CN104998636A - Synthetic method and application of PtRu binary metal nano-alloy catalyst - Google Patents
Synthetic method and application of PtRu binary metal nano-alloy catalyst Download PDFInfo
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- CN104998636A CN104998636A CN201510453973.5A CN201510453973A CN104998636A CN 104998636 A CN104998636 A CN 104998636A CN 201510453973 A CN201510453973 A CN 201510453973A CN 104998636 A CN104998636 A CN 104998636A
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Abstract
The invention discloses a PtRu binary metal nano-alloy catalyst which is of a flower-shaped (porous) structure. The synthetic method of the PtRu binary metal nano-alloy catalyst is characterized by comprising the steps that 1, a surface active agent and a reducing agent are added into water together, and stirring is conducted for 10-30 minutes at the indoor temperature, wherein the mass ratio of the surface active agent to the reducing agent is 1:2-2:1, and the amount of added water needs to meet the requirement that both the surface active agent and the reducing agent are completely dissolved in the water; 2, a metallic platinum salt pecursor solution and a metallic ruthenium salt pecursor solution are added in the mixed solution obtained in the first step, and stirring is conducted for 10-30 minutes at the indoor temperature,wherein the volume ratio of the platinum salt pecursor solution to the metallic ruthenium salt pecursor solution is 3:2-2:3, the ratio of the volume of the mixed solution to the total volume of the metallic pecursor solutions is 10:1-20:1, and the concentration of the metal salt precursor solution is 0.05-0.5 mol/L; 3, the mixed solution obtained in the second step is stirred for 5-30 minutes at the indoor temperature, a reaction is conducted in an autoclave for 1.5-3 hours, and the temperature is controlled to be 180-230 DEG C; 4, the product obtained in the third step is cooled and then is washed, and the PtRu binary metal nano-alloy catalyst of the flower-shaped (porous) structure is obtained after centrifugal separation.
Description
Technical field
The present invention relates to fuel-cell catalyst field, specifically a kind of synthesis of PtRu binary metal nanometer alloy catalyst and application thereof.
Background technology
Fuel cell due to its energy transformation ratio high; environmental pollution is few; be conducive to the environment that excessively uses and preserve our planet reducing traditional fossil fuel; can be used as the power resources of future ideality; thus be subject to the extensive concern of countries in the world scientist, for this reason, a large amount of manpowers has been dropped in countries in the world; material resources, and financial resources are studied.Methyl alcohol is the simplest liquid organic compound of a kind of structure at normal temperatures and pressures, and store simple, convenient sources, low price is a kind of desirable recyclable fuel.Pt catalyst because it is to the catalytic activity of methyl alcohol excellence and stability, and gets more and more people's extensive concerning.But, the commercialization that the price rare and expensive due to its reserves on earth limits fuel cell greatly uses, and the intermediate oxidation product CO of methyl alcohol can occupy the avtive spot on Pt surface, makes Pt catalyst poisoning, thus reduce electro-chemical activity and the stability of Pt.The key improving catalyst activity is the intermediate product being oxidized similar CO under electronegative potential.At present, the alloying of Pt is that a kind of common method that scientists is taked solves low and easy this problem poisoning of monometallic Pt catalytic activity.Binary nano-alloy based on Pt is more and more subject to people's attention due to the physical and chemical performance of its uniqueness.Wherein, PtRu binary nano-alloy is subject to extensive concern with its better electro-chemical activity and CO mithridatism.But reported PtRu binary metal nanometer alloy catalyst seldom can have high activity and high stability concurrently simultaneously.And the binary metal nanometer alloy catalyst of this flower-shaped (poroid) structure not only has catalytic activity and stability concurrently, and to have in these two aspects than the PtRu bielement nano catalyst reported before and promote largely.
Summary of the invention
The technical problem to be solved in the present invention is: the PtRu binary metal nanometer alloy catalyst providing a kind of flower-shaped (poroid) structure, enhances catalyst CO tolerance catalysts ability and improve the catalytic activity to methyl alcohol, formaldehyde, formic acid.
Technical scheme of the present invention is: a kind of preparation method of PtRu binary metal nanometer alloy catalyst of flower-shaped (poroid) structure, comprises following steps:
(1) surfactant is added to the water together with reducing agent, stirred at ambient temperature 10 ~ 30 minutes, the mass ratio of surfactant and reducing agent is 1:2 ~ 2:1; Institute's amount of water needs surfactant and reducing agent to dissolve completely;
(2) in the mixed solution of step (1) gained, add metal platinum salt precursor liquid solution and metal Ru salt precursor liquid solution respectively, the two volume ratio is: 3:2 ~ 2:3, and the ratio of mixed solution and metal precursor overall solution volume is 10:1 ~ 20:1; Stirring at room temperature 10 ~ 30 minutes, the concentration of slaine precursor solution is 0.05 ~ 0.5mol/L;
(3) by step (2) gained mixed solution stirred at ambient temperature 5 ~ 30 minutes, react 1.5 ~ 3 hours in autoclave, temperature controls at 180 ~ 230 DEG C;
(4) wash after step (3) products therefrom being cooled, after centrifugation, namely obtain a kind of PtRu binary metal nanometer alloy catalyst with flower-shaped (poroid) structure.
The aqueous solution described in step (1) is ultra-pure water, and mixing time is 20 minutes, and surfactant and reducing agent mass ratio are 2:3.
Surfactant in step (1) is PVP or CTAC or the two mixture; Reducing agent is Citric Acid Mono or natrium citricum.
Surfactant in step (1) is the mixture of PVP-8000 and CTAC; Reducing agent is Citric Acid Mono.
Described metal platinum salt precursor liquid solution is chloroplatinic acid or potassium chloroplatinate.
Described metal Ru salt precursor liquid solution is ruthenium trichloride.
The described stirred at ambient temperature of step (3) 20 minutes, react 2 hours in autoclave, temperature controls at about 210 DEG C.
Beneficial effect of the present invention:
The present invention studies and obtains a kind of PtRu binary metal nanometer alloy catalyst of flower-shaped (poroid) structure, enhances catalyst CO tolerance catalysts ability and the catalytic activity improving catalysis methanol, formaldehyde, formic acid preferably.For methyl alcohol, the peak point current of catalysis methanol is 10.98mA cm-2.
The peak point current swept under the condition of 0.6 v after 3600 s is 2.85 mA cm-2, than the 0.21mA cm-2 more than high ten times of business Pt black.
Accompanying drawing explanation
Fig. 1. be the PtRu binary alloy nano catalyst of flower-shaped (poroid) structure, with high resolution transmission electron microscope observed result figure;
Fig. 2. be the PtRu element spectrogram of flower-shaped (poroid) structure, can find out that the overall distribution of Pt and Ru atom in flower-shaped (poroid) structure particles is relatively more even, define alloy;
Fig. 3. the cyclic voltammetry curve of the PtRu binary alloy nano catalyst of flower-shaped (poroid) structure and commercial Pt black, PtRu black and PtRu/C black catalysis methanol in 0.1M HClO4+0.5M CH3OH solution;
Fig. 4. the i-t curve under the condition of the PtRu alloy nano catalyst of flower-shaped (poroid) structure and commercial Pt black, PtRu black and PtRu/C black 0.6 v in 0.1M HClO4+0.5M CH3OH solution;
Fig. 5. the cyclic voltammetry curve of the PtRu binary alloy nano catalyst of flower-shaped (poroid) structure and commercial Pt black, PtRu/C black catalysis formaldehyde in 0.1M HClO4+0.1M HCHO solution;
Fig. 6. the cyclic voltammetry curve of the PtRu binary alloy nano catalyst of flower-shaped (poroid) structure and commercial Pt black, PtRu/C black catalysis formic acid in 0.1M HClO4+0.1M HCOOH solution.
Detailed description of the invention
Concrete enforcement 1:
(1) by surfactant and reducing agent in mass ratio for 2:3 joins in the aqueous solution, stir 15 minutes;
(2) in step (1) mixed liquor (5.6mL), add platinum acid chloride solution, the ruthenium trichloride solution that volume ratio is 3:2, concentration is 0.1mol/L, and mixed solution colour is yellowish-brown, stirred at ambient temperature 15 minutes;
(3) proceed in reactor by step (2) gained solution, reaction 2h, temperature controls at about 200 DEG C;
(4) products obtained therefrom through centrifugation and after carrying out three washings with alcoholic solution distributed and saved in alcoholic solution, dispersed better, catalytic activity is general.
Concrete enforcement 2:
(1) by surfactant and reducing agent in mass ratio for 2:3 joins in the aqueous solution, stir 20 minutes;
(2) in step (1) mixed liquor (5.6mL), add platinum acid chloride solution, the ruthenium trichloride solution that volume ratio is 1:1, concentration is 0.1mol/L, and mixed solution colour is yellowish-brown, stirred at ambient temperature 20 minutes;
(3) proceed in reactor by step (2) gained solution, reaction 2h, temperature controls at about 210 DEG C;
(4) products obtained therefrom through centrifugation and after carrying out three washings with alcoholic solution distributed and saved in alcoholic solution, dispersed very well, catalytic capability is very high.
Concrete enforcement 3:
(1) by surfactant and reducing agent in mass ratio for 2:3 joins in the aqueous solution, stir 25 minutes;
(2) in step (1) mixed liquor (5.6mL), add platinum acid chloride solution, the ruthenium trichloride solution that volume ratio is 2:3, concentration is 0.1mol/L, and mixed solution colour is dark-brown, stirred at ambient temperature 25 minutes;
(3) proceed in reactor by step (2) gained solution, reaction 2h, temperature controls at about 220 DEG C;
(4) products obtained therefrom through centrifugation and after carrying out three washings with alcoholic solution distributed and saved in alcoholic solution, dispersed better, catalytic activity is higher.
Fig. 1, for embodiment gained catalyst is carried out high resolution transmission electron microscope, can find out flower-shaped (poroid) structure of PtRu binary alloy nano catalyst.
Fig. 2. be the PtRu element spectrogram of flower-shaped (poroid) structure, can find out that the overall distribution of Pt and Ru atom in flower-shaped (poroid) structure particles is even, define alloy.
Fig. 3. be the cyclic voltammetry curve by embodiment gained catalyst and commercial Pt black, PtRu black, PtRu/C black catalysis methanol in 0.1M HClO4+0.5M CH3OH solution, can find out that the peak point current of the PtRu of wherein flower-like structure is the highest, be 10.98 mA cm-2.
Fig. 4. survey i-t curve under the condition for Pt black, the PtRu black of embodiment gained catalyst and business, PtRu/C black 0.6v in 0.1MHClO4+0.5MCH3OH solution, testing time is 3600 s, result shows that the catalyst of the PtRu of flower-like structure is always high than Pt black, PtRu black and PtRu/C black at the peak point current of 3600 s, stability than business-like Pt black, PtRu black and PtRu/C black good.
Fig. 5. be the cyclic voltammetry curve of the catalysis formaldehyde in 0.1M HClO4+0.1M HCHO solution by embodiment gained catalyst and commercial Pt black, PtRu/C black.Wherein the peak point current of the PtRu of flower-like structure is the highest, is 12.16 mA cm-2.
Fig. 6. be the cyclic voltammetry curve of the catalysis formic acid in 0.1M HClO4+0.1M HCOOH solution by embodiment gained catalyst and commercial Pt black, PtRu/C black, wherein the peak point current of the PtRu of flower-shaped (poroid) structure is the highest, is 6.42 mA cm-2.
Claims (8)
1. the PtRu binary metal nanometer alloy catalyst of flower-shaped (poroid) structure, is characterized in that:
(1) surfactant is added to the water together with reducing agent, stirred at ambient temperature 10 ~ 30 minutes, the mass ratio of surfactant and reducing agent is 1:2 ~ 2:1; Institute's amount of water needs surfactant and reducing agent to dissolve completely;
(2) in the mixed solution of step (1) gained, add metal platinum salt precursor liquid solution and metal Ru salt precursor liquid solution respectively, the two volume ratio is: 3:2 ~ 2:3, and the ratio of mixed solution and metal precursor overall solution volume is 10:1 ~ 20:1; Stirring at room temperature 10 ~ 30 minutes, the concentration of slaine precursor solution is 0.05 ~ 0.5mol/L;
(3) by step (2) gained mixed solution stirred at ambient temperature 5 ~ 30 minutes, react 1.5 ~ 3 hours in autoclave, temperature controls at 180 ~ 230 DEG C;
(4) wash after step (3) products therefrom being cooled, after centrifugation, namely obtain a kind of PtRu binary metal nanometer alloy catalyst with flower-shaped (poroid) structure.
2. the preparation method of the PtRu nanometer alloy catalyst of one according to claim 1 flower-shaped (poroid) structure, it is characterized in that: the aqueous solution described in step (1) is ultra-pure water, mixing time is 20 minutes, and surfactant and reducing agent mass ratio are 2:3.
3. the preparation method of the PtRu nanometer alloy catalyst of one according to claim 1 flower-shaped (poroid) structure, is characterized in that: the surfactant in step (1) is PVP or CTAC or the two mixture; Reducing agent is Citric Acid Mono or natrium citricum.
4. the preparation method of the PtRu nanometer alloy catalyst of the one according to claim 1 or 3 flower-shaped (poroid) structure, is characterized in that: the surfactant in step (1) is the mixture of PVP-8000 and CTAC; Reducing agent is Citric Acid Mono.
5. the preparation method of the PtRu nanometer alloy catalyst of one according to claim 1 flower-shaped (poroid) structure, is characterized in that: described metal platinum salt precursor liquid solution is chloroplatinic acid or potassium chloroplatinate.
6. the PtRu nanometer alloy catalyst preparation method of one according to claim 1 flower-shaped (poroid) structure, is characterized in that: described metal Ru salt precursor liquid solution is ruthenium trichloride.
7. the preparation method of the PtRu nanometer alloy catalyst of one according to claim 1 flower-shaped (poroid) structure, is characterized in that: the described stirred at ambient temperature of step (3) 20 minutes, and react 2 hours in autoclave, temperature controls at about 210 DEG C.
8. the PtRu binary metal nanometer alloy catalyst according to claim 1-7 has reasonable catalytic efficiency and antitoxin voltinism energy in fuel cell field to organic molecules such as methyl alcohol, formaldehyde, formic acid.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105798325A (en) * | 2016-03-24 | 2016-07-27 | 贵州大学 | Sub-2nm ruthenium (Ru) nanowire network and preparation method thereof |
| CN105958087A (en) * | 2016-06-08 | 2016-09-21 | 贵州大学 | General preparation method for flower-like porous platinum-based nano-catalyst |
| CN106348247A (en) * | 2016-10-26 | 2017-01-25 | 贵州大学 | Synthesis method of ternary PtPdCu nano-crystal and application |
| CN106841355A (en) * | 2017-03-29 | 2017-06-13 | 贵州大学 | A kind of PtNi Nanoalloy electrochemical sensors for detecting dopamine |
| CN107570172A (en) * | 2017-08-30 | 2018-01-12 | 江苏大学 | A kind of preparation method and applications of ruthenium/nickel alloy nanocatalyst |
| CN107808964A (en) * | 2017-10-23 | 2018-03-16 | 济南大学 | A kind of method using polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry |
| CN108372315A (en) * | 2018-04-03 | 2018-08-07 | 贵州大学 | A kind of bianry alloy PtCu nanosponges |
| CN110988062A (en) * | 2019-11-25 | 2020-04-10 | 郑州炜盛电子科技有限公司 | Preparation method of gas diffusion electrode for measuring hydrogen sulfide gas |
| CN113458409A (en) * | 2021-06-17 | 2021-10-01 | 西南大学 | Method for synthesizing nano alloy catalyst at room temperature |
| CN114899438A (en) * | 2022-06-07 | 2022-08-12 | 江苏大学 | Preparation method of ternary alloy platinum ruthenium copper catalyst and application of ternary alloy platinum ruthenium copper catalyst in methanol catalysis |
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Cited By (14)
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| CN105798325B (en) * | 2016-03-24 | 2018-07-06 | 贵州大学 | A kind of ruthenium (Ru) nanometer line network of Asia 2nm and preparation method thereof |
| CN105798325A (en) * | 2016-03-24 | 2016-07-27 | 贵州大学 | Sub-2nm ruthenium (Ru) nanowire network and preparation method thereof |
| CN105958087A (en) * | 2016-06-08 | 2016-09-21 | 贵州大学 | General preparation method for flower-like porous platinum-based nano-catalyst |
| CN105958087B (en) * | 2016-06-08 | 2018-12-07 | 贵州大学 | A kind of general preparative methods of flower-shaped apertures platinum base nanocatalyst |
| CN106348247A (en) * | 2016-10-26 | 2017-01-25 | 贵州大学 | Synthesis method of ternary PtPdCu nano-crystal and application |
| CN106841355A (en) * | 2017-03-29 | 2017-06-13 | 贵州大学 | A kind of PtNi Nanoalloy electrochemical sensors for detecting dopamine |
| CN106841355B (en) * | 2017-03-29 | 2023-09-01 | 贵州大学 | PtNi nano alloy electrochemical sensor for detecting dopamine |
| CN107570172A (en) * | 2017-08-30 | 2018-01-12 | 江苏大学 | A kind of preparation method and applications of ruthenium/nickel alloy nanocatalyst |
| CN107808964A (en) * | 2017-10-23 | 2018-03-16 | 济南大学 | A kind of method using polygonal pattern PtCoFe nanocatalysts catalysis oxidation methanol electrochemistry |
| CN108372315A (en) * | 2018-04-03 | 2018-08-07 | 贵州大学 | A kind of bianry alloy PtCu nanosponges |
| CN110988062A (en) * | 2019-11-25 | 2020-04-10 | 郑州炜盛电子科技有限公司 | Preparation method of gas diffusion electrode for measuring hydrogen sulfide gas |
| CN110988062B (en) * | 2019-11-25 | 2022-07-26 | 郑州炜盛电子科技有限公司 | Preparation method of gas diffusion electrode for measuring hydrogen sulfide gas |
| CN113458409A (en) * | 2021-06-17 | 2021-10-01 | 西南大学 | Method for synthesizing nano alloy catalyst at room temperature |
| CN114899438A (en) * | 2022-06-07 | 2022-08-12 | 江苏大学 | Preparation method of ternary alloy platinum ruthenium copper catalyst and application of ternary alloy platinum ruthenium copper catalyst in methanol catalysis |
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Application publication date: 20151028 |