CN112736258A - Preparation method based on intramolecular or intermolecular asymmetric organic molecular electrocatalyst and application of electrocatalyst in zinc-air battery - Google Patents

Preparation method based on intramolecular or intermolecular asymmetric organic molecular electrocatalyst and application of electrocatalyst in zinc-air battery Download PDF

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CN112736258A
CN112736258A CN202011558627.0A CN202011558627A CN112736258A CN 112736258 A CN112736258 A CN 112736258A CN 202011558627 A CN202011558627 A CN 202011558627A CN 112736258 A CN112736258 A CN 112736258A
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龙晓静
王彬彬
王美龙
宋伟琛
赵子杰
张乾坤
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Abstract

The invention relates to the field of oxygen reduction electrocatalysts, in particular to a preparation method of an electrocatalyst based on intramolecular or intermolecular asymmetric organic molecules and application of the electrocatalyst in a zinc-air battery. The asymmetric organic molecule oxygen reduction electrocatalyst is prepared, the structure of the asymmetric organic molecule is adjustable, the active site is controllable, and the problem that the recognition of a heteroatom/defect catalytic center and the active site is not clear due to the fact that the exact molecular structure cannot be accurately synthesized by a conventional carbonization or doping method can be effectively solved. The asymmetric molecular structure is helpful for breaking the integrity of a pi conjugated system, so that electrons on a conjugated framework are redistributed in a large area, and the catalytic activity and the number of active sites of the material are further influenced. By adjusting the degree of asymmetry of the organic molecules, the invention obviously increases the catalytic activity of the oxygen reduction electrocatalyst under the alkaline condition compared with the corresponding symmetric organic molecules, thereby providing a new thought for disclosing the catalytic action mechanism research of the asymmetric heterocyclic organic molecules.

Description

Preparation method based on intramolecular or intermolecular asymmetric organic molecular electrocatalyst and application of electrocatalyst in zinc-air battery
Technical Field
The invention relates to the technical field of oxygen reduction electrocatalysts, in particular to a preparation method of an intramolecular or intermolecular asymmetric organic molecular electrocatalyst and application of the intramolecular or intermolecular asymmetric organic molecular electrocatalyst in a zinc-air battery.
Background
Energy and environment are important supports for human survival and development, and traditional fossil energy is always the main energy source of human society. With the rapid development of global economy and the continuous deepening of industrialization, the bottleneck of energy resources is increasingly prominent, and the environmental constraint is also increased. Therefore, the development of new energy with high efficiency, no pollution, good stability and reproducibility becomes an important direction for the development of future energy. In recent years, among various energy conversion technologies, a fuel cell, as a device for converting chemical energy into electric energy, provides a new idea for solving the bottleneck problem of energy resources. The efficiency of the cathode Oxygen Reduction Reaction (ORR) determines the performance of the overall fuel cell. Oxygen reduction electrocatalysts are one of their key materials. As a substitute for noble metal platinum (Pt) catalysts, non-metallic carbon materials exhibit excellent ORR performance due to the advantages of abundant sources, low cost and the like, and have attracted great attention of researchers at home and abroad in recent years.
Researchers use various carbon material systems, various non-metal heteroatom dopants and carbonization modes in different temperature ranges to develop a non-metal carbon-oxygen reduction electrocatalyst with high catalytic efficiency through strategies such as chemical doping, defect induction and the like, and on one hand, the regulation and control modes are simple and effective methods for realizing carbon material functionalization; on the other hand, the uncertainty of the active site caused by chemical doping and defect induction methods in the material preparation process and the limitation of the uncontrollable active site on the research of the catalytic reaction mechanism are reflected. Although researchers have conducted a great deal of research on the catalytic activity, the catalytic activity sites cannot be precisely synthesized and regulated, and a material system with high catalytic activity cannot be further accurately designed. Therefore, the electronic structure of the carbon material is changed by adopting an asymmetric strategy, the distribution balance of charges is broken, the uniformly distributed charges are changed into localized aggregation, and the new activity is expressed, so that the method has important scientific significance and technical prospect for accelerating the development of the high-activity oxygen reduction electrocatalyst.
Disclosure of Invention
The invention provides a method for developing a non-metal, non-carbonized, adjustable-structure and controllable-active-site high-molecular catalytic material by adopting an asymmetric molecular strategy to controllably adjust charge distribution and design catalytic active sites. By designing two types of structural units with intramolecular asymmetry and intermolecular asymmetry, the heterocyclic organic molecular oxygen reduction electrocatalyst with an asymmetric structure is constructed by taking the structural units as core units.
In order to solve the above technical problem, the technical solution of the present application specifically includes the following two aspects:
1. based on the intramolecular structural asymmetry: fixing a phenyl structure, and respectively combining with non-phenyl heterocyclic structures such as thiophene, selenophene, pyridine, pyrazine and the like; or fixing thiophene structure, combining with non-thiophene heterocyclic structure such as selenophene, pyridine, pyrazine and the like, or introducing hetero atoms such as boron, nitrogen and the like into the symmetrical molecular structure to realize controllable development of the intramolecular asymmetrical structure.
2. Based on the structural asymmetry between molecules: connecting organic molecules with structural difference at one side of the symmetrical molecules; or two organic molecules with structural difference are respectively connected to two sides of the symmetrical molecules to realize the controllable development of the asymmetrical structure between the molecules. By controllable synthesis of the structure, the influence of the asymmetry of the heterocyclic structure and molecules on the catalytic performance is explored, and the micro-interface oxygen reduction reaction and the catalytic action mechanism of the asymmetric heterocyclic polymer are disclosed.
The method comprises the following specific steps:
a preparation method based on intramolecular or intermolecular asymmetric organic molecule electrocatalyst comprises the following specific steps:
carrying out ultrasonic treatment on an intramolecular asymmetric organic compound or an intermolecular asymmetric organic compound and a certain proportion of graphene in a solvent by using an ultrasonic probe until the organic compound or the intermolecular asymmetric organic compound and the graphene are fully mixed, and removing the solvent to obtain the electrocatalyst, wherein the mass ratio of the organic compound to the graphene is 100: 1-1: 100 (preferably 1: 1);
the intramolecular asymmetric organic compound is selected from one of the following compounds:
1. phenyl unit based small and high molecules:
Figure BDA0002858800080000021
2. thiophene unit based small and high molecules:
Figure BDA0002858800080000022
3. bipyridine unit-based small molecules and macromolecules:
Figure BDA0002858800080000023
Figure BDA0002858800080000031
wherein the content of the first and second substances,
Figure BDA0002858800080000032
Figure BDA0002858800080000033
Figure BDA0002858800080000034
R1＝CnH2n+1，n＝1～24；R2＝CmH2m+1m is 1-24, and m is not equal to n; x ═ B, P, N or Si; y ═ C or N;
R3＝F、
Figure BDA0002858800080000035
the intermolecular asymmetric organic compound is selected from one of the following compounds:
Figure BDA0002858800080000036
the symmetric molecule is:
Figure BDA0002858800080000041
in an organic compound which is not symmetrical between molecules,
Figure BDA0002858800080000042
are respectively selected from one of the following molecular formulas, and
Figure BDA0002858800080000043
and
Figure BDA0002858800080000044
the difference is as follows:
Figure BDA0002858800080000045
the above intermolecular asymmetric organic compounds and intramolecular asymmetric organic compounds can be either purchased directly or obtained by a common chemical synthesis method.
The following scheme for the synthesis of some compounds is exemplified:
1. small molecule/high molecule synthetic route with asymmetric intramolecular structure
A. Small and high molecules based on phenyl and thiophene units:
Figure BDA0002858800080000046
wherein
Figure BDA0002858800080000047
B. Bipyridine unit-based small molecules and macromolecules:
Figure BDA0002858800080000051
yamamoto reaction to obtain homopolymer polymer
Figure BDA0002858800080000052
Stille reaction to obtain the copolymer
Figure BDA0002858800080000053
Stille reaction to obtain the copolymer micromolecule
Figure BDA0002858800080000054
2. The synthesis route of micromolecules/macromolecules with asymmetric structures among molecules is as follows:
Figure BDA0002858800080000055
further, the solvent is dichloromethane, chloroform, n-hexane or tetrahydrofuran.
The invention also provides application of the electrocatalyst prepared by the preparation method in a zinc-air battery.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) compared with the noble metal and non-noble metal catalysts which are widely used at present, the catalyst developed by the invention is a non-metallic carbon material system, and can effectively avoid the problems of high cost, carbon monoxide poisoning, metal dissolution and low utilization rate.
(2) Compared with the commonly used methods of doping, defect and high-temperature carbonization at present, the method accurately designs the molecular structure from the molecular and atomic angles, can define the catalytic active site and effectively regulate the catalytic activity.
Conjugated polymers constructed with a single heterocycle, multiple heterocycles and fused heterocycles can precisely localize the catalytically active site using the exact molecular structure and their local structural differences. In addition, the intramolecular and intermolecular interaction and the strong dipole moment of the material can also promote the rapid transmission of electrons at the cathode, which is beneficial to the improvement of oxygen reduction activity;
compared with the traditional carbon catalytic material, the conjugated polymer has a determined energy level structure, and the reduction reaction is accelerated by establishing an extremely poor orbital energy level-electron transfer energy to transfer electrons to the LUMO energy level of oxygen;
(3) in general, oxygen-reduced heteroatom/defective carbon catalysts prepared by doping or carbonization exhibit high catalytic activity due to the break of self-charge distribution balance. The invention provides a non-metal, non-carbonized, adjustable-structure and active-site-controllable high-molecular catalytic material developed by adopting an asymmetric molecular strategy. By adjusting the degree of asymmetry, the controllability adjustment of charge distribution and the reasonable design of catalytic active sites are realized; the asymmetric molecular structure is beneficial to breaking the integrity of pi conjugated whole, changing the electronic structure of specific atoms of a molecular skeleton and destroying the original charge balance, thereby obviously improving the catalytic activity.
According to the application, the molecular structure, the electronic structure and the catalytic active site are associated together by utilizing the asymmetry of heterocyclic molecules and the controllable regulation of the heterocyclic structure, so that the deep analysis of the structure-activity relationship of the structure and the activity is realized, and a theoretical basis is provided for the development of a high-catalytic-activity material system.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound 2.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the polymer P-1B.
FIG. 3 is a nuclear magnetic hydrogen spectrum of Compound 4.
FIG. 4 is a nuclear magnetic hydrogen spectrum of Compound 5.
FIG. 5 is a nuclear magnetic hydrogen spectrum of Compound 6.
FIG. 6 is a nuclear magnetic hydrogen spectrum of polymer P-2B-A.
FIG. 7 is a nuclear magnetic hydrogen spectrum of polymer P-0B.
FIG. 8 is a nuclear magnetic hydrogen spectrum of polymer P-2B.
FIG. 9 is a nuclear magnetic hydrogen spectrum of compound as-BNT.
FIG. 10 is a nuclear magnetic hydrogen spectrum of compound s-BN.
FIG. 11 is a nuclear magnetic hydrogen spectrum of compound s-BN 2T.
In FIG. 12, a, B, c and d are SEM images of P-1B/graphene, P-0B/graphene, P-2B/graphene and P-2B-A/graphene catalysts, respectively.
FIG. 13 is a graph at O2LSV curves of P-0B/graphene, P-1B/graphene, P-2B/graphene and P-2B-A/graphene at 1600rpm in saturated 0.1M KOH electrolyte.
In FIG. 14, a, b and c are SEM images of the as-BNT/graphene catalyst, s-BN/graphene catalyst and s-BN 2T/graphene catalyst respectively.
FIG. 15 is a graph at O2LSV curves of s-BN/graphene, as-BNT/graphene and s-BN 2T/graphene at 1600rpm in saturated 0.1M KOH electrolyte.
Detailed Description
Example 1:
preparation of compound 2:
800.2mg of Compound 1 (preparation method see reference: Polymer accumulator Based on Double B ← N bridge Bipyridine (BNBP) Unit for High-Efficiency Al-Polymer Solar cells. adv. Mater, 2016,28(30): 6504-: 570mg (67%).1H NMR(400MHz,CDCl3,20℃): δ10.75-10.72(m,1H),8.09(d,J＝2.0Hz,1H),7.94(d,J＝2.0Hz,1H),7.41(d,J＝1.6Hz, 1H),7.30(d,J＝2.0Hz,1H),3.39(d,J＝7.2Hz,2H),3.15-3.13(m,2H),1.81-1.78(m,1H), 1.43-1.22(m,50H),0.88-0.85(m,12H).
Figure BDA0002858800080000071
P-1B：
401.4mg of the compound 2, 204.1mg of 2, 5-bis (trimethyltin) thiophene, 0.02 equivalent of tris (dibenzylideneacetone) dipalladium and 0.16 equivalent of tris (o-methylphenyl) phosphorus were dissolved in dried toluene (30mL) under an argon atmosphere, and after refluxing at 120 ℃ for 48 hours, 1mL of bromobenzene was added thereto to carry out the end-capping reaction. After 3 hours the reaction was stopped and cooled to room temperature and extracted with chloroform (120 mL). Precipitating the obtained polymer in an acetonitrile solution, and extracting a solid product obtained by suction filtration by using acetone, normal hexane and tetrahydrofuran in sequence to obtain a polymer P-1B, wherein the yield is as follows: 379mg (96%).1H NMR(400MHz,C6D4Cl2,100℃):δ11.28(s,1H),8.70-8.58(m,2H),7.85(d,J＝8.8 Hz,1H),7.71-7.52(m,3H),3.94(s,2H),3.58(s,2H),2.33(s,1H),2.16(s,1H),1.84-1.35 (m,53H),1.13-1.07(m,12H).
Figure BDA0002858800080000081
In order to explore the advantages of the asymmetric structure polymer in various properties, a polymer with a corresponding symmetric structure is synthesized and prepared as a comparative example according to the same method, and the synthetic route is as follows:
comparative example 1
Polymers P-0B and P-2B were also prepared in the same manner.
P-0B: 389.2mg of the compound 1, 205.7mg of 2, 5-bis (trimethyltin) thiophene, 0.02 equivalent of tris (dibenzylideneacetone) dipalladium and 0.16 equivalent of tris (o-methylphenyl) phosphorus were dissolved in dry toluene (10mL) under an argon atmosphere, and after refluxing at 120 ℃ for 48 hours, 1mL of bromobenzene was added thereto for termination. After 3 hours the reaction was stopped and cooled to room temperature and extracted with chloroform (120 mL). Precipitating the obtained polymer in acetonitrile solution, and sequentially using acetone and n-hexyl for a solid product obtained by suction filtrationExtraction of alkane and tetrahydrofuran to obtain polymer P-0B in the following yield: 364mg (97%).1H NMR(400MHz,C6D4Cl2,100℃):δ10.64(s,1H),8.53(s,1H),7.55(d,J＝31.2Hz,2H), 3.56(s,2H),2.13(s,1H),1.87–1.34(m,24H),1.13–1.06(m,6H).
P-2B: 354.8mg of compound 8, 163.6mg of 2, 5-bis (trimethyltin) thiophene, 0.02 equivalent of tris (dibenzylideneacetone) dipalladium and 0.16 equivalent of tris (o-methylphenyl) phosphorus were dissolved in dry toluene (10mL) under argon, refluxed at 120 ℃ for 48h and then capped with 1mL of bromobenzene. After 3 hours the reaction was stopped and cooled to room temperature and extracted with chloroform (120 mL). Precipitating the obtained polymer in an acetonitrile solution, and extracting a solid product obtained by suction filtration by using acetone, normal hexane and tetrahydrofuran in sequence to obtain a polymer P-2B, wherein the yield is as follows: 323mg (96%).1H NMR (400MHz,C6D4Cl2,100℃):δ8.73(s,1H),8.01(s,1H),7.64(s,1H),3.98(s,2H),2.31(s, 1H),1.80–1.38(m,24H),1.09–1.06(m,6H).
Figure BDA0002858800080000091
Example 2:
compound 4:
400.3mg of Compound 3 and 2-fold equivalent of NaH were dissolved in dry THF (10mL), and after refluxing at 70 ℃ for 2 hours, 3-fold equivalent of C was added dropwise to the reaction4H9After further refluxing at 70 ℃ for 24h, Br, was cooled to room temperature and quenched by the addition of a small amount of water, extracted with dichloromethane (150mL), and separated by column chromatography (dichloromethane: petroleum ether mobile phase) to give compound 4 in yield: 241mg (52%).1HNMR(400MHz,CDCl3,20℃):δ9.41(s,1H),7.94 (d,J＝2.0Hz,1H),7.86(d,J＝2.0Hz,1H),7.17(d,J＝2.0Hz,1H),7.11(d,J＝1.6Hz,1H), 6.52(s,2H),3.18-3.13(m,2H),1.74-1.67(m,2H),1.52-1.46(m,2H),1.01-0.97(m,3H).
Figure BDA0002858800080000092
Compound 5:
210.4mg of Compound 4 and 4-fold equivalent of NaH were dissolved in dry THF (10mL), refluxed at 70 ℃ for 2 hours, and then 4-fold equivalent of C was added dropwise to the reaction16H33I, after further refluxing at 70 ℃ for 24h, cooling to room temperature and quenching the reaction dropwise with a small amount of water, extraction with dichloromethane (150mL), column chromatography (dichloromethane: petroleum ether mobile phase) to afford compound 5, yield: 272mg (83%).1H NMR(400MHz,CDCl3,20℃):δ9.72(d,J＝36.4 Hz,2H),7.83-7.81(m,2H),7.01(m,2H),3.18-3.13(m,2H),3.06-3.04(m,2H),2.00(d,J＝ 6.4Hz,1H),1.74-1.67(m,2H),1.52-1.46(m,2H),1.40-1.26(m,25H),1.01-0.97(m,3H), 0.89-0.86(m,6H).
Figure BDA0002858800080000101
Compound 6:
under argon protection, 80.2mg of compound 5 was dissolved in dry dichloromethane (5mL), 40 equivalents of boron trifluoride diethyl etherate and 20 equivalents of triethylamine were slowly added dropwise thereto, refluxed at 50 ℃ for 2 hours and cooled to room temperature, the solvent was distilled off, the organic phase was extracted with n-hexane, and column chromatography (dichloromethane: petroleum ether mobile phase) was performed to obtain compound 6, yield: 85mg (92%).1H NMR(400MHz,CDCl3,20℃):δ8.20-8.19(m,2H),7.66-7.62(m, 2H),3.59-3.55(m,2H),3.47(d,J＝7.2Hz,2H),2.00(d,J＝6.0Hz,1H),1.65-1.64(m,2H), 1.47-1.42(m,2H),1.30-1.23(m,25H),1.02-0.98(m,3H),0.89-0.84(m,6H).
Figure BDA0002858800080000102
P-2B-A：
Under argon, 73.1mg of compound 6, 42.8mg of 2, 5-bis (trimethyltin) thiophene, 0.02 equivalent of tris (dibenzylideneacetone) dipalladium and 0.16 equivalent of tris (o-methylphenyl) phosphorus were dissolved in dry toluene (10 mL). Refluxing was carried out at 120 ℃ for 48h, and then 1mL of bromobenzene was added for the end-capping reaction. After 3 hoursThe reaction was stopped, cooled to room temperature, and extracted with chloroform (120 mL). Precipitating the obtained polymer in an acetonitrile solution, and extracting a solid product obtained by suction filtration by using acetone, normal hexane and tetrahydrofuran in sequence to obtain a polymer P-2B-A, wherein the yield is as follows: 63mg (86%).1HNMR(400MHz, C6D4Cl2,100℃):δ8.69(s,1H),8.00-7.84(m,1H),7.63-7.56(m,1H),3.98(s,2H),2.31(s, 1H),2.08(s,1H),1.79-1.46(m,11H),1.29(s,2H),1.06(s,3H).
Figure BDA0002858800080000103
And (2) putting 3mg of graphene into a 2mL centrifuge tube, adding 1mL of dichloromethane, sealing, performing ultrasonic treatment for 30 minutes in an ultrasonic device, performing ultrasonic treatment for 30 seconds by using an ultrasonic probe, adding 3mg of the polymer P-1B obtained in the example 1, performing ultrasonic treatment again by using the method until the solvent is ultra-dry, vacuumizing for one hour, and scraping to obtain the catalyst P-1B/graphene.
Taking 1.5mg of catalyst P-1B/graphene, adding 65 mu L of water, 65 mu L of ethanol and 20 mu L of nafion solution, uniformly mixing by using an ultrasonic probe, then taking 5 mu L of catalyst P-1B/graphene, coating on a glassy carbon electrode, drying by using argon and then testing.
P-0B, P-2B, P-2B-A is also blended with graphene according to the method to prepare catalysts P-0B/graphene, P-2B/graphene and P-2B-A/graphene respectively, and tests are carried out.
Example 3:
as-BNT：
200.2mg of compound 9, 158.9mg of 2-tributylstannyl thiophene, 0.02 equivalent of tris (dibenzylideneacetone) dipalladium and 0.16 equivalent of tris (o-methylphenyl) phosphorus were dissolved in dry toluene (20mL) under argon. Refluxing at 100 deg.C for 24h, cooling to room temperature, extracting with dichloromethane (150mL), and column chromatography (dichloromethane: petroleum ether mobile phase) to obtain as-BNT, yield: 196mg (97%).1H NMR(400MHz,CDCl3,20℃): δ8.41(d,J＝1.6Hz,1H),8.17-8.16(m,1H),7.68(d,J＝1.2Hz,1H),7.58-7.48(m,4H), 7.21-7.18(m,1H),3.59-3.53(m,4H),1.71(d,J＝6Hz,2H),1.45-1.25(m,16H),0.97-0.86 (m,12H).
Figure BDA0002858800080000111
In order to explore the advantages of small molecules with asymmetric structures on various performances, the small molecules with corresponding symmetric structures are synthesized and prepared according to the same method, and the synthetic route is as follows:
comparative example 2:
reference is made to the reference: electron-purifying Building Block based on B ← N Unit for Polymer accumulator of All-Polymer Solar cells, Angew. chem. int. Ed.2016,55(4): 1436-.
s-BN2T：
200.6mg of compound 11, 280.3mg of 2-tributylstannyl thiophene, 0.02-fold equivalent of tris (dibenzylideneacetone) dipalladium and 0.16-fold equivalent of tris (o-methylphenyl) phosphorus were dissolved in dry toluene (20mL) under argon. Reflux at 100 ℃ for 24h, cooling to room temperature, extraction with dichloromethane (150mL), column chromatography (dichloromethane: petroleum ether mobile phase) to afford s-BN2T in yield: 195mg (96%).1H NMR(400MHz,CDCl3,20℃): δ8.42(s,1H),7.67(s,1H),7.52-7.49(m,2H),7.21-7.19(m,1H),3.58(d,J＝6.8Hz,2H), 1.76-1.73(m,1H),1.47-1.25(m,9H),0.98-0.86(m,6H).
Figure BDA0002858800080000121
And (2) adding 1mL of dichloromethane into 3mg of graphene in a 2mL centrifuge tube, sealing, performing ultrasonic treatment in an ultrasonic device for 30 minutes, performing ultrasonic treatment for 30 seconds by using an ultrasonic probe, adding 3mg of the prepared micromolecule as-BNT, performing ultrasonic treatment according to the method until the solvent is ultra-dry, and pumping for one hour under vacuum to obtain the target catalyst as-BNT/graphene. Then 1.5mg of catalyst is taken, 65 mu L of water, 65 mu L of ethanol and 20 mu L of nafion solution are added, the mixture is uniformly mixed by an ultrasonic probe, 5 mu L of the mixture is coated on a glassy carbon electrode, and the test is carried out after the mixture is dried by argon.
Catalysts s-BN/graphene and s-BN 2T/graphene were also prepared from s-BN and s-BN2T, respectively, according to the above-described method and tested.
The electrochemical tests of the examples of the present application were carried out using a half cell of a three-electrode system, using a glassy carbon electrode coated with a catalyst as a working electrode, wherein the catalyst was the target catalyst in each of examples 1, 2 and 3 and comparative examples 1 and 2, the auxiliary electrode and the reference electrode were a platinum electrode and an Ag/AgCl saturated calomel electrode, respectively, and the electrolyte was 0.1M KOH aqueous solution.
Analysis of data test plots:
the zinc-air battery catalyst prepared by the invention has good ORR catalytic activity, and as can be seen from nuclear magnetic hydrogen spectrograms in figures 1-11, the target organic molecule is successfully synthesized, the structure is confirmed to be correct, the catalyst is uniformly blended with graphene, and no agglomeration and phase separation are found in SEM pictures in figures 12 and 14. As can be seen from the ORR performance comparison of fig. 13 and fig. 15, the catalyst with asymmetric structure has better performance at the starting point and half-wave potential, so has better ORR electrocatalytic activity. The asymmetric molecular structure is helpful for breaking the integrity of a pi conjugated system, so that electrons on a conjugated framework are redistributed in a large area, and the catalytic activity and the number of active sites of the material are further influenced. The ORR catalyst prepared by the invention not only has excellent catalytic performance, but also finds a new direction to help us to further research the catalytic mechanism.

Claims (3)

1. A preparation method based on intramolecular or intermolecular asymmetric organic molecule electrocatalyst comprises the following specific steps:
ultrasonically treating an intramolecular asymmetric organic compound or an intermolecular asymmetric organic compound and graphene in a solvent until the intramolecular asymmetric organic compound or the intermolecular asymmetric organic compound and the graphene are fully mixed, and removing the solvent to obtain the electrocatalyst, wherein the mass ratio of the organic compound to the graphene is 100: 1-1: 100;
the intramolecular asymmetric organic compound is selected from one of the following compounds:
Figure FDA0002858800070000011
wherein the content of the first and second substances,
Figure FDA0002858800070000012
Figure FDA0002858800070000013
Figure FDA0002858800070000021
R＝CnH2n+1，n＝1～24；
R1＝CnH2n+1，n＝1～24；R2＝CmH2m+1m is 1-24, and m is not equal to n; x ═ B, P, N or Si; y ═ C or N;
R3＝F、
Figure FDA0002858800070000022
the intermolecular asymmetric organic compound is selected from one of the following compounds:
Figure FDA0002858800070000023
the symmetric molecule is:
Figure FDA0002858800070000024
in an organic compound which is not symmetrical between molecules,
Figure FDA0002858800070000026
are respectively selected from one of the following molecular formulas, and
Figure FDA0002858800070000027
and
Figure FDA0002858800070000028
the difference is as follows:
Figure FDA0002858800070000025
2. the method according to claim 1, wherein the solvent is dichloromethane, chloroform, n-hexane or tetrahydrofuran.
3. Use of an electrocatalyst prepared according to the preparation method of claim 1 or 2 in a zinc air battery.
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