CN116936835A - Ordered Pt of double noble metals 3-x M x Co/NMC intermetallic compound catalyst and preparation method and application thereof - Google Patents
Ordered Pt of double noble metals 3-x M x Co/NMC intermetallic compound catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a double noble metal ordered Pt 3‑x M x Co/NMC intermetallic compound catalyst, preparation method and application thereof; the preparation method of the invention comprises the following steps: synthesizing an NMC carbon carrier; preparing a precursor solution; immersing the obtained NMC carbon carrier into a precursor solution, immersing the solution into NMC pore channels by ultrasonic, and then freeze-drying; roasting the obtained product at high temperature in a reducing atmosphere environment to obtain the double noble metal ordered Pt 3‑x M x Co/NMC intermetallic catalyst. The invention utilizes non-platinum noble metal to partially replace ordered Pt 3 Preparation of ordered double noble metal Pt-based intermetallic compound by platinum element in Co intermetallic compound and ordered Pt 3 Compared with Co intermetallic compound, the activity and stability of the Co intermetallic compound are greatly improved, pt 3‑x M x Co/NMC for oxygen reduction and fuel cell cathodeThe catalyst exhibits excellent catalytic performance.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a double noble metal ordered Pt 3-x M x Co/NMC intermetallic compound catalyst and its preparation method and application.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of high energy conversion efficiency, no pollution and the like, and are one of the most important new energy technologies in the 21 st century. Commercialization of fuel cells still faces significant challenges due to cost and durability issues. One of the main factors affecting fuel cell performance and cost is the catalyst of the cathode. Therefore, it is of great importance to develop a cathode catalyst having high activity and high stability.
PtM intermetallic catalysts (M is a transition metal element) are considered to be the most promising fuel cell catalysts in the future due to their structural stability and electrochemical stability. Almost all intermetallic compounds at present are heat treated at high temperature to order the atomic arrangement of the catalyst. Almost all preparation processes of the method need to use a carbon carrier for loading so as to disperse intermetallic compounds and prevent agglomeration of the catalyst. Although carbon may act as a carrier for dispersing intermetallic compounds, it does not possess electrocatalytic activity. Therefore, it is of great importance to find a method for synthesizing an intermetallic catalyst with high activity/stability. Based on this, a great deal of research has been conducted on the preparation method of intermetallic compounds. Chinese patent No. CN109873174a reports disordered PtPdCo/C nanoalloys for oxygen reduction with initial and post-stability mass specific activities of 764 and 758A mg, respectively -1 Pt Although the activity of the catalyst is kept better after 5000 cycles of stability circulation, the initial mass specific activity of the catalyst is lower, and the catalyst cannot meet the commercialization requirement of proton exchange membrane fuel cells. Zhao et al (Zhao w., et al, ACS catalyst.2022, 12, 7571-7578) partially replaces ordered Pt with Ti 3 Co preparation in Co has electronic structure superior to ordered Pt 3 The ordered Pt-Co-Ti intermetallic compound of Co finds that the introduction of Ti metal has good regulation and control effect on the electronic structure of Pt, and d band center is reduced, and is worth noting that the acid resistance of Ti well reduces the dissolution of Co, thereby stabilizing the oxygen reduction activity of PtCoTi. However, the catalyst also has proton exchangeAnd the performance of the single cell of the membrane-changed fuel cell is insufficient.
Although many studies on intermetallic compound catalysts have been reported, these catalysts have such or other disadvantages that Pt-based intermetallic compound catalysts are not commercially available on a large scale at present, such as insufficient activity of Pt-based intermetallic compound catalysts, insufficient retention of ordered structures of catalysts after multi-hybridization, insufficient stability, and limited optimization of electronic structures to substitution of non-Pt elements. Therefore, the preparation of the novel multi-element Pt-based intermetallic compound catalyst with better activity and stability has very important significance.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide the double noble metal ordered Pt 3- x M x Co/NMC intermetallic compound catalyst, preparation method and application thereof; the double noble metal intermetallic compound has small particle size, highly ordered atomic arrangement, high dispersion and high activity. In the preparation process, NMC has the functions of a template agent and a carrier, and the method is simple, efficient and universal.
The invention adopts nitrogen doped mesoporous carbon (NMC) as a hard template agent and a carrier, controls the size of intermetallic compound nano particles, and utilizes a third component non-Pt noble metal M part to replace Pt 3 The Pt element in the Co intermetallic compound optimizes the electronic structure of Pt by introducing noble metal M, so that the d-band center of the catalyst is lowered, and the oxygen reduction activity is further improved.
The invention adopts non-platinum noble metal part to replace binary ordered Pt by using nitrogen doped mesoporous carbon (NMC) as a hard template and a carrier 3 Pt in Co intermetallic compounds with small particle size, high dispersion, high performance, ordered structure, pt containing two noble metals 3-x M x Co intermetallic catalyst. The method comprises the steps of impregnating nitrogen-doped mesoporous carbon with a solution containing noble metal platinum salt or acid, non-platinum noble metal salt or acid precursor and non-noble metal salt precursor, freeze-drying, and then performing high-temperature treatment in an environment containing a reducing atmosphere. Can be obtainedTo double noble metal ordered Pt 3-x M x Co intermetallic catalyst. The intermetallic nano particles in the catalyst have small granularity and uniform particle size and are uniformly distributed on the surface and inside the mesopores of the porous carbon.
The invention aims at realizing the following technical scheme:
ordered Pt of double noble metals 3-x M x The preparation method of the Co/NMC intermetallic compound catalyst comprises the following steps:
(1) Synthesizing an NMC carbon carrier, carrying out high-temperature pyrolysis on a ZIF-8 material prepared from soluble zinc salt and 2-methylimidazole in anhydrous methanol under inert gas, and then carrying out acid washing, drying and grinding for later use;
(2) Preparing a precursor solution, dissolving a noble metal Pt precursor, a non-Pt noble metal M precursor and a non-noble metal precursor in deionized water, and uniformly mixing by ultrasonic dissolution; the non-Pt noble metal M precursor comprises an acid or salt containing one of Ru, pd, ir and Au; the non-noble metal precursor includes a Co salt;
(3) Immersing the NMC carbon carrier obtained in the step (1) into the precursor solution obtained in the step (2), immersing the solution into the pore channels of NMC by ultrasonic waves, and then freeze-drying;
(4) Roasting the product obtained in the step (3) at high temperature in a reducing atmosphere environment to obtain the double noble metal ordered Pt 3- x M x Co/NMC intermetallic catalyst.
Preferably, in the step (1), the molar ratio of the 2-methylimidazole to the zinc ions in the soluble zinc salt is in the range of 3 to 6;
further preferably, in the step (1), the molar ratio of zinc ions to 2-methylimidazole in the soluble zinc salt is 1:4;
preferably, in step (1), the soluble zinc salt is zinc nitrate hexahydrate.
Preferably, in step (1), the molar volume ratio of the soluble zinc salt to the anhydrous methanol is 0.05-0.2moL/L.
Preferably, in the step (1), the thermal cracking temperature is 900-1100 ℃ and the time is 1-3 hours; the inert gas is high-purity argon.
Preferably, in the step (1), the pickling temperature is 60-90 ℃ and the pickling time is 8-12 hours.
Preferably, in the step (2), the molar ratio of the noble metal Pt to the non-Pt noble metal M in the precursor solution is (3-x) x, wherein x is more than or equal to 0.01 and less than or equal to 0.5;
preferably, in step (2), the molar ratio of total noble metal to non-noble metal in the precursor solution ranges from 1 to 3.
Preferably, in the step (2), when the non-Pt noble metal precursor is palladium chloride acid, chloroauric acid, iridium chloride acid or rhodium chloride, the non-noble metal precursor is cobalt chloride, cobalt nitrate, cobalt acetate or sulfated cobalt.
Preferably, in the step (3), the impregnation process is to drop the precursor solution into the NMC carbon carrier dropwise and uniformly; the ultrasonic time is 0.5-2 hours;
preferably, in step (3), the ratio of the mass of the NMC carbon carrier to the total mass of metal in the precursor solution ranges from 1 to 4.
Further preferably, in the step (3), the ratio of the mass of the NMC carbon carrier to the total mass of the metal in the precursor solution is 4:1.
Preferably, in the step (4), the reducing atmosphere is H 2 Ar mixed gas; the roasting temperature is 600-850 ℃ and the time is 1.5-4 hours.
Further preferably, the H 2 H in Ar mixed gas 2 The volume fraction of (2) is in the range of 5-15%.
The double noble metal ordered Pt prepared by the preparation method 3-x M x Co/NMC intermetallic catalyst.
The double noble metal ordered Pt 3-x M x The atomic arrangement of Co/NMC intermetallic compounds is highly ordered.
The double noble metal ordered Pt 3-x M x The Co/NMC intermetallic compound catalyst is used as the fuel cell catalyst.
Compared with the prior art, the invention has the following advantages:
(1) Ordered Pt of double noble metals 3-x M x The Co/NMC intermetallic compound catalyst has the advantages of good crystal structure and highly ordered atomic arrangement, the non-Pt noble metal M is introduced into the catalyst to successfully replace the Pt position, and the Pt before replacement is well maintained 3 Ordered crystal structure of Co;
(2) Ordered Pt of double noble metals 3-x M x The Co/NMC intermetallic compound catalyst has the advantages of small scale and good dispersion;
(3) Ordered Pt of double noble metals 3-x M x Co/NMC intermetallic catalyst having lower Pt 3 D band center of Co/NMC intermetallic compound catalyst;
(4) Ordered Pt of double noble metals 3-x M x Co/NMC intermetallic catalyst has higher Pt than that of Co/NMC intermetallic catalyst 3 The electrochemically active area of the Co/NMC intermetallic catalyst;
(5) Ordered Pt of double noble metals 3-x M x Co/NMC intermetallic catalyst has higher Pt than that of Co/NMC intermetallic catalyst 3 Oxygen reduction activity of Co/NMC intermetallic catalyst;
(6) Ru and Ir doped double noble metal ordered Pt 3-x M x Ordered Pt of double noble metals doped with Co/NMC intermetallic compound compared with Pd 3-x M x Co/NMC intermetallic compounds have higher oxygen reduction activity.
Drawings
FIG. 1 shows ordered Pt prepared in examples 2-5 3-x M x XRD pattern of Co/NMC intermetallic compound.
FIG. 2 is an ordered Pt prepared in example 2 2.9 Pd 0.1 TEM image of Co/NMC intermetallic compound.
FIG. 3 is an ordered Pt prepared in example 2 2.9 Pd 0.1 STEM diagram of Co intermetallic compound.
Fig. 4 is a graph of a line intensity file for section 1 of fig. 3.
FIG. 5 is an ordered Pt prepared in example 2 2.9 Pd 0.1 Co and ordered Pt prepared in comparative example 1 3 Valence band spectrum contrast plot of Co intermetallic compound.
FIG. 6 is a Pt prepared in example 2 2.9 M 0.1 Co/NMC intermetallic electrochemical active area histogram.
FIG. 7 Pt prepared in examples 1-4 2.9 M 0.1 Oxygen reduction performance curve graph of Co/NMC intermetallic compound, the inset is the enlarged graph of the solid line box.
FIG. 8 shows the Pt-containing composition prepared in example 1 2.9 Pd 0.1 Oxygen reduction performance graph after stability test of Co/NMC intermetallic compound, the inset is the enlarged graph of the solid line box.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters that are not specifically noted.
Example 1
8.042g of 2-methylimidazole and 7.212g of zinc nitrate hexahydrate are respectively stirred and dissolved in a beaker filled with 80mL and 240mL of absolute methanol, the solution is stirred for 30min in a sealing manner until the solution is uniform, then the solution is mixed, stirred for 24h in a sealing manner until the reaction is complete, then the solution is centrifugally washed for 4 times by the absolute methanol, and finally the solution is dried for 12h in a vacuum oven at 60 ℃ to obtain ZIF-8.
Thermally cracking ZIF-8 in Ar environment at 950 ℃ for 3h to obtain ZIF-8 derived carbon 0.5. 0.5M H 2 SO 4 Washing with water until pH is neutral after washing with acid at 80deg.C for 10h, vacuum drying at 80deg.C, and grinding to obtain NMC.
Example 2
Respectively dissolving chloroplatinic acid, cobalt chloride and a certain amount of chloropalladate in deionized water, and carrying out ultrasonic dissolution to obtain a metal precursor solution, wherein the concentrations of the chloroplatinic acid, the cobalt chloride and the chloropalladate are respectively 0.386mol L -1 、0.386mol L -1 And 0.1mol L -1 . Taking 64uL, 22uL and 8.5uL of metal precursor solutions respectively, uniformly mixing the solutions by ultrasonic, uniformly dripping the solutions into 20mg of NMC (the NMC is the ground material) drop by drop, performing ultrasonic treatment for 1h, and then performing freeze drying. The dried product is treated in H 2 /Ar(H 2 And (5-15%) by volume fraction of the catalyst is calcined at 750 deg.C for 2 hours in an atmosphere. Obtaining NMC-loaded Pt 2.9 Pd 0.1 Co/NMC catalyst.
Example 3
Respectively dissolving chloroplatinic acid, cobalt chloride and a certain amount of ruthenium chloride in deionized water, and carrying out ultrasonic dissolution to obtain a metal precursor solution, wherein the concentrations of the chloroplatinic acid, the cobalt chloride and the ruthenium chloride are respectively 0.386mol L -1 、0.386mol L -1 And 0.1mol L -1 . Taking 64uL, 22uL and 8.5uL of metal precursor solutions respectively, uniformly mixing the solutions by ultrasonic, uniformly dripping the solutions into 20mg of NMC (the NMC is the ground material) drop by drop, performing ultrasonic treatment for 1h, and then performing freeze drying. The dried product is treated in H 2 /Ar(H 2 And (5-15%) by volume fraction of the catalyst is calcined at 750 deg.C for 2 hours in an atmosphere. Obtaining NMC-loaded Pt 2.9 Ru 0.1 Co/NMC catalyst.
Example 4
Dissolving chloroplatinic acid, cobalt chloride and chloroiridium acid in deionized water respectively, and performing ultrasonic dissolution to obtain metal precursor solution, wherein the concentrations of the chloroplatinic acid, the cobalt chloride and the chloroiridium acid are respectively 0.386mol L -1 、0.386mol L -1 And 0.1mol L -1 . Taking 64uL, 22uL and 8.5uL of metal precursor solutions respectively, uniformly mixing the solutions by ultrasonic, uniformly dripping the solutions into 20mg of NMC (the NMC is the ground material) drop by drop, performing ultrasonic treatment for 1h, and then performing freeze drying. The dried product is treated in H 2 /Ar(H 2 And (5-15%) by volume fraction of the catalyst is calcined at 750 deg.C for 2 hours in an atmosphere. Obtaining NMC-loaded Pt 2.9 Ir 0.1 Co/NMC catalyst.
Example 5
Dissolving chloroplatinic acid, cobalt chloride and chloroauric acid in deionized water respectively, and performing ultrasonic dissolution to obtain metal precursor solution, wherein the concentrations of the chloroplatinic acid, the cobalt chloride and the chloroauric acid are respectively 0.386mol L -1 、0.386mol L -1 And 0.1mol L -1 . Taking 64uL, 22uL and 8.5uL of metal precursor solutions respectively, uniformly mixing the solutions by ultrasonic, uniformly dripping the solutions into 20mg of NMC (the NMC is the ground material) drop by drop, performing ultrasonic treatment for 1h, and then performing freeze drying. The dried product is treated in H 2 /Ar(H 2 And (5-15%) by volume fraction of the catalyst is calcined at 750 deg.C for 2 hours in an atmosphere. Obtaining NMC-loaded Pt 2.9 Au 0.1 Co/NMC catalyst.
Comparative example 1
Dissolving chloroplatinic acid and cobalt chloride in deionized water respectively, and ultrasonically dissolving to obtain metal precursor solution, wherein the concentration of chloroplatinic acid and cobalt chloride is 0.386mol L respectively -1 And 0.386mol/L. Respectively taking 66ul and 22ul of metal precursor solutions, uniformly mixing by ultrasonic, dropwise and uniformly dripping 20mg of NMC (NMC is the ground material) into the solution, performing ultrasonic treatment for 1h, and then performing freeze drying. The dried product is treated in H 2 /Ar(H 2 And (5-15%) by volume fraction of the catalyst is calcined at 750 deg.C for 2 hours in an atmosphere. Obtaining NMC-loaded Pt 3 Co/NMC catalyst.
Example 6
3mg of the active materials prepared in examples 1 to 4 were weighed and dispersed in a mixture of 300. Mu.L of Nafion (0.25%) in isopropanol and 300. Mu.L of deionized water, and after uniform dispersion, 5. Mu.L of the active materials were removed by a pipette and dropped onto the surface of a glassy carbon electrode, and dried and then added with 0.1M HClO 4 The oxygen reduction catalytic activity was tested in solution.
Ordered Pt prepared in examples 2-5 3-x M x Co/NMC and ordered Pt prepared in comparative example 1 3 XRD contrast patterns of Co/NMC intermetallic catalyst, as shown in FIG. 1, can be seen as ordered Pt 3-x M x Co/NMC catalyst has no simple substance diffraction peak of Pt, co, M and other elements, and Pt 3-x M x Diffraction peak and ordered Pt of Co/NMC catalyst 3 Co/NMC and standard ordered Pt 3 The PDF cards of Co can be perfectly matched, indicating that the crystal structure of the catalyst is highly ordered.
EXAMPLE 2 preparation of Pt 2.9 Pd 0.1 As shown in a TEM image of the Co/NMC intermetallic compound catalyst in figure 2, the morphology of the dodecahedron of ZIF-8 is maintained in the whole NMC loaded with the intermetallic compound catalyst, and the Pt loaded by the NMC 2.9 Pd 0.1 Co particles are uniformly dispersed, and agglomeration phenomenon does not occur.
EXAMPLE 2 preparation of Pt 2.9 Pd 0.1 The Co/NMC intermetallic compound catalyst HAADF-STEM is shown in figure 3, and the atomic arrangement of the intermetallic nano particles has the characteristic of long-range order.
EXAMPLE 2 preparation of Pt 2.9 Pd 0.1 Co/NMC intermetallicThe compound catalyst HAADF-STEM line intensity profile is shown in fig. 4, where Pd can be observed to replace the Pt atom originally at that position.
Pt prepared in example 2 2.9 Pd 0.1 Co/NMC and ordered Pt prepared in comparative example 1 3 Valence band spectrum contrast of Co/NMC intermetallic compound catalyst, as shown in FIG. 5, pt 2.9 Pd 0.1 Valence band of Co/NMC catalyst compared to Pt 3 The Co/NMC catalyst was reduced by 0.24eV.
EXAMPLES 2-5 preparation of Pt 2.9 M 0.1 Co/NMC and ordered Pt prepared in comparative example 1 3 The electrochemical active area histogram of Co/NMC intermetallic catalyst, as shown in FIG. 6, shows Pt 2.9 Pd 0.1 The electrochemical area of Co/NMC is higher than any other catalyst.
EXAMPLES 2-5 preparation of Pt 2.9 M 0.1 The oxygen reduction polarization curve of Co/NMC intermetallic catalyst is shown in FIG. 7, pt 2.9 Pd 0.1 The half-wave potential of the polarization curve of the Co/NMC intermetallic compound catalyst is higher than Pt 3 Co/NMC intermetallic catalysts and other catalysts.
EXAMPLE 2 preparation of Pt 2.9 Pd 0.1 The polarization curve after the oxygen reduction catalytic stability test of the Co/NMC intermetallic catalyst is shown in the graph, and the inset shows that after 30 000 circles of cyclic test, the half-wave potential of the catalyst is only reduced by 8mV.
EXAMPLES 2-5 preparation of Pt 2.9 M 0.1 The initial mass specific activity of the Co/NMC intermetallic catalyst is shown in Table 1;
TABLE 1
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. Ordered Pt of double noble metals 3-x M x The preparation method of the Co/NMC intermetallic compound catalyst is characterized by comprising the following steps:
(1) Synthesizing an NMC carbon carrier, carrying out high-temperature pyrolysis on a ZIF-8 material prepared from soluble zinc salt and 2-methylimidazole in anhydrous methanol under inert gas, and then carrying out acid washing, drying and grinding for later use;
(2) Preparing a precursor solution, dissolving a noble metal Pt precursor, a non-Pt noble metal M precursor and a non-noble metal precursor in deionized water, and uniformly mixing by ultrasonic dissolution; the non-Pt noble metal M precursor comprises an acid or salt containing one of Ru, pd, ir and Au; the non-noble metal precursor includes a Co salt;
(3) Immersing the NMC carbon carrier obtained in the step (1) into the precursor solution obtained in the step (2), immersing the solution into the pore channels of NMC by ultrasonic waves, and then freeze-drying;
(4) Roasting the product obtained in the step (3) at high temperature in a reducing atmosphere environment to obtain the double noble metal ordered Pt 3-x M x Co/NMC intermetallic catalyst.
2. The process according to claim 1, wherein in step (1), the molar ratio of 2-methylimidazole to zinc ions in the soluble zinc salt is in the range of 3 to 6;
in step (1), the soluble zinc salt is zinc nitrate hexahydrate.
3. The process of claim 1, wherein in step (1), the thermal cracking temperature is 900 to 1100 ℃ for 1 to 3 hours; the inert gas is argon;
the pickling temperature is 60-90 ℃ and the pickling time is 8-12 hours.
4. The preparation method according to claim 1, wherein in the step (2), the molar ratio of the noble metal Pt to the non-Pt noble metal M in the precursor solution is (3-x) x, wherein x is more than or equal to 0.01 and less than or equal to 0.5;
in the step (2), the molar ratio of the total noble metal to the non-noble metal in the precursor solution ranges from 1 to 3.
5. The method of claim 1, wherein in step (2), when the non-Pt noble metal precursor is chloropalladac acid, chloroauric acid, chloroiridic acid or rhodium chloride, the non-noble metal precursor is cobalt chloride, cobalt nitrate, cobalt acetate or sulfated cobalt.
6. The method according to claim 1, wherein in the step (3), the impregnation process is to drop the precursor solution into the NMC carbon carrier drop by drop uniformly; the time of the ultrasonic treatment is 0.5-2 hours.
7. The method of claim 1, wherein in step (3), the ratio of the mass of the NMC carbon support to the total mass of metal in the precursor solution is in the range of 1 to 4.
8. The method according to claim 1, wherein in the step (4), the reducing atmosphere is H 2 Ar mixed gas; the roasting temperature is 600-850 ℃ and the time is 1.5-4 hours.
9. The ordered Pt of double noble metals produced by the production process of any one of claims 1 to 8 3-x M x Co/NMC intermetallic catalyst.
10. The double noble metal ordered Pt of claim 9 3-x M x The Co/NMC intermetallic compound catalyst is used as the fuel cell catalyst.
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| CN119419299A (en) * | 2024-11-01 | 2025-02-11 | 北京科技大学 | A platinum-palladium-based multi-element alloy sub-nanobelt catalyst and its preparation method and application |
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