CN114284514A - Fuel cell electrocatalyst Pt3M-N/C and preparation method thereof - Google Patents
Fuel cell electrocatalyst Pt3M-N/C and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a fuel cell electrocatalyst Pt3The M-N/C and the preparation method thereof comprise the following steps: firstly, taking metal phthalocyanine MPc, carbon black and H2PtCl6·6H2Uniformly mixing O and an organic solvent A, reacting for 1-2 h, and heating and stirring until the organic solvent A is evaporated to form slurry; drying the slurry, and grinding to obtain a powdery product; and finally, calcining the powdery product at 800-1000 ℃ in the coexistence atmosphere of reducing gas and inert gas, and cooling to room temperature after calcining to obtain the fuel cell electrocatalyst Pt3M-N/C; wherein the metal phthalocyanine MPc, carbon black and H2PtCl6·6H2The mass ratio of O is 10: (24-30): (7-11). The Pt in the catalyst prepared by the method disclosed by the invention achieves a low load of 6.9-11%, the cost is effectively reduced, and the electrochemical performance is more excellent compared with that of commercial platinum carbon with a load of 40%.
Description
Technical Field
The invention belongs to the field of hydrogen fuel cell catalysts, and particularly relates to a fuel cell electrocatalyst Pt3M-N/C and a preparation method thereof.
Background
Energy is vital to human production and life. The energy we now use is mainly fossil fuels, including coal, oil and natural gas. However, fossil fuel is a primary energy source and is not renewable, and the combustion of fossil fuel brings about many environmental problems, most typically greenhouse effect and air pollution, so that the development of clean and sustainable new energy sources becomes a hot research subject at present. The fuel cell can directly convert externally supplied hydrogen energy into electric energy through electrochemical reaction without combustion, so that the fuel cell is not limited by Carnot cycle, the energy conversion efficiency can reach 40-60%, nitrogen and sulfur oxides are hardly discharged, and the fuel cell is green and pollution-free. However, as the oxygen reduction reaction which is important in the fuel cell and the metal-air cell, the commercialization of the fuel cell and the metal-air cell is limited due to the problems that the slow reaction kinetics require the noble metal Pt or the like to accelerate the oxygen reduction reaction, and the noble metal Pt has a limited storage capacity and is expensive. Therefore, it is very important to develop a platinum-based alloy catalyst with high activity, low cost and high stability.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a fuel cell electrocatalyst Pt3The M-N/C and the preparation method thereof effectively reduce the platinum loading capacity, and the prepared electrocatalyst has better catalytic activity.
In order to achieve the technical purpose, the technical scheme of the electrocatalyst is as follows:
the method comprises the following steps: firstly, taking metal phthalocyanine MPc, carbon black and H2PtCl6·6H2Uniformly mixing O and an organic solvent A, reacting for 1-2 h, and heating and stirring until the organic solvent A is evaporated to form slurry; drying the slurry, and grinding to obtain a powdery product; and finally, calcining the powdery product at 800-1000 ℃ in the coexistence atmosphere of reducing gas and inert gas, and cooling to room temperature after calcining to obtain the fuel cell electrocatalyst Pt3M-N/C；
Wherein the metal phthalocyanine MPc, carbon black and H2PtCl6·6H2The mass ratio of O is 10: (24-30): (7-11).
Further, the ratio of the metal phthalocyanine MPc and the organic solvent a was 10 mg: 50 mL; the reaction is carried out for 1-2 h under the ultrasonic condition of 600w and 40 KHZ.
Further, the organic solvent A is absolute ethyl alcohol.
Further, the heating temperature of the organic solvent A during evaporation is 35-45 ℃; and drying the slurry at 60-80 ℃.
Further, the reducing gas is H accounting for 10 percent of the total volume of the atmosphere2The inert gas is N accounting for 90 percent of the total volume of the atmosphere2。
Further, before calcination, the powder product is subjected to heat preservation for 0.5-2 hours at the temperature of 150-200 ℃ for pre-sintering, and then is subjected to heat preservation for 0.5-2 hours at the temperature of 800-1000 ℃ for calcination, wherein the heating rate is 5 ℃/min.
Further, the preparation steps of the metal phthalocyanine MPc comprise: adding a transition metal salt and a ligand into an organic solvent B, uniformly dispersing, adding a catalyst, and heating at 180-200 ℃ for 15-30 min to obtain an intermediate product; cooling the intermediate product to room temperature, filtering, washing and drying to obtain a solid; finally, adding a hydrochloric acid solution into the solid, stirring for 2-4 h at 60-80 ℃, filtering and washing until the filtrate is neutral, and drying to obtain metal phthalocyanine MPC; wherein the molar ratio of the transition metal salt to the ligand is 1: (3-4).
Further, transition metalsThe salt being CoCl2、FeCl3Or Ni (NO)3)2(ii) a The ligand is phthalic nitrile; the organic solvent B is ethylene glycol; the catalyst was DBU.
Further, the proportion of the added catalyst to the transition metal salt is (2-4) mL:1 g; the mass concentration of the added hydrochloric acid solution is 2%, and the ratio of the added hydrochloric acid solution to the transition metal salt is (80-120) mL:1 g.
Fuel cell electrocatalyst Pt prepared by the preparation method described above3M-N/C。
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares Pt by taking metal phthalocyanine MPc as a template3The Co-N/C catalyst improves the electrochemical activity and obviously reduces the dosage of Pt. Compared with the traditional preparation method, the Pt loading capacity of the catalyst prepared by the method is lower, reaches 6.9-11% of low loading capacity, and effectively reduces the cost; meanwhile, because the metal phthalocyanine MPc contains nitrogen, MN is generated after reaction4Pt and MN4The catalyst has more excellent oxygen reduction catalytic activity due to the synergistic effect of the sites, the half-wave potential reaches 810-850 mV, the half-wave potential can be improved by 70mV at most relative to 40% of commercial platinum carbon, and the electrochemical performance is more excellent; constant potential test shows that the catalyst obtained by the invention has better cycle stability.
Furthermore, the method for synthesizing the metal phthalocyanine MPc template has simple steps and cheap raw materials, and is beneficial to reducing the cost.
Drawings
FIG. 1 is a graph showing oxygen reduction performance test of a catalyst obtained in one example of the present invention and a commercial platinum-carbon catalyst;
FIG. 2 is a graph showing stability tests of a catalyst obtained in accordance with one embodiment of the present invention and a commercial platinum-carbon catalyst;
FIG. 3 shows two different embodiments H of the present invention2PtCl6·6H2And O addition amount is obtained as an oxygen reduction performance test chart of the catalyst.
FIG. 4 is a graph showing the oxygen reduction performance of catalysts obtained from three different solvents according to the example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and the detailed description. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The preparation method comprises the following steps:
(1) preparing a metal phthalocyanine MPC template: metal phthalocyanine is obtained by coordination of metal salt as metal source, phthalodinitrile as ligand and metal source, DBU as catalyst to accelerate reaction rate, and CoCl is used as catalyst2For example, the specific steps are as follows:
adding metal salt CoCl2And phthalic nitrile are added into a round-bottom flask filled with 100mL of ethylene glycol according to the molar ratio of 1 (3-4), ultrasonic treatment is carried out for 15-30 minutes to enable the phthalic nitrile and the ethylene glycol to be uniformly dispersed, and 2-4 mL of 1, 8-diazabicyclo [5.4.0 ] is added]Undec-7-ene (DBU) and then heating for 15-30 min at 180-200 ℃ in a microwave reactor. The solution turned dark green, cooled to room temperature, filtered, rinsed with methanol and dried. And adding a hydrochloric acid solution with the mass fraction of 2% into the obtained solid, stirring for 2-4 h at the temperature of 60-80 ℃, filtering, washing with deionized water until the filtrate is neutral, and drying to obtain cobalt phthalocyanine CoPc.
(2) In a 100mL flask, 24-30 mg of carbon black EC-600 and 7-11 mg of H are added per 10mg of CoPc2PtCl6·6H2Performing ultrasonic treatment on O and 50mL of absolute ethyl alcohol for 1-2 h under the conditions of 600w and 40KHZ, heating the obtained suspension under magnetic stirring at 35-45 ℃ until the solvent is slowly evaporated to form smooth and thick slurry, and generally reducing the volume of the slurry to below 1/25 of the original volume of the suspension; and drying the slurry in an oven at the temperature of 60-80 ℃. After grinding in an agate mortar, the resulting black powder was placed in a tube furnace at 10% H2/90％N2Heating to 150-200 ℃ at a speed of 5 ℃/min under the atmosphere, preserving heat for 0.5-2 hours, heating to 800-1000 ℃ at a speed of 5 ℃/min, preserving heat for 0.5-2 hours, and naturally cooling to room temperature to obtain Pt3Co-N/C。
Metal salt in step (1)Can also be replaced by FeCl3Or Ni (NO)3)2The preparation steps are not changed.
In the step (2), the evaporation temperature is not high enough, and too fast evaporation causes uneven solvent removal, so that smooth slurry cannot be formed, and the performance of the final product is influenced.
The present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments.
Example one
(1) 1g of CoCl2And 3.94g of phthalodinitrile (molar ratio about 1:4) were added to a round-bottomed flask containing 100mL of ethylene glycol, sonicated for 15 minutes to disperse uniformly into ethylene glycol, and 3mL of 1, 8-diazabicyclo [5.4.0 ] was added]Undec-7-ene (DBU), then heated in a microwave reactor at 180 ℃ for 15 min. The solution turned dark green, cooled to room temperature, filtered, rinsed with methanol and dried. And adding 100mL of 2% hydrochloric acid solution into the obtained solid, stirring for 2h at 60 ℃, filtering, washing with deionized water until the filtrate is neutral, and drying to obtain CoPc.
(2) A100 mL flask was charged with 10mg CoPc, 24mg EC-600, 9mg H2PtCl6·6H2O and 50mL of absolute ethyl alcohol, and ultrasonic treatment is carried out for 1h, the suspension is heated at 40 ℃ under magnetic stirring until the solvent is evaporated and a smooth and thick slurry is formed, and the slurry is dried in an oven at 60 ℃. After grinding in an agate mortar, the black powder obtained was placed in a tube furnace in H2/N2Heating to 200 ℃ at the speed of 5 ℃/min under the atmosphere, preserving heat for 2 hours, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for two hours, and naturally cooling to room temperature to obtain Pt3Co-N/C。
By ICP testing, Pt obtained in this example3The Pt loading in Co-N/C was 9% and the commercial JC 40% Pt/C was 40%.
At a voltage range of 0-1.2V (vs. RHE), at saturation O2、0.1mol/LHClO4The catalyst Pt obtained in the example3The LSV tests were conducted on Co-N/C and commercial JC 40% Pt/C, the results of which are shown in FIG. 1, wherein the catalyst Pt obtained in the first example is3The half-wave potential of Co-N/C is higher than JC 40% Pt/C70 mvLeft and right.
Specifically, the catalyst Pt obtained in example one3The half-wave potential of Co-N/C is about 850 mV; the half-wave potential of commercial JC 40% Pt/C is about 780 mV.
As can be seen from the tests, in the first embodiment of the present invention, Pt3The Pt loading of the Co-N/C catalyst is 9 percent and is far lower than 40 percent of commercial platinum carbon, but the electrochemical performance of the catalyst is obviously better than JC 40 percent Pt/C, because the phthalic nitrile contains nitrogen in the invention, the prepared cobalt phthalocyanine is used as a template to prepare the electrocatalyst, and the obtained electrocatalyst contains CoN4Sites, Pt and CoN4The synergistic effect between the sites enables the catalyst to have more excellent oxygen reduction catalytic activity.
At the same time, Pt is compared by a constant potential method3Stability of Co-N/C with JC 40% Pt/C. In particular, HClO at 0.1mol/L filled with oxygen4In the solution, 0.6V (vs RHE) was used as a constant potential, and the change of current density with time at this potential was measured, and the results are shown in FIG. 2. As can be seen from FIG. 2, Pt was measured after the potentiostatic test for 50000 seconds3The current density of Co-N/C was reduced by 3.1%, while that of JC 40% Pt/C was reduced by 43%. From this data, it can be found that Pt3The cycling stability of Co-N/C is far beyond JC 40% Pt/C. This also indicates that the addition of N is advantageous for improving the stability of the catalyst.
Example 2: investigating different quantities of H2PtCl6·6H2Effect of O on the Performance of the resulting catalyst
5mg, 7mg, 11mg and 15mg of H were added respectively2PtCl6·6H2O, other conditions were the same as in example 1.
ICP test was carried out on the obtained catalyst to obtain Pt3The Pt loadings in Co-N/C were 5%, 6.9%, 10.31% and 13.67%, respectively.
The LSV test was carried out on the catalyst obtained under the same test conditions as in example one, and the results are shown in FIG. 3. The half-wave potential of the catalyst obtained when 5mg was added was less than 800mV, the half-wave potential was around 810mV when 7mg and 15mg were added, and around 830mV when 15mg was added, which was slightly less than 7mg, and 11mg was added.
From the above results, H is2PtCl6·6H2When the amount of O added is too small, the structure of the catalyst may not be formed, and thus the catalyst performance is poor. When H is present2PtCl6·6H2When O is added excessively, complete loading cannot be achieved, the performance of the resulting catalyst is not particularly good, and the cost is increased much, so that H in the present invention2PtCl6·6H2The dosage of O is selected from 7-11 mg, preferably 9 mg.
Example 3
The effect of different solvents on the resulting catalyst was investigated.
The solvent used in the second reaction was changed to methanol and water, and the catalyst obtained was tested under the same conditions as in example 1, and the results are shown in FIG. 4.
When the solvent adopts water, the half-wave potential of the obtained catalyst is obviously lower than 800mV, and when the solvent is methanol, the half-wave potential of the obtained catalyst is about 800mV and is lower than that of the catalyst in the first embodiment.
From the above results, it is understood that when water is used as a solvent, the oxygen reduction performance of the catalyst is poor. The catalyst performance obtained by using ethanol as the solvent is the best, and ethanol is used as the solvent in the second step of the method.
Meanwhile, the glycol is more suitable for the preparation of the liquid phase catalyst due to high boiling point and is not suitable for the impregnation method.
Example four
(1) 1g of CoCl2And 2.96g of phthalodinitrile (molar ratio about 1:3) were added to a round-bottomed flask containing 100mL of ethylene glycol, sonicated for 30 minutes to disperse uniformly into ethylene glycol, and 2mL of 1, 8-diazabicyclo [5.4.0 ] was added]Undec-7-ene (DBU), then heated in a microwave reactor at 200 ℃ for 20 min. The solution turned dark green, cooled to room temperature, filtered, rinsed with methanol and dried. And adding 80mL of 2% hydrochloric acid solution into the obtained solid, stirring for 4h at 70 ℃, filtering, washing with deionized water until the filtrate is neutral, and drying to obtain CoPc.
(2) A100 mL flask was charged with 10mg CoPc, 27mg EC-600, and 9mg H2PtCl6·6H2O and 50mL of absolute ethyl alcohol, and ultrasonic treatment is carried out for 1.5h, the suspension is heated at 35 ℃ under magnetic stirring until the solvent is evaporated and a smooth and thick slurry is formed, and the slurry is dried in an oven at 70 ℃. After grinding in an agate mortar, the black powder obtained was placed in a tube furnace in H2/N2Heating to 150 ℃ at the speed of 5 ℃/min under the atmosphere, preserving heat for 1 hour, heating to 1000 ℃ at the speed of 5 ℃/min, preserving heat for 0.5 hour, and naturally cooling to room temperature to obtain Pt3Co-N/C。
The Pt obtained in this example was subjected to ICP and LSV tests3The Pt loading in Co-N/C was 8.7% and the half-wave potential was 820 mV.
EXAMPLE five
(1) 1g of CoCl2And 3.45g of phthalodinitrile (molar ratio about 1:3.5) were added to a round-bottomed flask containing 100mL of ethylene glycol, sonicated for 20 minutes to disperse uniformly into ethylene glycol, and 4mL of 1, 8-diazabicyclo [5.4.0 ] was added]Undec-7-ene (DBU), then heated in a microwave reactor at 190 ℃ for 30 min. The solution turned dark green, cooled to room temperature, filtered, rinsed with methanol and dried. And adding 120mL of 2% hydrochloric acid solution into the obtained solid, stirring for 2.5h at 80 ℃, filtering, washing with deionized water until the filtrate is neutral, and drying to obtain CoPc.
(2) A100 mL flask was charged with 10mg CoPc, 30mg EC-600, 9mg H2PtCl6·6H2O and 50mL of absolute ethyl alcohol, and ultrasonic treatment is carried out for 2h, the suspension is heated at 45 ℃ under magnetic stirring until the solvent is evaporated and a smooth and thick slurry is formed, and the slurry is dried in an oven at 80 ℃. After grinding in an agate mortar, the black powder obtained was placed in a tube furnace in H2/N2Heating to 180 ℃ at the speed of 5 ℃/min under the atmosphere, preserving heat for 0.5 hour, then heating to 900 ℃ at the speed of 5 ℃/min, preserving heat for 1 hour, and then naturally cooling to room temperature to obtain Pt3Co-N/C。
The Pt obtained in this example was subjected to ICP and LSV tests3The Pt loading in Co-N/C was 8.78% and the half-wave potential was 824 mV.
EXAMPLE six
Adding CoCl2By substitution of FeCl3And Ni (NO)3)2Otherwise, as in example one, the catalyst obtained was tested to have Pt loading of 8.15% and 8.34%, respectively, and half-wave potentials of 826mV and 819mV, which are close to the catalytic activity of example four.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. Fuel cell electrocatalyst Pt3The preparation method of M-N/C is characterized by comprising the following steps: the method comprises the following steps: firstly, taking metal phthalocyanine MPc, carbon black and H2PtCl6·6H2Uniformly mixing O and an organic solvent A, reacting for 1-2 h, and heating and stirring until the organic solvent A is evaporated to form slurry; drying the slurry, and grinding to obtain a powdery product; and finally, calcining the powdery product at 800-1000 ℃ in the coexistence atmosphere of reducing gas and inert gas, and cooling to room temperature after calcining to obtain the fuel cell electrocatalyst Pt3M-N/C；
Wherein the metal phthalocyanine MPc, carbon black and H2PtCl6·6H2The mass ratio of O is 10: (24-30): (7-11).
2. A fuel cell electrocatalyst, Pt, according to claim 13The preparation method of M-N/C is characterized by comprising the following steps: the ratio of the metal phthalocyanine MPc to the organic solvent a is 10 mg: 50 mL; the reaction is carried out for 1-2 h under the ultrasonic condition of 600w and 40 KHZ.
3. A fuel cell electrocatalyst, Pt, according to claim 13The preparation method of M-N/C is characterized by comprising the following steps: the organic solvent A is absolute ethyl alcohol.
4. A fuel cell electrocatalyst, Pt, according to claim 13The preparation method of M-N/C is characterized by comprising the following steps: addition of organic solvent A on evaporationThe heat temperature is 35-45 ℃; and drying the slurry at 60-80 ℃.
5. A fuel cell electrocatalyst, Pt, according to claim 13The preparation method of M-N/C is characterized by comprising the following steps: the reducing gas is H accounting for 10 percent of the total volume of the atmosphere2The inert gas is N accounting for 90 percent of the total volume of the atmosphere2。
6. A fuel cell electrocatalyst, Pt, according to claim 13The preparation method of M-N/C is characterized by comprising the following steps: before calcination, the powder product is subjected to pre-sintering by heat preservation for 0.5-2 hours at 150-200 ℃, and then is subjected to calcination by heat preservation for 0.5-2 hours at 800-1000 ℃, wherein the heating rate is 5 ℃/min.
7. A fuel cell electrocatalyst, Pt, according to claim 13The preparation method of M-N/C is characterized by comprising the following steps: the preparation method of the metal phthalocyanine MPc comprises the following steps: adding a transition metal salt and a ligand into an organic solvent B, uniformly dispersing, adding a catalyst, and heating at 180-200 ℃ for 15-30 min to obtain an intermediate product; cooling the intermediate product to room temperature, filtering, washing and drying to obtain a solid; finally, adding a hydrochloric acid solution into the solid, stirring for 2-4 h at 60-80 ℃, filtering and washing until the filtrate is neutral, and drying to obtain metal phthalocyanine MPC; wherein the molar ratio of the transition metal salt to the ligand is 1: (3-4).
8. A fuel cell electrocatalyst Pt according to claim 73The preparation method of M-N/C is characterized by comprising the following steps: the transition metal salt is CoCl2、FeCl3Or Ni (NO)3)2(ii) a The ligand is phthalic nitrile; the organic solvent B is ethylene glycol; the catalyst was DBU.
9. A fuel cell electrocatalyst Pt according to claim 73The preparation method of M-N/C is characterized by comprising the following steps: the proportion of the added catalyst to the transition metal salt is (2-4) mL:1 g; adding hydrochloric acid for dissolvingThe mass concentration of the liquid is 2% and the ratio of the liquid to the transition metal salt is (80-120) mL:1 g.
10. Fuel cell electrocatalyst Pt prepared according to the preparation method of any one of claims 1 to 93M-N/C。
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