered intermetallic structure without the occurrence of severe nanoparticle agglomeration.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Pt 3 Preparation method of Mn catalyst and application of catalyst, and Pt prepared by using thermal shock method 3 Mn/CNTs catalyst. The preparation method is simple, and at the same time, pt 3 Mn can be uniformly loaded on the carbon nano tube, and the problem of agglomeration of platinum-based bimetallic intermetallic compound particles is solved.
To solve the above technical problems, the present 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, carrying out thermal shock after freeze drying the first mixed solution to obtain Pt 3 Mn/CNTs catalyst.
Further, the precursor metal salt solution comprises a chloroplatinic acid aqueous solution and a manganese salt aqueous solution, wherein the concentrations of the chloroplatinic acid aqueous solution and the manganese salt aqueous solution are 0.01-0.2mol/L respectively.
Further, the concentration of the carbon nano tube solution is 5-25mg/mL.
Further, the step of freeze drying is to place the first mixed solution in a freeze dryer, freeze for 3-24h, and vacuum dry for 12-48h to obtain a sample to be thermally shocked.
Further, the thermal shock step is that a sample to be subjected to thermal shock is uniformly laid on the carbon cloth, the shock voltage is 20V, the shock current is 9+2 (n-1) A, and n is the shock times; the impact current impacts for 10s each time, and the intermittent time between two adjacent impacts is 5s, until the surface temperature of the sample to be thermally 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 impacts 10S from 9A, and the temperature of the surface of the sample is detected. And then stopping impacting, and subjecting the surface of the sample to a temperature reduction process. 11A impacts the sample, the surface of the sample begins to heat up again, keeps for 10S, and then goes through the process of cooling. And so on until the sample surface reaches 800 ℃. Therefore, each time the sample is impacted, the surface of the sample is subjected to the processes of temperature rise and temperature reduction, the annealing temperature is accurately controlled, and the degree of order of the structure of the intermetallic compound can be promoted.
The second invention provides Pt obtained by the above preparation method 3 Mn/CNTs catalyst.
The third aspect of the present invention is to provide the above Pt 3 The Mn/CNTs catalyst is applied to the synthesis of tetrahydrofolic acid.
Further, pt is added 3 Adding a Mn/CNTs catalyst and a folic acid solution into a reaction kettle, filling hydrogen into the reaction kettle, carrying out hydrogenation reaction on folic acid and the hydrogen under the conditions that the internal pressure of the reaction kettle is 20-80bar and the internal temperature is 40-90 ℃, and obtaining tetrahydrofolic acid after the reaction is finished.
Further, the folic acid is in contact with the Pt 3 The mass ratio of the Mn/CNTs catalyst is 100 (0.1-20).
Furthermore, the reaction time of the folic acid and the hydrogen gas in the hydrogenation reaction is 6-24h.
Through the technical scheme, carbon-nitrogen double bonds in folic acid are reduced by hydrogen, and particularly, hydrogen is adsorbed on Pt 3 On the surface of the Mn/CNTs catalyst, folic acid is coordinated with the catalyst, and hydrogen molecules of hydrogen are in Pt 3 The bonds are broken under the catalysis of the Mn/CNTs catalyst to form active hydrogen atoms, and the hydrogen atoms of the hydrogen gas are combined with carbon-nitrogen double bonds of folic acid to be reduced to form carbon-nitrogen single bonds to generate the tetrahydrofolic acid.
Wherein, pt 3 The Mn/CNTs catalyst refers to a catalyst in which intermetallic compound particles are uniformly loaded on carbon nanotubes.
Further, filling hydrogen into the reaction kettle until the reaction kettle does not contain gases except the hydrogen;
in the presence of Pt 3 Before the Mn/CNTs catalyst and the folic acid solution are added into the reaction kettle, nitrogen or inert gas is filled into the reaction kettle to ensure that an oxygen-free environment is formed in the reaction kettle.
Further, the step of obtaining tetrahydrofolic acid after the hydrogenation reaction is finished comprises:
after the reaction is finished, obtaining a solution containing tetrahydrofolic acid, adjusting the pH value of the solution containing the tetrahydrofolic acid precipitate to 3-3.5 by using an acid solution to obtain a solution containing the tetrahydrofolic acid precipitate, filtering the solution containing the tetrahydrofolic acid precipitate, collecting the tetrahydrofolic acid precipitate, and drying the precipitate to obtain the tetrahydrofolic acid.
By the technical scheme, after the reaction is finished, the whole system is homogeneous, the tetrahydrofolic acid can be separated out under an acidic condition, and the pH value of 3-3.5 is the time when the yield of the separated tetrahydrofolic acid is highest;
the tetrahydrofolic acid is sensitive to oxygen and is easily oxidized into dihydrofolic acid, so the whole reaction process needs an oxygen-free environment;
further, the drying mode comprises freeze drying, vacuum drying and the like, and the drying is carried out under the condition of no oxygen, so that the tetrahydrofolic acid is prevented from being oxidized;
filtering under the condition of nitrogen or inert gas to avoid the oxidation of the 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 until an oxygen-free environment is formed in the flask, adding a buffer solution with the pH of 4-7 into the flask, stirring uniformly to obtain a mixed solution, and adjusting the pH of the mixed solution to 6-7 by using an alkali solution to obtain a folic acid solution.
Further, the folic acid solution is prepared at room temperature, namely 25-35 ℃.
Furthermore, the buffer is added to control the pH of the solution and avoid titration leaps;
further, when folic acid is dissolved in an alkali solution and the pH of the folic acid solution is adjusted to =7 with an alkali, the yield of folic acid produced by the reaction of folic acid is maximized.
Further, the buffer solution includes any one of a disodium hydrogen phosphate-citric acid buffer solution, a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution, a disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution, a barbituric sodium-hydrochloric acid buffer solution, a Tris buffer solution, a boric acid-borax buffer solution, a glycine-sodium hydroxide buffer solution, a borax-sodium hydroxide buffer solution, a sodium carbonate-sodium bicarbonate buffer solution, a Britton-Robinson buffer solution, and a Tris buffer salt solution.
Further, the alkali solution includes any one of a NaOH solution and a KOH solution.
Further, the amount of the buffer solution is 10 to 15ml per 1g of the solid folic acid.
In conclusion, 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 and is suitable for large-scale production.
2. Pt prepared by the invention 3 The Mn intermetallic compound has good dispersibility and Pt 3 Mn intermetallic compound particles can be uniformly distributed on the carbon nano tube, and the problem of nano particle agglomeration is effectively solved.
3. Compared with the traditional calcining process, the thermal shock can obtain a sample in a short time; and fine and uniform intermetallic compound particles can be prepared because the heating and cooling processes can be realized in a short time by thermal shock. However, the calcination requires a long time for heating and cooling, and the long time for firing makes it difficult to control the particle size and the agglomeration state of the catalyst.
4. The invention is realized by adding folic acid into Pt 3 The tetrahydrofolic acid is prepared by reduction under the catalysis of Mn/CNTs catalyst, the yield of the tetrahydrofolic acid is up to 96 percent, therefore, 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 solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 shows carbon nanotubes and Pt 3 Scanning electron micrographs of Mn catalyst.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of tetrahydrofolic acid.
FIG. 3 is a NMR carbon spectrum of tetrahydrofolic acid.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials and reagents used in the following examples, etc., are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of the technical solutions by those skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, the combination of the technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
Preparation of Pt 3 Mn/CNTs catalyst
Example 1
S1, preparing a carbon nano tube solution: weighing 100mg of industrial grade porous Carbon Nanotubes (CNTs), putting into a beaker, adding into 10mL of deionized water, and uniformly mixing, wherein a scanning electron microscope image of the carbon nanotubes is shown in figure 1; preparing a precursor metal salt solution: respectively taking chloroplatinic acid hexahydrate and manganese acetate tetrahydrate, and preparing a chloroplatinic acid aqueous solution with the concentration of 0.1mol/L and a manganese acetate aqueous solution 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 performing ultrasonic treatment for 2H 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 The CNTs solution is placed in a freeze dryer, after being frozen for 5H, the freeze dryer is dried for 12H in vacuum, and dried H is obtained 2 PtCl 6 Mn(Ac) 2 CNTs sample;
will H 2 PtCl 6 Mn(Ac) 2 Uniformly paving the/CNTs sample on the carbon cloth, wherein the impulse voltage is 20V, the initial impulse current is 9A and the impact current is 10S, and stopping for 5S; then increasing the impact current in sequence, namely 11A impacting 10S, and stopping for 5S;13A impact 10S, stop 5S;15A impact 10S, stop 5S; by analogy in the following order,up to H 2 PtCl 6 Mn(Ac) 2 the/CNTs sample temperature reached 800 ℃ and the impact was stopped. After the thermal shock is complete, pt is obtained 3 Mn/CNTs catalyst.
Pt 3 The scanning electron micrograph of the Mn/CNTs catalyst is shown in FIG. 1, and it can be seen from the micrograph that Pt and Mn form ordered intermetallic compound particles, pt 3 Mn is uniformly distributed on the carbon nano tube.
Example 2 differs from example 1 in the concentration and amount of the carbon nanotube solution and the precursor metal salt solution.
Respectively mixing 660 mu L of chloroplatinic acid aqueous solution (0.1 mol/L), 220 mu L of manganese acetate aqueous solution (0.1 mol/L) and 4.0mL of carbon nano tube solution (16 mg/mL), and continuously performing ultrasonic treatment for 2 hours to form 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 gas 3 times, and then 5mL of 0.2mol/L NaH having pH 7 was added to the flask 2 PO 4 -Na 2 HPO 4 The buffer solution is stirred uniformly to obtain a mixed solution, and the pH value of the mixed solution is adjusted to 7 by using a 20% NaOH solution to obtain a folic acid solution;
10mg of Pt prepared in example 2 was added to the reaction kettle 3 The method comprises the following steps of (1) replacing a reaction kettle with nitrogen for 3 times by using a Mn/CNTs catalyst, adding folic acid solution with the pH of 7 into the reaction kettle, replacing the reaction kettle with hydrogen for 5 times, filling the hydrogen into the reaction kettle, adjusting the pressure of the reaction kettle to 50bar, placing the reaction kettle in an environment at 60 ℃ to perform hydrogenation reaction, and reacting for 15 hours to obtain a solution containing tetrahydrofolic acid;
and (3) regulating the pH of the solution containing the tetrahydrofolic acid to 3 by using a 1mol/L hydrochloric acid solution, separating out a tetrahydrofolic acid precipitate, filtering the precipitate, and drying for 8 hours by using a vacuum drying oven to obtain the tetrahydrofolic acid.
FIG. 2 is the NMR chart of the product tetrahydrofolic acid, the results of which 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 is the NMR chart of the product tetrahydrofolic acid, which is as follows:
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 The Mn/CNTs catalyst can promote folic acid to react with hydrogen to generate tetrahydrofolic acid.
Application examples 2 and 3 were the same as the procedure in application example 1 except that the reaction parameters were different, and the specific reaction parameters are shown in Table 1.
TABLE 1 parameters of the reaction conditions in the respective application examples
Comparative application example 1 differs from application example 1 in that the catalyst was PtCo-IMC.
Comparative application example 2 differs from application example 1 in that the catalyst was PtMn-IMC.
Comparative application example 3 differs from application example 1 in that the catalyst was a PtCo alloy.
Comparative application example 4 differs from application example 1 in that the catalyst was Fe/Ni-N-C.
The yield of tetrahydrofolic acid measured by using examples 1 to 3 and comparative examples 1 to 4 is shown in Table 2.
TABLE 2 yield (%)
| Application example 1 | 96 | Application comparative example 1 | 5 |
| Application example 2 | 85 | Comparative application example 2 | 40 |
| Application example 3 | 88 | Comparative application example 3 | 4 |
| Application comparative example 4 | 0 |
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being included in the description of the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to 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 nanotube 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, carrying out thermal shock after freeze drying the first mixed solution 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 a chloroplatinic acid aqueous solution and a manganese salt aqueous solution, wherein 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 nano tube 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 step of freeze drying is to put the first mixed solution into a freeze dryer, freeze for 3-24h, and vacuum dry for 12-48h to obtain a sample to be thermally shocked.
5. Pt according to claim 4 3 The preparation method of the Mn/CNTs catalyst is characterized by comprising the following steps: the thermal shock step is that the sample to be thermally shocked is evenly laid on the carbon cloth and is punchedThe striking voltage is 20V, the impact current is 9+2 (n-1) A, and n is the impact frequency; the impact current impacts for 10s each time, and the intermittent time between two adjacent impacts is 5s, until the surface temperature of the sample to be thermally impacted reaches 800 ℃, and the impact is stopped.
6.Pt 3 Mn/CNTs catalyst, characterized by the fact that Pt according to any of claims 1 to 5 3 The Mn/CNTs catalyst is prepared by a preparation method.
7. Pt according to claim 6 3 The Mn/CNTs catalyst is applied to the synthesis of tetrahydrofolic acid.
8. Pt according to claim 7 3 The application of the Mn/CNTs catalyst in the synthesis of tetrahydrofolic acid is characterized in that: mixing Pt 3 Adding a Mn/CNTs catalyst and a folic acid solution into a reaction kettle, filling hydrogen into the reaction kettle, carrying out hydrogenation reaction on folic acid and the hydrogen under the conditions that the internal pressure of the reaction kettle is 20-80bar and the internal temperature is 40-90 ℃, and obtaining tetrahydrofolic acid after the reaction is finished.
9. Pt according to claim 8 3 The application of the Mn/CNTs catalyst in the synthesis of tetrahydrofolic acid is characterized in that: the folic acid and the Pt 3 The mass ratio of the Mn/CNTs catalyst is 100 (0.1-20).
10. Pt according to claim 8 3 The application of the Mn/CNTs catalyst in the synthesis of tetrahydrofolic acid is characterized in that: the reaction time of the folic acid and the hydrogen for hydrogenation reaction is 6-24h.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030013606A1 (en) * | 1998-02-24 | 2003-01-16 | Hampden-Smith Mark J. | Method for the production of electrocatalyst powders |
| CN1433422A (en) * | 1999-12-21 | 2003-07-30 | 孟山都技术有限责任公司 | Use of supplemental promoter in conjunction with carbon-supported, noble-metal-containing catalyst in liquid phase oxidation reactions |
| US20040171480A1 (en) * | 1998-08-27 | 2004-09-02 | Hampden-Smith Mark J. | Electrocatalyst powders, methods for producing powders and devices fabricated from same |
| KR100965834B1 (en) * | 2009-08-05 | 2010-06-25 | 한국과학기술원 | Double metal-carbonnanotube hybrid catalyst and method for preparation thereof |
| CN101964423A (en) * | 2010-09-11 | 2011-02-02 | 华南理工大学 | Direct methanol fuel cell anode catalyst Pt/ MnO2-RuO2/ CNTs and preparation method thereof |
| DE102010044288A1 (en) * | 2010-09-03 | 2012-03-08 | Elcomax Gmbh | Process for the preparation of platinum transition metal catalyst particles |
| CN103657649A (en) * | 2013-12-27 | 2014-03-26 | 中国科学院上海高等研究院 | Method for preparing carbon-supported nano-platinum-chromium intermetallic compound serving as cathode catalyst of proton exchange membrane fuel cell |
| WO2014153570A2 (en) * | 2013-03-15 | 2014-09-25 | Transtar Group, Ltd | New and improved system for processing various chemicals and materials |
| KR20160039749A (en) * | 2014-10-01 | 2016-04-12 | 포항공과대학교 산학협력단 | Catalyst composite including intermetallic nano particle and method for preparing the same |
| CN109225351A (en) * | 2018-09-18 | 2019-01-18 | 北京国能中林科技开发有限公司 | It is a kind of based on carbon nanotube/alumina composite carrier hydrogenation catalyst and its preparation method and application |
| CN110560081A (en) * | 2019-07-26 | 2019-12-13 | 浙江大学 | Alloy nano-particles and preparation method and application thereof |
| CN114163439A (en) * | 2021-12-01 | 2022-03-11 | 哈尔滨工业大学（深圳） | Method for preparing tetrahydrofolic acid by catalytic hydrogenation |
| CN114181210A (en) * | 2021-12-01 | 2022-03-15 | 深圳奥萨制药有限公司 | Preparation method of tetrahydrofolic acid |
| WO2022067085A1 (en) * | 2020-09-24 | 2022-03-31 | William Marsh Rice University | Ultrafast flash joule heating synthesis methods and systems for performing same |
-
2022
- 2022-09-30 CN CN202211208270.2A patent/CN115672321B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030013606A1 (en) * | 1998-02-24 | 2003-01-16 | Hampden-Smith Mark J. | Method for the production of electrocatalyst powders |
| US20040171480A1 (en) * | 1998-08-27 | 2004-09-02 | Hampden-Smith Mark J. | Electrocatalyst powders, methods for producing powders and devices fabricated from same |
| CN1433422A (en) * | 1999-12-21 | 2003-07-30 | 孟山都技术有限责任公司 | Use of supplemental promoter in conjunction with carbon-supported, noble-metal-containing catalyst in liquid phase oxidation reactions |
| KR100965834B1 (en) * | 2009-08-05 | 2010-06-25 | 한국과학기술원 | Double metal-carbonnanotube hybrid catalyst and method for preparation thereof |
| DE102010044288A1 (en) * | 2010-09-03 | 2012-03-08 | Elcomax Gmbh | Process for the preparation of platinum transition metal catalyst particles |
| CN101964423A (en) * | 2010-09-11 | 2011-02-02 | 华南理工大学 | Direct methanol fuel cell anode catalyst Pt/ MnO2-RuO2/ CNTs and preparation method thereof |
| WO2014153570A2 (en) * | 2013-03-15 | 2014-09-25 | Transtar Group, Ltd | New and improved system for processing various chemicals and materials |
| CN103657649A (en) * | 2013-12-27 | 2014-03-26 | 中国科学院上海高等研究院 | Method for preparing carbon-supported nano-platinum-chromium intermetallic compound serving as cathode catalyst of proton exchange membrane fuel cell |
| KR20160039749A (en) * | 2014-10-01 | 2016-04-12 | 포항공과대학교 산학협력단 | Catalyst composite including intermetallic nano particle and method for preparing the same |
| CN109225351A (en) * | 2018-09-18 | 2019-01-18 | 北京国能中林科技开发有限公司 | It is a kind of based on carbon nanotube/alumina composite carrier hydrogenation catalyst and its preparation method and application |
| CN110560081A (en) * | 2019-07-26 | 2019-12-13 | 浙江大学 | Alloy nano-particles and preparation method and application thereof |
| WO2022067085A1 (en) * | 2020-09-24 | 2022-03-31 | William Marsh Rice University | Ultrafast flash joule heating synthesis methods and systems for performing same |
| CN114163439A (en) * | 2021-12-01 | 2022-03-11 | 哈尔滨工业大学（深圳） | Method for preparing tetrahydrofolic acid by catalytic hydrogenation |
| CN114181210A (en) * | 2021-12-01 | 2022-03-15 | 深圳奥萨制药有限公司 | Preparation method of tetrahydrofolic acid |
Non-Patent Citations (3)
| Title |
|---|
| JEONGHOON LIM等: "Atomically ordered Pt3Mn intermetallic electrocatalysts for the oxygen reduction in fuel cells", 《J. MATER.CHEM.A》, vol. 10, pages 7399 - 7408 * |
| WU XX等: "A highly sensitive electrochemical sensor for Cd(II) based on protic salt derived nitrogen and sulfur co-doped porous carbon", 《ANALYTICA CHIMICA ACTA》, vol. 1046, pages 115 - 122 * |
| 李瑞松等: "染料电池中铂基催化剂的设计与合成", 《化工进展》, vol. 40, no. 9, pages 4931 - 4947 * |
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