CN111659389A - Platinum-based catalyst containing actinide simple substance or compound - Google Patents

Abstract

The invention belongs to the technical field of catalysts, and relates to a platinum-based catalyst containing an actinide element simple substance or compound. The platinum-based catalyst comprises a catalytic active substance and a catalytic auxiliary substance, wherein the catalytic active substance comprises platinum metal, the catalytic auxiliary substance comprises a cocatalyst, and the cocatalyst comprises one or more of simple substances or compounds of actinide or protactinium. The platinum-based catalyst containing the actinide simple substance or compound has better catalytic performance and stability.

Description

A platinum-based catalyst containing actinide element or compound

technical field

The invention belongs to the technical field of catalysts, and relates to a platinum-based catalyst containing actinide elements or compounds.

Background technique

Catalyst materials and catalytic technology are one of the basic and key materials and technologies for the development of today's chemical industry. In modern industry, the output value generated by the use of catalytic technology has accounted for about 30% of the total output value of the national economy.

The outer electron arrangement of noble metal Pt is 5d ⁸ 6s ² , followed by 8 d electrons in the outer layer, and the orbitals are not filled. And because the energy level contains unpaired electrons, Pt can show strong ferromagnetism or paramagnetism in physical properties; and in the process of chemical adsorption, these d electrons of Pt can interact with the p electrons in the adsorbate. Or s electron pairing, chemical adsorption occurs, and intermediate products are generated, thereby activating the adsorbed molecules.

In modern industry, platinum catalysts are mainly used in the purification and treatment of inorganic chemicals, petroleum refining, organic chemicals, C1 chemicals, fine chemicals, automobile exhaust and industrial gases, as well as fuel cells and sensors. Energy technology has a very important position and shows broad application prospects.

However, pure Pt as a catalyst has three main disadvantages, namely, low utilization rate, low anti-poisoning ability and high price. In view of these shortcomings, a large number of researches worldwide are devoted to developing high-activity platinum catalysts and reducing the amount of platinum catalysts to improve the catalytic activity, selectivity, and prolong life of Pt catalysts.

Regarding Pt catalysts, the current main research directions are:

1. One-way Pt-based catalyst

The research direction of one-element Pt-based catalysts focuses on finding catalyst supports with excellent performance and changing the size and surface state of Pt particles. For example, Zhu et al. used functionalized multi-walled carbon nanotubes dispersed in polyaniline as a carrier to synthesize a catalyst with good dispersibility of Pt/MWCNT/PAN. The research results show that the catalyst exhibits higher catalytic activity than pure polyaniline-supported catalyst. Another example is Wu et al. prepared a "shell-core" structure of carbon nanomaterials, with carbon black particles as the "core" load, and the type-doped graphite layer as the "shell", this catalyst has high catalytic activity. Another example is Zhang et al. prepared nanoflowers with novel morphology by template-free electrodeposition method, and their morphology is porous and can provide larger active centers.

2. Binary Pt-based catalyst

Adding a second metal that is easy to adsorb oxygen-containing substances to the pure Pt catalyst to prepare an alloy type catalyst will improve the anti-toxicity of the catalyst, thereby greatly improving the performance of the catalyst. At present, Pt-based binary catalysts with more research and better catalytic effect include PtRu, PtPd, PtSn, PtAu, PtNi, PtCo and metal oxides (Pt+MO _x , where M=Ti, W, Zr, Ce, Ta) and other composite catalysts.

3. Multi-component Pt-based catalyst

The researchers tried to improve the Pt-based alloy by adding a third or even a fourth metal, thereby increasing its catalytic activity. For example, Park et al. studied the electronic and chemical effects of Pt/Ni and Pt/Ru/Ni nanocatalysts during methanol oxidation. Another example is Jeon et al. synthesized a PtCoCr ternary catalyst. The experimental results show that Pt ₃₀ Co ₃₀ Cr ₄₀ has very good methanol electro-oxidation, stability and catalytic effect, and is an excellent methanol electro-oxidation catalyst.

In summary, although scientists have carried out a number of works in the field of noble metal Pt catalysis, different methods have their own advantages and disadvantages. And the industrial application of these Pt catalytic materials still faces many challenges, such as large-scale and controllable synthesis methods, stability of catalytic materials, precise regulation of metal loading, anti-poisoning ability of catalysts, and how to better advance metal materials. The preparation method can be effectively combined with carbon-supported materials and so on. Therefore, it is urgent to develop new ideas for noble metal Pt catalysis.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a platinum-based catalyst containing actinide element or compound, so as to have better catalytic performance and stability.

In order to achieve this purpose, in a basic embodiment, the present invention provides a platinum-based catalyst containing an actinide element or compound, the platinum-based catalyst comprises a catalytically active substance and a catalytic auxiliary substance, and the catalytically active substance It contains metal platinum, the catalytic auxiliary material contains a promoter, and the promoter contains one or more of actinide or protactinium element or compound (the platinum-based catalyst can be used in a fuel cell).

In a preferred embodiment, the present invention provides a platinum-based catalyst containing an actinide element or compound, wherein the mass ratio of the catalytically active substance to the catalytic auxiliary substance is 1:0.01-10.

In a preferred embodiment, the present invention provides a platinum-based catalyst containing an actinide element or compound, wherein the mass ratio of the catalytically active substance to the promoter is 1:0.0001-1.

In a preferred embodiment, the present invention provides a platinum-based catalyst containing an actinide element or compound, wherein the cocatalyst further comprises a catalyst selected from the group consisting of gold, silver, cobalt, nickel, palladium, ruthenium, tin, One or more elements or oxides of bismuth, copper, iron, iridium, manganese, molybdenum, rhodium, tungsten and zinc.

In a preferred embodiment, the present invention provides a platinum-based catalyst containing an actinide element or compound, wherein the catalytic auxiliary material further comprises a catalyst carrier selected from the group consisting of activated carbon, silicon carbide, aluminum oxide, One or more of graphene, silica and zeolite.

In a preferred embodiment, the present invention provides a platinum-based catalyst containing an actinide element or compound, wherein the compound is an inorganic compound or an organic compound.

In a preferred embodiment, the present invention provides a platinum-based catalyst containing an actinide element or compound, wherein the compound is an oxide.

The beneficial effect of the present invention is that the platinum-based catalyst containing actinide element or compound of the present invention has better catalytic performance and stability.

Detailed ways

The specific embodiments of the present invention will be further described below through examples.

Example 1: Preparation Example

Take 0.6g of Vulcan XC-72 carbon powder, 0.1g of Ac ₂ O ₃ powder, 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution and 17.04mL of NiSO ₄ (0.1mol/L) solution and add it to 80mL In deionized water, sonicate for 30min to make it disperse uniformly, then adjust the pH to 8-9 with 1mol/L NaOH solution under stirring, slowly add excess 2.0mg/mL _NaBH4 solution, and continue stirring for 3h. After washing with ultrapure water until there is no ^Cl- , vacuum drying at 60 °C for 4 h to obtain a Pt-Ni-Ac ₂ O ₃ /C catalyst.

Example 2: Comparative Preparation Example

Mix 0.6g Vulcan XC-72 carbon powder, 10.25mL H ₂ PtCl ₆ (0.1mol/L) solution and 17.04mL NiSO ₄ (0.1mol/L) solution into 80mL deionized water, ultrasonicate for 30min to disperse After the pH value was adjusted to 8-9 with 1 mol/L NaOH solution under stirring, an excess of 2.0 mg/mL NaBH ₄ solution was slowly added, and stirring was continued for 3 h. After washing with ultrapure water to no ^Cl- , vacuum drying at 60 °C for 4 h to obtain a Pt-Ni/C catalyst.

Example 3: Preparation Example

Take 0.6g of Vulcan XC-72 carbon powder, 0.1g of Ac ₂ O ₃ powder, and 80mL of ethylene glycol into a 250mL beaker, ultrasonically shake for 2h, dropwise add 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution and 16.97 mL of CoCl ₂ (0.1 mol/L) solution, add 21 mL of formic acid, stir at room temperature for 30 min, put it in a microwave oven to heat for 20 s, stop for 10 s and repeat 5 times, then heat for 10 s and stop for 10 s and repeat 5 times, cool and suction filter, vacuum dry, A Pt-Co-Ac ₂ O ₃ /C catalyst was obtained.

Example 4: Comparative Preparation Example

Take 0.6g of Vulcan XC-72 carbon powder, add 80mL of ethylene glycol into a 250mL beaker, ultrasonically shake for 2h, dropwise add 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution and 16.97mL of CoCl ₂ (0.1mol/L) L) solution, then add 21 mL of formic acid, stir at room temperature for 30 min, put it into a microwave oven and heat for 20 s, stop for 10 s and repeat 5 times, then heat for 10 s and stop for 10 s and repeat 5 times, cool and suction filter, and vacuum dry to obtain a Pt-Co/C catalyst.

Example 5: Preparation Example

Take 0.6 g of Vulcan XC-72 carbon powder and 0.1 g of Ac ₂ O ₃ powder and add it to an aqueous solution with a HCOOH content of 0.7 mol. After sonicating for 30 min, the obtained suspension was heated to 80 ° C, and under constant stirring, 10.25 mL of H ₂ PtCl ₆ (0.1 mol/L) solution and 9.4 mL of PdCl ₂ (0.1 mol/L) solution were added dropwise to the suspension. Continue stirring at 80 °C for 2 h to ensure complete reduction of Pd and Pt. After cooling, it was washed several times with ultrapure water suction filtration until there was no ^Cl- . Finally, the obtained catalyst was vacuum-dried in an oven at 60°C to obtain a Pt-Pd-Ac ₂ O ₃ /C catalyst.

Example 6: Comparative Preparation Example

Take 0.6 g of Vulcan XC-72 carbon powder and add it to an aqueous solution with a HCOOH content of 0.7 mol. After ultrasonication for 30 min, the obtained suspension was heated to 80° C. Under constant stirring, 10.25 mL of H ₂ PtCl ₆ (0.1 mol/L) solution and 9.4 mL of PdCl ₂ (0.1 mol/L) solution were added dropwise to the suspension. Continue stirring at 80 °C for 2 h to ensure complete reduction of Pd and Pt. After cooling, it was washed several times with ultrapure water suction filtration until there was no ^Cl- . Finally, the obtained catalyst was vacuum-dried in an oven at 60 °C to obtain a Pt-Pd/C catalyst.

Example 7: Preparation Example

Take 0.6g Vulcan XC-72 activated carbon, 0.1g Ac ₂ O ₃ powder, 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution, 5.08mL of HAuCl ₄ (0.1mol/L) solution and 17.04mL of NiSO ₄ (0.1 mol/L) solution was mixed and added to 80 mL of ultrapure water, and the obtained suspension was sonicated for 1 h. Then 200 mL of ethylene glycol (EG) solution was added, and after sonication for 1 h, the resulting solution was heated to 90° C. in a water bath and stirred continuously for 4 h. After cooling to room temperature and filtering, the obtained catalyst was washed several times with a mixed solution of distilled water and ethanol, and vacuum dried at 60°C to obtain a Pt-Au-Ni-Ac ₂ O ₃ /C catalyst.

Example 8: Comparative Preparation Example

Mix 0.6g Vulcan XC-72 activated carbon, 10.25mL H ₂ PtCl ₆ (0.1mol/L) solution, 5.08mL HAuCl ₄ (0.1mol/L) solution and 17.04mL NiSO ₄ (0.1mol/L) solution It was added to 80 mL of ultrapure water, and the resulting suspension was sonicated for 1 h. Then 200 mL of ethylene glycol (EG) solution was added, and after sonication for 1 h, the resulting solution was heated to 90° C. in a water bath and stirred continuously for 4 h. After cooling to room temperature and filtering, the obtained catalyst was washed several times with a mixed solution of distilled water and ethanol, and vacuum-dried at 60°C to obtain a Pt-Au-Ni/C catalyst.

Example 9: Preparation Example

Take 0.6g of brownish yellow graphene oxide, add 0.1g of Ac ₂ O ₃ powder to 50mL of deionized water, disperse it ultrasonically for 30min, and use a pipette to remove 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution, 17.04 mL of NiSO ₄ (0.1 mol/L) solution and 15.74 mL of CuCl ₂ (0.1 mol/L) solution were mixed into the graphene oxide solution, stirred for 10 min, and then transferred to a two-necked flask, and 9.5 mL of deionized water was added. After mixing uniformly at 0°C under _N2 gas atmosphere, ₅ mL of 7.72 mmol/L KBH4 solution was rapidly injected with a syringe, and the color of the solution changed from brown to black. Continue to stir at 0°C under _N2 gas atmosphere for 30 min to make it fully reaction, finally suction filtration washing, drying and grinding to obtain a Pt-Ni-Cu-Ac ₂ O ₃ /C catalyst.

Example 10: Comparative Preparation Example

Take 0.6g of brown-yellow graphene oxide and add it to 50mL of deionized water, ultrasonically disperse for 30min, and use a pipette to pipette 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution, 17.04mL of NiSO ₄ (0.1mol/L) solution L) solution and 15.74mL of CuCl ₂ (0.1mol/L) solution were mixed into the graphene oxide solution, stirred for 10min and then transferred to a two-necked flask, 9.5mL of deionized water was added, at 0°C, under _N2 gas atmosphere After mixing evenly, quickly inject 5mL of 7.72mmol/L _KBH4 solution with a syringe, the color of the solution changes from brown to black, continue to stir at 0 °C for 30min under _N2 gas atmosphere to make it fully react, and finally filter and wash, bake. Dry grinding to obtain a Pt-Ni-Cu/C catalyst.

Example 11: Preparation Example

Take 0.6g of Vulcan XC-72 activated carbon and 0.1g of Ac ₂ O ₃ powder, add it into a mixed solution of ultrapure water and isopropanol (volume ratio 2:1), and ultrasonically disperse for 0.5h. Then 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution, 9.4mL of PdCl ₂ (0.1mol/L) solution, 15.74mL of CuCl ₂ (0.1mol/L) solution and 20mg of sodium citrate were added dropwise in sequence, Stir for 1 h. The pH of the solution was adjusted to >12, the temperature was raised to 80 °C, and an excess of 0.2 mol/L sodium borohydride solution was slowly added dropwise for 2 h. Subsequently, stirring was continued at room temperature for 3 hours, and the mixture was washed with suction, and dried by blowing at 60° C. to obtain a Pt-Pd-Cu-Ac ₂ O ₃ /C catalyst.

Example 12: Comparative Preparation Example

Take 0.6g of Vulcan XC-72 activated carbon, add it to a mixed solution of ultrapure water and isopropanol (volume ratio 2:1), and disperse it ultrasonically for 0.5h. Then 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution, 9.4mL of PdCl ₂ (0.1mol/L) solution, 15.74mL of CuCl ₂ (0.1mol/L) solution and 20mg of sodium citrate were added dropwise in sequence, Stir for 1 h. The pH of the solution was adjusted to >12, the temperature was raised to 80 °C, and an excess of 0.2 mol/L sodium borohydride solution was slowly added dropwise for 2 h. Subsequently, stirring was continued for 3 h at room temperature, suction filtration and washing, and air drying at 60 °C was performed to obtain a Pt-Pd-Cu/C catalyst.

Example 13: Preparation Example

Take 0.6g Vulcan XC-72 carbon powder, 0.1g PaO ₂ powder, 10.25mL H ₂ PtCl ₆ (0.1mol/L) solution and 17.04mL NiSO ₄ (0.1mol/L) solution and add it to 80mL deionized In water, ultrasonicate for 30min to make it dispersed evenly, then adjust the pH to 8-9 with 1mol/L NaOH solution under stirring, slowly add excess 2.0mg/mL _NaBH4 solution, and continue stirring for 3h. After washing with ultrapure water until Cl ^- free, vacuum drying at 60 ℃ for 4 h to obtain Pt-Ni-PaO ₂ /C catalyst.

Example 14: Preparation Example

Take 0.6g Vulcan XC-72 carbon powder, 0.1g PaO ₂ powder, and 80mL ethylene glycol into a 250mL beaker, ultrasonically shake for 2h, dropwise add 10.25mL H ₂ PtCl ₆ (0.1mol/L) solution and 16.97mL CoCl ₂ (0.1mol/L) solution, then add 21mL of formic acid, stir at room temperature for 30min, put it in a microwave oven to heat for 20s, stop for 10s and repeat 5 times, then heat for 10s and stop for 10s and repeat 5 times, cool and suction filter, and vacuum dry to obtain Pt -Co-PaO ₂ /C catalyst.

Example 15: Preparation Example

Take 0.6 g of Vulcan XC-72 carbon powder and 0.1 g of PaO ₂ powder and add it to an aqueous solution with a HCOOH content of 0.7 mol. After sonicating for 30 min, the resulting suspension was heated to 80 °C, and under constant stirring, 10.25 mL of H ₂ PtCl ₆ (0.1 mol/L) solution and 9.4 mL of PdCl ₂ (0.1 mol/L) solution were added dropwise to the suspension. Continue stirring at 80 °C for 2 h to ensure complete reduction of Pd and Pt. After cooling, it was washed several times with ultrapure water suction filtration until there was no ^Cl- . Finally, the obtained catalyst was vacuum-dried in an oven at 60 °C to obtain a Pt-Pd-PaO ₂ /C catalyst.

Example 16: Preparation Example

Take 0.6g Vulcan XC-72 activated carbon, 0.1g PaO ₂ powder, 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution, 5.08mL of HAuCl ₄ (0.1mol/L) solution and 17.04mL of NiSO ₄ (0.1 mol/L) solution was mixed into 80 mL of ultrapure water, and the resulting suspension was sonicated for 1 h. Then 200 mL of ethylene glycol (EG) solution was added, and after sonication for 1 h, the resulting solution was heated to 90° C. in a water bath and stirred continuously for 4 h. After cooling to room temperature and filtering, the obtained catalyst was washed several times with a mixed solution of distilled water and ethanol, and dried in vacuum at 60°C to obtain a Pt-Au-Ni-PaO ₂ /C catalyst.

Example 17: Preparation Example

Take 0.6g of brown-yellow graphene oxide, add 0.1g PaO ₂ powder to 50mL of deionized water, ultrasonically disperse for 30min, use a pipette to remove 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution, 17.04mL of NiSO ₄ (0.1 mol/L) solution and 15.74 mL of CuCl ₂ (0.1 mol/L) solution were mixed into the graphene oxide solution, stirred for 10 min, and then transferred to a two-necked flask. , After mixing evenly under _N2 gas atmosphere, quickly inject 5mL 7.72mmol/L _KBH4 solution with a syringe, the color of the solution changes from brown to black, continue to stir at 0 °C under _N2 gas atmosphere for 30min to make it fully react, Finally, suction filtration washing, drying and grinding to obtain a Pt-Ni-Cu-PaO ₂ /C catalyst.

Example 18: Preparation Example

Take 0.6g of Vulcan XC-72 activated carbon and 0.1g of PaO ₂ powder, add it to the mixed solution of ultrapure water and isopropanol (volume ratio 2:1), and disperse by ultrasonic for 0.5h. Then 10.25mL of H ₂ PtCl ₆ (0.1mol/L) solution, 9.4mL of PdCl ₂ (0.1mol/L) solution, 15.74mL of CuCl ₂ (0.1mol/L) solution and 20mg of sodium citrate were added dropwise in sequence, Stir for 1 h. The pH of the solution was adjusted to >12, the temperature was raised to 80 °C, and an excess of 0.2 mol/L sodium borohydride solution was slowly added dropwise for 2 h. Subsequently, stirring was continued at room temperature for 3 hours, suction filtration and washing, and air drying at 60° C. to obtain a Pt-Pd-Cu-PaO ₂ /C catalyst.

Example 19: Stability Test Example

The stability of the catalysts obtained in Examples 1-18 was measured respectively, and the specific method was as follows: using the electrochemical workstation three-electrode system to test the It curve of the catalyst, and judge the stability of the catalyst accordingly, wherein the glassy carbon electrode on which the catalyst was dripped was used as the working electrode. , saturated calomel electrode as the reference electrode, platinum wire electrode as the counter electrode. The solution to be tested is 0.5mol/LC ₂ H ₅ OH+0.5mol/LH ₂ SO ₄ , and high-purity nitrogen gas was passed into the solution for 15 minutes before the test to eliminate the interference of oxygen. The test potential of all catalysts was uniformly 0.6 V, and the test time was 1000 s. The results are shown in Table 1 below.

Table 1 Catalyst stability test results

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. Thus, provided that these modifications and variations of the present invention fall within the scope of the claims of the present invention and their technical equivalents, the present invention is also intended to include such modifications and variations. The above-mentioned embodiments or implementations are merely illustrative of the present invention, and the present invention may also be implemented in other specific forms or other specific forms without departing from the gist or essential characteristics of the present invention. Accordingly, the described embodiments are to be regarded in all respects as illustrative and not restrictive. The scope of the present invention should be indicated by the appended claims, and any changes equivalent to the intent and scope of the claims should also be included within the scope of the present invention.

Claims (7)

1. A platinum-based catalyst comprising an actinide element or compound, characterized in that: the platinum-based catalyst comprises a catalytic active substance and a catalytic auxiliary substance, wherein the catalytic active substance comprises platinum metal, the catalytic auxiliary substance comprises a cocatalyst, and the cocatalyst comprises one or more of simple substances or compounds of actinide or protactinium.

2. The platinum-based catalyst according to claim 1, characterized in that: the mass ratio of the catalytic active substance to the catalytic auxiliary substance is 1: 0.01-10.

3. The platinum-based catalyst according to claim 1, characterized in that: the mass ratio of the catalytic active substance to the cocatalyst is 1: 0.0001-1.

4. The platinum-based catalyst according to claim 1, characterized in that: the catalyst promoter also comprises one or more of simple substances or oxides of gold, silver, cobalt, nickel, palladium, ruthenium, tin, bismuth, copper, iron, iridium, manganese, molybdenum, rhodium, tungsten and zinc.

5. The platinum-based catalyst according to claim 1, characterized in that: the catalytic auxiliary substance also comprises a catalyst carrier which is selected from one or more of active carbon, silicon carbide, aluminum oxide, graphene, silicon dioxide and zeolite.

6. The platinum-based catalyst according to claim 1, characterized in that: the compound is an inorganic compound or an organic compound.

7. The platinum-based catalyst according to claim 1, characterized in that: the compound is an oxide.