CN108923050B - Core-shell carbon nanostructure electrocatalyst with high catalytic performance and preparation method thereof - Google Patents

Core-shell carbon nanostructure electrocatalyst with high catalytic performance and preparation method thereof Download PDF

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CN108923050B
CN108923050B CN201810724471.5A CN201810724471A CN108923050B CN 108923050 B CN108923050 B CN 108923050B CN 201810724471 A CN201810724471 A CN 201810724471A CN 108923050 B CN108923050 B CN 108923050B
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陈胜利
张世明
张鹤友
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    • H—ELECTRICITY
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Abstract

The invention discloses a core-shell carbon nano-structure electrocatalyst with high catalytic performance and a preparation method thereof. Fe-N with edge structure closed poly-iron phthalocyanine as shell, conductive carbon as core and iron phthalocyanine unit4The central structure is its active site. The preparation method comprises the following steps: 1) adding conductive carbon into a mixed solution of pyromellitic dianhydride and phthalic anhydride, and drying to obtain powder A; 2) and uniformly mixing the powder A with an iron compound, ammonium molybdate and urea to obtain powder B, heating the powder B to be molten liquid, carrying out microwave reaction to carry out in-situ polymerization reaction, washing and drying to obtain the core-shell carbon nano-structure electrocatalyst with high catalytic performance. The novel core-shell carbon catalyst has high oxygen reduction catalytic activity, excellent cycle stability and excellent CH which are obviously superior to those of commercial Pt/C catalysts3OH/CO tolerance; the raw materials used for synthesizing the catalyst are all market-mature products, the cost is low, the preparation process is simple and feasible, and the method is suitable for commercial large-scale production.

Description

Core-shell carbon nanostructure electrocatalyst with high catalytic performance and preparation method thereof
Technical Field
The invention belongs to the field of fuel cells, and relates to a core-shell carbon nanostructure electrocatalyst for a fuel cell cathode and a preparation method thereof.
Background
Energy crisis and environmental deterioration are major problems facing the development of today's human society. The fuel cell has the characteristics of abundant fuel hydrogen resources, high specific energy, no pollution in emission and the like, and is considered as one of main power supply devices for solving the future energy problem. For many years, the key to the scaling of fuel cells has been their high cost. It is exciting that japan realized the breakthrough of fuel cell technology in the near term, and the cost thereof is greatly reduced, and Toyota company introduced Mirai fuel cell automobile mass production marketing plan in 2014, which has brought a new development era for the commercial popularization of fuel cells.
Nevertheless, the limited resource of the noble metal Pt and the slow kinetics of the oxygen electrode, etc., remain difficult and challenging to commercialize fuel cells. Therefore, the design development of low-Pt catalyst with low cost and high performance and even brand-new non-noble metal catalyst needs to be realized. A large number of studies have shown that Fe-NxThe catalytic performance of carbon-doped catalysts has shown great Pt-substituting potential, Fe-N4The structure is a strong active center. Based on this, we chose to have a definite Fe-N4The iron phthalocyanine compound with the structure is designed and developed into an iron phthalocyanine @ carbon black core-shell carbon catalyst (CN201310218713.0) with high catalytic performance. However, in subsequent engineering application research, the problem that the performance of the assembled battery cannot be well exerted and the problem of poor cycle stability greatly restricts the industrialization process is found, which is the technical key to be urgently broken through of the catalyst.
Disclosure of Invention
Aiming at the problems and the defects, the invention constructs the c-pFePC @ CB core-shell carbon nano-structure electrocatalyst by polymerizing the conductive carbon surface to form a poly-iron phthalocyanine thin shell with stable structure and closed edge groups, so as to improve the cycle stability of the carbon catalyst, enhance the intrinsic activity of active sites and the carbon catalyst and improve the performance of the fuel cell.
The invention can be realized by the following technical scheme:
a preparation method of a core-shell carbon nano-structure electrocatalyst with high catalytic performance comprises the following steps:
1) dissolving pyromellitic dianhydride and phthalic anhydride in a solvent, adding conductive carbon, performing ultrasonic dispersion to obtain a uniformly mixed suspension, and drying to obtain powder A;
2) uniformly mixing the powder A with an iron compound, ammonium molybdate and urea to obtain powder B, heating the powder B to obtain molten liquid, transferring the molten liquid into a microwave reactor to perform in-situ polymerization reaction, polymerizing around conductive carbon to form a poly-phthalocyanine iron shell layer with an enclosed edge structure, and washing and drying to obtain the core-shell carbon nano-structure electrocatalyst.
Preferably, in step 1), the solvent is one or a mixture of ethanol, acetone, dimethyl sulfoxide, dimethylformamide and water.
Preferably, in step 1), the conductive carbon has a specific surface area of more than 200m2One or more of spherical, linear, flaky or blocky carbon materials per gram.
Preferably, the spherical carbon material comprises one or more of EC600JD, EC300J, Vulcan XC72, BP2000, etc., the linear carbon material comprises one or more of carbon nanotubes, carbon fibers, carbon nanorods, etc., and the sheet/bulk carbon material comprises one or more of graphene, nanobelts, activated carbon, etc.
Preferably, in step 2), the heating temperature is not lower than 120 ℃ to obtain the molten liquid.
Preferably, in step 2), the microwave power is not lower than 100W, so that in-situ polymerization reaction occurs in the melt.
Preferably, in step 2), the iron ion in the iron compound has a valence of +2 and/or + 3.
Preferably, the + 2-valent iron compound includes one or more of ferrous sulfate, ferrous ammonium sulfate, ferrous chloride, ferrous nitrate, ferric oxalate, ferric phthalocyanine, ferrous oxide and the like, and the + 3-valent iron compound includes one or more of ferric sulfate, ferric trichloride, ferric nitrate, ferric acetate, ferric acetylacetonate, ferriporphyrin, ferric oxide and the like.
Preferably, the mass ratio of the pyromellitic dianhydride to the conductive carbon is 0.01-1: 1; the mass ratio of phthalic anhydride to conductive carbon is 0.2-2: 1; the mass ratio of the iron compound to the conductive carbon is 0.2-1: 1; the mass ratio of the ammonium molybdate to the conductive carbon is 0.5-5: 1; the mass ratio of the urea to the conductive carbon is 0.2-10: 1.
preferably, the prepared core-shell carbon nanostructure electrocatalyst can be subjected to post-treatment such as acid washing, secondary high temperature treatment, pore forming and the like, and the post-treatment does not change the form of the catalyst.
The invention also provides a core-shell carbon nano-structure electrocatalyst with high catalytic performance, wherein the shell is a thin layer of poly-iron phthalocyanine, and the core is conductive carbon, and the electrocatalyst is prepared by the method.
Preferably, the mass ratio of the poly-iron phthalocyanine shell to the conductive carbon core is 0.1-10: 1.
In the catalyst, the shell is a thin layer of poly-iron phthalocyanine, the edge structure is closed, and the core is conductive carbon.
In the catalyst, the Fe-N of the poly-iron phthalocyanine4The structure is an active site.
In the catalyst prepared by the invention, the atomic percentage of Fe is 0-2 at%, but not 0; fe exists mainly in a +2 valence form and is coupled with N to form Fe-N4And (5) structure. The atomic percentage of N is 0-16 at%, but not 0; n mainly exists in the forms of pyridine N, pyrrole N and other species.
Compared with the prior art, the invention has the following characteristics:
1) the shell layer of the constructed core-shell carbon nano-structure electrocatalyst has high-density Fe-N4The active sites are completely exposed on the surface layer of the catalyst, so that the utilization rate of the active sites is greatly improved.
2) The structural stability of the poly-iron phthalocyanine is greatly improved through a regulation and control mode of 'edge group closure'. On one hand, the circulation stability of the carbon catalyst is improved; on the other hand, the intrinsic activity of the active sites and the carbon catalyst is enhanced.
3) The core-shell carbon nano-structure electrocatalyst has high oxygen reduction catalytic activity, is equivalent to the activity of a commercialized 60 wt% Pt/C catalyst, and is obviously better than the performance of a commercialized 20 wt% Pt/C catalyst.
4) Compared with the carbon-based catalyst reported in the current research, the catalytic activity of the core-shell carbon nano-structured electrocatalyst has remarkable advantages.
5) The performance of the fuel cell assembled by the catalyst of the invention is comparable to 60 wt% Pt/C catalyst, and is superior to the reported carbon-based catalyst.
Drawings
The invention is further illustrated by means of the attached drawings, the examples of which are not to be construed as limiting the invention in any way.
FIG. 1 is a scheme showing the synthesis of edge-blocked iron (c-pFepc @ CB) phthalocyanine prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the c-pFepc @ CB carbon catalyst prepared in example 1;
FIG. 3 is an oxygen reduction polarization curve of the prepared C-pFePC @ CB carbon catalyst versus commercial 20 wt% Pt/C and 60 wt% Pt/C catalysts in a 0.1M KOH electrolyte;
FIG. 4 is an oxygen reduction polarization curve of the c-pFePC @ CB carbon catalyst prepared in example 1 before and after 1000 cycles of potential range scanning at 0.02-1.22V (vs. RHE);
FIG. 5 is a graph showing performance tests of C-pFePC @ CB prepared in example 1 and commercial 60 wt% Pt/C as assembled single cells of a fuel cell cathode catalyst, respectively.
Detailed Description
In order that the invention may be better understood, the invention will now be further described with reference to the following examples.
Example 1
1) Preparation of c-pFePC @ CB core-shell carbon nanostructure electrocatalyst
Respectively weighing solid powder of pyromellitic dianhydride and phthalic anhydride, dissolving the solid powder in an acetone solvent, adding a certain mass of EC300J conductive carbon, performing ultrasonic dispersion to obtain a uniformly mixed suspension, and drying to obtain precursor powder. Further, uniformly mixing the precursor powder with ferrous sulfate, ammonium molybdate and urea, heating the mixture to form a molten liquid, quickly transferring the molten liquid into a microwave reactor to enable the molten liquid to generate an in-situ polymerization reaction, and polymerizing the molten liquid around conductive carbon to form a poly-phthalocyanine iron shell layer with an enclosed edge structure, thereby obtaining the c-pFePC @ CB core-shell carbon nano-structure electrocatalyst.
Wherein the mass ratio of pyromellitic dianhydride to conductive carbon is 0.01-1: 1; the mass ratio of phthalic anhydride to conductive carbon is 0.2-2: 1; the mass ratio of the iron compound to the conductive carbon is 0.2-1: 1; the mass ratio of ammonium molybdate to conductive carbon is 0.5-5: 1; the mass ratio of the urea to the conductive carbon is 0.2-10: 1.
the synthetic route of the edge structure closed type poly-iron phthalocyanine is shown in figure 1, and the TEM for preparing the core-shell carbon nano-structure electrocatalyst is shown in figure 2.
2) Structural composition analysis of electrocatalyst
The structural composition of the prepared c-pFePC @ CB core-shell carbon nanostructure electrocatalyst is deeply analyzed by combining a plurality of characterization technologies:
Figure BDA0001719391200000041
the test pattern shows that c-pFePC @ CB shows the same bimodal feature as FePc, and the result shows that the c-pFePC has Fe-N consistent with the FePc4And (5) structure. The XPS result shows that the content of Fe and N on the surface of the c-pFePC @ CB catalyst is respectively 8.08at percent and 0.93at percent, and the ratio of the Fe content to the N content is very close to the theoretical ratio of poly-iron phthalocyanine molecules, namely 8: 1, and the fine spectrum result of N1s shows that the N element exists in the form of pyridine N and pyrrole N, and the ratio of the pyridine N to the pyrrole N is 2.97: 1 is very close to 3 in the molecular unit of iron phthalocyanine: 1. in addition, the infrared spectrum curves of c-pFePC and FePc are further compared, and the results show that the characteristic peak positions of the c-pFePC and the FePc are the same, but the peak intensity of the c-pFePC is obviously improved.
3) Electrochemical performance test analysis of electrocatalyst
Respectively weighing a certain mass of C-pFePC @ CB carbon catalyst and a commercial Pt/C catalyst, uniformly dispersing the C-pFePC @ CB carbon catalyst and the commercial Pt/C catalyst in an isopropanol solution of Nafion to obtain catalyst ink, dripping a certain volume of the catalyst ink on the surface of the glassy carbon electrode, and fully drying to prepare the working electrode. And (3) testing the electrochemical performance of the prepared working electrode by adopting a three-electrode system at room temperature: the platinum sheet is a counter electrode, the mercury/mercury oxide is a reference electrode, and 0.1M KOH is electrolyte.
The oxygen reduction reaction test was carried out in an oxygen-saturated electrolyte at an electrode speed of 1600rpm and a potential sweep rate of 5 mV/s. The results show that C-pFepc @ CB exhibits superior catalytic activity to commercial Pt/C, as can be seen from the polarization curve shown in FIG. 3: at the same catalyst loading, the C-pFePC @ CB half-wave potential is shifted by about 10mV more positively than the commercial 60 wt% Pt/C and by about 50mV more positively than the commercial 20 wt% Pt/C.
In addition, the prepared c-pFePC @ CB carbon catalyst was subjected to a methanol resistance test using a 0.1M KOH solution to which 0.1M methanol was added, and the other conditions were the same as those of the oxygen reduction reaction test. The results show that the polarization curves before and after the addition of 0.1M methanol are basically coincident, i.e. the catalytic activity of c-pFePC @ CB is not attenuated, which indicates that the catalyst has very excellent methanol resistance.
Further, the cyclic stability performance of the c-pFePC @ CB carbon catalyst was tested. And (3) placing the prepared c-pFePC @ CB working electrode in 0.1M KOH electrolyte saturated by argon, and scanning in a full potential range of 0.02-1.22V (vs. RHE), wherein the potential scanning speed is 50 mV/s. After 1000 cycles of cyclic scanning, the carbon catalyst is placed in 0.1M KOH electrolyte saturated by oxygen for oxygen reduction reaction test, and the test result is shown in figure 4, so that the polarization curves before and after 1000 cycles of cyclic scanning are basically consistent, and the C-pFePC @ CB carbon catalyst has excellent cyclic stability, is not only superior to a commercial Pt/C catalyst, but also has better stability compared with a catalyst (CN201310218713.0) taking small-molecule iron phthalocyanine as a shell structure.
Next, a fuel cell was assembled using C-pFePC @ CB with a comparison of commercial 60 wt% Pt/C as the cathode catalyst and commercial 60 wt% Pt-Ru/C as the anode catalyst, respectively, and the results of the tests showed that C-pFePC @ CB had almost identical fuel cell performance to the commercial 60 wt% Pt/C, which was significantly superior to the catalyst (CN201310218713.0) having a shell structure of small molecule iron phthalocyanine (see FIG. 5).
The EC300J conductive carbon used in the present embodiment can be replaced by one or more of spherical conductive carbon such as EC600JD, Vulcan XC72, BP2000, etc., and one or more of linear carbon materials such as nanotubes, carbon fibers, carbon nanorods, etc., and sheet/bulk carbon materials such as graphene, nanobelts, activated carbon, etc., without affecting various properties of the resulting catalyst.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. A preparation method of a core-shell carbon nano-structure electrocatalyst with high catalytic performance is characterized by comprising the following steps:
1) dissolving pyromellitic dianhydride and phthalic anhydride in a solvent, adding conductive carbon, performing ultrasonic dispersion to obtain a uniformly mixed suspension, and drying to obtain powder A;
2) uniformly mixing the powder A with an iron compound, ammonium molybdate and urea to obtain powder B, heating the powder B to obtain a molten liquid, transferring the molten liquid into a microwave reactor to perform in-situ polymerization reaction, polymerizing the molten liquid around conductive carbon to form a poly-phthalocyanine iron shell layer with an enclosed edge structure, and washing and drying to obtain the core-shell carbon nano-structure electrocatalyst, wherein the mass ratio of pyromellitic dianhydride to conductive carbon is (0.01-1): 1; the mass ratio of phthalic anhydride to conductive carbon is 0.2-2: 1.
2. the preparation method according to claim 1, wherein in step 1), the solvent is one or more of ethanol, acetone, dimethyl sulfoxide, dimethylformamide and water.
3. The method according to claim 1, wherein the conductive carbon has a specific surface area of more than 200m in step 1)2One or more of spherical, linear, flaky or blocky carbon materials per gram.
4. The method according to claim 1, wherein the heating temperature in step 2) is not lower than 120 ℃ to obtain the melt.
5. The method according to claim 1, wherein the microwave power in step 2) is not less than 100W, so that the in-situ polymerization reaction occurs in the melt.
6. The method according to claim 1, wherein in the step 2), the iron ion in the iron compound has a + 2-valent state and/or a + 3-valent state.
7. The preparation method according to claim 1, wherein the mass ratio of the iron compound to the conductive carbon is 0.2-1: 1; the mass ratio of the ammonium molybdate to the conductive carbon is 0.5-5: 1; the mass ratio of the urea to the conductive carbon is 0.2-10: 1.
8. a core-shell carbon nanostructure electrocatalyst with high catalytic performance is characterized by being prepared by the method of any one of claims 1 to 7, wherein the shell is an edge-closed poly-iron phthalocyanine layer, and the core is conductive carbon.
9. The high-catalytic-performance core-shell carbon nanostructure electrocatalyst is characterized in that the mass ratio of the iron phthalocyanine poly shell to the conductive carbon core is 0.1-10: 1.
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CN109273725A (en) * 2018-08-17 2019-01-25 上海中聚佳华电池科技有限公司 Poly- metal phthalocyanine composition, Its Preparation Method And Use
CN109387508B (en) * 2018-11-18 2021-06-04 扬州大学 Preparation method of magnetic carbon tube-molybdenum disulfide nanoenzyme and method for detecting hydrogen peroxide and glucose by using magnetic carbon tube-molybdenum disulfide nanoenzyme
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CN114427104B (en) * 2021-12-13 2023-03-21 深圳先进技术研究院 Copper phthalocyanine polymer @ copper nanowire core-shell nano material as well as preparation method and application thereof
CN114899436A (en) * 2022-06-06 2022-08-12 山东能源集团有限公司 Phthalocyanine-like polymer carbonization-derived Fe/N/C oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell

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