CN109659569B - Method for constructing single-site electrocatalyst by using metal phthalocyanine molecular precursors and application - Google Patents
Method for constructing single-site electrocatalyst by using metal phthalocyanine molecular precursors and application Download PDFInfo
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Abstract
The invention provides a method for constructing a single-site electrocatalyst by using a metal phthalocyanine molecular precursor and application thereof, wherein the method comprises the following steps: and carrying out coordination reaction on the zeolite imidazole ester framework material and metal phthalocyanine molecules, and carrying out high-temperature cracking on a coordination reaction product so as to obtain the electrocatalyst, wherein the zeolite imidazole ester framework material comprises a metal site to be coordinated and an imidazole nitrogen site to be coordinated. According to the method, zeolite imidazole ester framework materials (ZIFs) with high specific surface area and metal phthalocyanine molecules with high stability are subjected to coordination and compounding, so that the number of active sites of the catalyst is remarkably increased, and the agglomeration of metal atoms can be effectively avoided. The prepared electro-catalyst has the advantages of high single-site metal loading, good stability, high catalytic activity and the like.
Description
Technical Field
The invention relates to the field of electrocatalysis, in particular to a method for constructing a single-site electrocatalyst by using a metal phthalocyanine molecular precursor and application thereof, and more particularly relates to a preparation method for constructing the single-site electrocatalyst by using the metal phthalocyanine molecular precursor and a method for catalyzing oxygen reduction.
Background
With the rapid development of society, the demand of human beings on energy is increasing day by day, and the traditional fossil energy is gradually difficult to meet the demand due to the problems of non-regeneration, limited reserves and the like. Meanwhile, harmful gases such as carbon dioxide, sulfur dioxide, nitrogen oxides and the like generated in the use process of fossil fuels cause increasingly serious environmental problems. Therefore, the development of renewable and sustainable energy conversion technology is necessary and one of the challenges facing the world today to develop green and pollution-free renewable energy to replace fossil energy. Electrochemical has attracted increasing attention as an effective means of converting chemical and electrical energy. The electrochemical reaction condition is mild, the influence on the environment is small, the process is clean and environment-friendly, and the chemical energy has the characteristics of easy storage and suitability for large-scale application. Therefore, the storage and conversion of energy by electrochemical methods are of great significance for solving energy and environmental problems.
Fuel cells, metal-air batteries, and the like can convert chemical energy into electric energy in an electrochemical manner, and are clean and efficient energy conversion manners. The process of converting the chemical energy into the electric energy is a direct process which does not involve combustion, has little influence on the environment and can avoid the environmental problems caused by combustion. However, fuel cells and metal-air batteries also face a challenge, the most significant of which is that the cathode Oxygen Reduction Reaction (ORR) is a slow kinetic process, and thus ORR is the rate-determining step of the cell reaction, limiting the energy conversion efficiency of the cell. To address this problem, higher catalyst loadings are often required to increase the actual energy density. The electrocatalyst not only determines the performance of the electrochemical energy conversion system, but also has important influence on the stability and cost of the system, and is an important bottleneck for the development of the electrochemical energy system.
At present, although the precious metal platinum-based catalyst has very excellent electrocatalytic activity, the precious metal Pt is expensive, low in storage capacity and easy to poison, and therefore, the precious metal Pt is always an important factor for limiting the large-scale application of the precious metal Pt in the oxygen reduction catalyst. Therefore, the search for cheap and efficient electrocatalysts (non-metals, non-noble metals, single-site electrocatalysts, etc. and their composites, etc.) becomes the key to the development of electrochemical energy system research and industrial application. Non-noble metal catalysts, particularly single-site metal catalysts such as those having Fe-N/C or Co-N/C structures, have been shown to have superior catalytic activity in basic or acidic systems. Furthermore, single-site electrocatalysts have been the focus of research due to their advantages of high mass and specific activity, many active sites, etc. However, current single-site electrocatalysts also have a number of disadvantages, such as the tendency to agglomerate metal atoms during the preparation process, poor stability, low single-site metal loading or low catalytic activity.
Therefore, in the preparation of single-site electrocatalysts, it is a challenge how to avoid the agglomeration of metal atoms, and to develop a catalyst with high loading, good stability and high activity.
Disclosure of Invention
The present application is based on the discovery and recognition by the inventors of the following facts and problems:
the current research on non-noble metal single-site electrocatalysts in oxygen reduction is limited to alkaline electrolytes, but the successful application of commercial proton exchange membranes makes it of great significance to develop non-noble metal oxygen reduction electrocatalysts with high activity and stability in acidic electrolytes. Based on the above problems, the inventors have made extensive experimental studies and proposed a novel method for preparing a single-site electrocatalyst, which allows coordination-recombination of zeolitic imidazolate framework materials (ZIFs) having a high specific surface area and metal phthalocyanine molecules having high stability, significantly increases the number of active sites of the catalyst, and can effectively prevent agglomeration of metal atoms. The prepared electro-catalyst has the advantages of high single-site metal loading, good stability, high catalytic activity and the like.
To this end, in a first aspect of the invention, the invention proposes a method of preparing a single-site electrocatalyst. According to an embodiment of the invention, the method comprises: performing coordination reaction on zeolite imidazolate framework materials (ZIFs) and metal phthalocyanine molecules to realize efficient packaging, and cracking the coordination reaction products at high temperature (700-1100 ℃) to obtain the electrocatalyst, wherein the zeolite imidazolate framework materials comprise metal sites to be coordinated and imidazole nitrogen (namely nitrogen atoms in imidazole) sites to be coordinated. The inventors have found that the stability of the metal phthalocyanine molecules allows them to form electrocatalyst materials with a single site distribution of metal more efficiently than other metal salt precursors. According to the method provided by the embodiment of the invention, the metal center (such as iron ion) of the metal phthalocyanine molecule is coordinated with imidazole nitrogen of ZIFs, or the functional group (such as cyano group) of the metal phthalocyanine molecule is further coordinated with the metal center (zinc ion) of the ZIFs, namely the metal phthalocyanine molecule is introduced into the framework of the ZIFs by a chemical method (coordination combination) instead of physically coating the metal phthalocyanine molecule in a cavity of the ZIFs structure, so that the metal phthalocyanine molecule is better dispersed in ZIF-8, the agglomeration of metal atoms can be effectively avoided, and the number of active sites of the catalyst is obviously increased. The electrocatalyst prepared by the method disclosed by the embodiment of the invention has the advantages of high loading (not less than 1.2 wt%), good stability and high catalytic activity, and particularly has a half-wave potential of not less than 0.75V in an acid electrolyte.
According to an embodiment of the present invention, the method may further include at least one of the following additional technical features:
according to the embodiment of the invention, the metal phthalocyanine molecule is a compound shown in a formula (I) or a mixture of at least one compound in the compounds shown in the formula (I),
wherein:
each R is independently H, F, Cl, Br, I, hydroxyl, cyano, amino, sulfydryl, nitro, carboxyl and C1-6Alkoxy, -COO C1-6Alkyl or C1-6An alkylamino group(s) of an alkyl group,
m is Fe, Co, Ni, Cu, Zn or Mn. According to an embodiment of the invention, each R is independently H, F, Cl, Br, I, hydroxy, cyano, amino, mercapto, nitro, carboxy, C1-4Alkoxy, -COO C1-4Alkyl or C1-4An alkylamino group.
According to the embodiment of the invention, the metal phthalocyanine molecule is a compound represented by formulas (1) to (11) or a mixture of at least one compound represented by formulas (1) to (11),
according to an embodiment of the invention, the zeolitic imidazolate framework material is ZIF-8. In some embodiments, the ZIF-8 is obtained by coordinating zinc nitrate with 2-methylimidazole.
According to an embodiment of the invention, the molar ratio of the zinc nitrate to the 2-methylimidazole is 1:4 to 1:8, such as 1:5, 1:6 or 1: 7. The inventor finds that when the molar ratio of the zinc nitrate to the 2-methylimidazole is 1: 4-1: 8, the prepared electrocatalyst is better in stability, higher in unit-site metal loading capacity and better in catalytic activity.
According to the embodiment of the invention, the zeolite imidazole ester framework material is obtained by carrying out coordination reaction on zinc nitrate, ferric nitrate and 2-methylimidazole. The inventor finds that the number of active sites on the surface of the catalyst can be increased by introducing ferric nitrate, so that the catalytic activity of the catalyst in an acidic medium is further improved.
According to an embodiment of the invention, the molar fraction of the iron nitrate in the mixture of zinc nitrate and iron nitrate is 0-20%, such as 3, 5, 7, 10, 13, 15 or 17%. The inventors have found that if the molar fraction of the iron nitrate is too high, agglomeration of metal atoms is caused, resulting in a decrease in the performance of the catalyst produced. Therefore, when the mole fraction of the iron nitrate in the mixture of the zinc nitrate and the iron nitrate is 0-20%, the number of active sites in the prepared electrocatalyst is larger, and the catalytic activity in an acidic medium is better.
According to an embodiment of the invention, the molar ratio of the mixture of zinc nitrate and iron nitrate to the 2-methylimidazole is 1:4 to 1:8, such as 1:5, 1:6 or 1: 7. The inventor finds that when the molar ratio of the mixture of the zinc nitrate and the iron nitrate to the 2-methylimidazole is 1: 4-1: 8, the prepared electrocatalyst has the advantages of better stability, higher single-site metal loading and better catalytic activity.
According to an embodiment of the present invention, the zinc nitrate, the iron nitrate or the 2-methylimidazole are each independently provided in a form dissolved in at least one of anhydrous methanol, dimethyl sulfoxide or N, N-dimethylformamide.
According to an embodiment of the present invention, the metal phthalocyanine-based molecule is provided in a form dissolved in dimethyl sulfoxide or N, N-dimethylformamide.
According to an embodiment of the present invention, the concentration of the metal phthalocyanine molecule in the dimethyl sulfoxide or the N, N-dimethylformamide is 0 to 49mg/mL, such as 5, 10, 15, 20, 25, 30, 35, 40 or 45 mg/mL. The inventors found that if the concentration of the metal phthalocyanine-based molecule is too high, agglomeration of metal atoms is caused, resulting in a decrease in the performance of the catalyst produced. Therefore, when the concentration of the metal phthalocyanine molecules in the dimethyl sulfoxide or the N, N-dimethylformamide is 0-49 mg/mL, the prepared electrocatalyst is better in stability, higher in single-site metal loading capacity and better in catalytic activity.
According to the embodiment of the invention, the coordination reaction is carried out for 3-24 hours at room temperature. The room temperature is 20-30 ℃, for example, 25 ℃. The inventor finds that when the coordination reaction is carried out under the conditions, the prepared electrocatalyst has better stability, higher single-site metal loading and better catalytic activity.
According to an embodiment of the invention, after the coordination reaction, the method further comprises subjecting the coordination reaction product to a post-treatment in order to obtain the electrocatalyst, the post-treatment comprising: 1) carrying out centrifugal treatment on the coordination reaction product; 2) carrying out quick freezing treatment on the centrifugal precipitate obtained in the step 1) in liquid nitrogen and carrying out freeze drying treatment in a freeze dryer; 3) heating the freeze-dried product obtained in the step 2) for 0.5-5 hours at the temperature of 700-1100 ℃; 4) naturally cooling the heat-treated product obtained in the step 3) to room temperature so as to obtain the electrocatalyst.
In a second aspect of the invention, a method of catalytic oxygen reduction is presented. According to an embodiment of the present invention, the oxygen is catalyzed by an electrocatalyst for the reduction reaction, the electrocatalyst being obtained by the method of any one of the above. The method provided by the embodiment of the invention has the advantages of higher reduction efficiency and higher reduction speed.
Drawings
FIG. 1 is a single site electrocatalyst, C-FePc (CN), in example 2, according to the present invention8The transmission electron microscope dark field image of/ZIF-8,
wherein, (a) is a dark field image with a ruler of 100nm, and (b) is a dark field image with a ruler of 5nm, wherein a unit point Fe is marked by a white circle;
FIG. 2 is a view according to the present inventionCatalysts of inventive examples 1, 2 and control catalyst (C-Fe (AcAc))3ZIF-8) polarization diagram in 0.1M oxygen-saturated KOH solution, with a loading of 0.2mg cm-2The rotating speed is 1600 rpm;
FIG. 3 shows catalysts according to examples 2 and 3 of the present invention and a control catalyst (C-Fe (NO)3)3ZIF-8) HClO saturated with oxygen at 0.1M4Polarization curve in solution with a loading of 0.6mg cm-2The rotation speed is 1600 rpm.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
It should be noted that, unless otherwise explicitly indicated, the description of the invention as used herein "… each independently" is to be understood in a broad sense and refers to the fact that in different groups, the particular items expressed between the same symbols do not affect each other, or the fact that in the same groups, the particular items expressed between the same symbols do not affect each other.
The term "optional" or "optionally" means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain monovalent hydrocarbon radical containing from 1 to 20 carbon atoms, wherein the alkyl group may be optionally substituted with one or more substituents as described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) N-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2)，2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3) N-heptyl, n-octyl, and the like.
The term "alkoxy" means an alkyl group attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy group contains 1 to 12 carbon atoms. In one embodiment, the alkoxy group contains 1 to 6 carbon atoms; in another embodiment, the alkoxy group contains 1 to 4 carbon atoms; in yet another embodiment, the alkoxy group contains 1 to 3 carbon atoms.
Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH)3) Ethoxy (EtO, -OCH)2CH3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH2CH3) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)3)2) 1-butoxy (n-BuO, n-butoxy, -OCH)2CH2CH2CH3) 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH)2CH(CH3)2) 2-butoxy (s-BuO, s-butoxy, -OCH (CH)3)CH2CH3) 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC (CH)3)3) 1-pentyloxy (n-pentyloxy, -OCH)2CH2CH2CH2CH3) 2-pentyloxy (-OCH (CH)3)CH2CH2CH3) 3-pentyloxy (-OCH (CH))2CH3)2) 2-methyl-2-butoxy (-OC (CH))3)2CH2CH3) 3-methyl-2-butoxy (-OCH (CH)3)CH(CH3)2) 3-methyl-l-butoxy (-OCH)2CH2CH(CH3)2) 2-methyl-l-butoxy (-OCH)2CH(CH3)CH2CH3) And so on.
The term "alkylamino" or "alkaneThe "alkylamino group" includes "N-alkylamino" and "N, N-dialkylamino" wherein the amino groups are each independently substituted with one or two alkyl groups, wherein the alkyl groups have the meaning as described herein. In one embodiment, alkylamino is one or two C1-6Lower alkylamino groups in which the alkyl group is attached to the nitrogen atom. In another embodiment, alkylamino is C1-3Lower alkylamino groups of (a). Suitable alkylamino groups can be monoalkylamino or dialkylamino, and such examples include, but are not limited to, N-methylamino, N-ethylamino, N-dimethylamino, N-diethylamino, and the like. The alkylamino group is optionally substituted with one or more substituents described herein.
The term "-COO C1-6Alkyl "denotes an alkyl group containing 1 to 6 carbon atoms via an ester group
Attached to the rest of the molecule of formula I, wherein the attachment point
represents-COO C1-6Alkyl "is attached to the rest of the molecule of formula I through this attachment point, the alkyl group having the meaning as described herein. "-COO C1-4Alkyl "denotes an alkyl group containing 1 to 4 carbon atoms via an ester group
Attached to the rest of the molecule of formula I, the remaining meaning being given by the term-COO C1-6Alkyl groups "are the same.
It is to be noted that, in the specific compound of the present invention, for example, in the compound (6), the substituent on each ring A, B, C, D is-NO2It is meant that each substituent may be substituted at either of the outer two positions on the ring to which it is directly attached. For example, the substituent-NO on the A ring in the compound (6)2Represents the formula-NO2Can be substituted at any position of a and b to form a compound shown as a formula or bCompound, substituent-NO in ring B, C, D2Has the same meaning as ring A, and each-NO2The choice of substitution sites in the A, B, C, D loop did not interfere with each other.
The invention relates to application of a single-site electrocatalyst constructed by metal phthalocyanine molecule precursors in the field of electrocatalysis. In particular to a method for preparing a nitrogen-doped carbon material electrocatalyst with metal unit-site distribution by using metal phthalocyanine molecules/metal-organic Framework Structures (ZIFs) as precursors and adopting a one-step pyrolysis method. The invention aims to provide a universal material design method for preparing an oxygen reduction catalyst with high activity (especially in an acidic medium) and high stability. On the basis, the activity of the catalyst is regulated and controlled by the optimized design of the catalyst precursor, and the structure and the performance of the catalyst are deeply researched.
The invention discloses a method for preparing a nitrogen-doped carbon material with metal unit site distribution by introducing metal phthalocyanine molecules serving as precursors into ZIF (zinc-aluminum) with a metal-organic framework structure, which is applied to high-efficiency electrocatalysis of oxygen reduction reaction. The stability of the metal phthalocyanine molecules makes them more effective in forming metal single-site distributed electrocatalyst materials than other metal salt precursors. Researches find that the cyano-substituted iron phthalocyanine is beneficial to introducing molecules into ZIF-8 species to form more active sites. The electrocatalyst can effectively catalyze the oxygen reduction reaction in alkaline and acidic electrolytes. Further, by introducing the combined action of metal inorganic salt (ferric nitrate) and cyano-substituted iron phthalocyanine, the number of active sites on the surface of the catalyst can be increased, and the electrocatalytic performance of the catalyst is remarkably improved.
An object of the present invention is to propose a method for preparing a catalyst for oxygen reduction having high activity by coordinating a metal center in a metal phthalocyanine-based molecule with imidazole while introducing a functional group of a metal phthalocyanine-based molecule derivative with zinc ions into zeolite imidazole ZIF-8 having a porous structure, and then by means of pyrolysis. The single-site electrocatalyst can have oxygen reduction performance exceeding the activity of noble metal Pt in an alkaline electrolyte, the catalytic active sites of the single-site electrocatalyst can be increased in an acidic medium through metal phthalocyanine molecule derivatives, and the number of the active sites on the surface of the single-site electrocatalyst is further increased through metal inorganic salts, so that the activity of the single-site electrocatalyst in the acidic medium is further improved. The method can be generally applied to the synthesis of various metal single-site electrocatalysts, and has the advantages of simple preparation method, controllable preparation and large-scale synthesis.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the single-site electrocatalyst by using the metal phthalocyanine molecule/metal-organic framework structure precursor comprises the following steps:
the method comprises the following steps: zinc nitrate (or a mixture of the zinc nitrate and ferric nitrate) and 2-methylimidazole are weighed according to a molar ratio of 1: 4-1: 8, and are dissolved in anhydrous methanol, dimethyl sulfoxide or N, N-dimethylformamide under the assistance of ultrasound respectively.
Step two: weighing 0-144.8 mg of metal phthalocyanine molecules, and dissolving in 3-20 mL of N, N-dimethylformamide or dimethyl sulfoxide solution under the ultrasonic action.
Step three: and (2) slowly and dropwise adding the 2-methylimidazole solution in the step one into the zinc nitrate (or the mixture of the zinc nitrate and the ferric nitrate) solution in the step one.
Step four: and (3) adding the metal phthalocyanine molecular solution in the step (II) into the mixed solution in the step (III), and stirring for 3-24 hours at room temperature under the action of magnetic stirring.
Step five: and (4) centrifuging the catalyst precursor obtained in the step four at a high speed, washing and centrifuging the catalyst precursor for three times by using N, N-dimethylformamide and methanol respectively, and finally quickly freezing the solid in liquid nitrogen, and freeze-drying the solid in a freeze dryer for 24 hours.
Step six: and putting the solid powder in the fifth step into a tubular furnace, heating to 700-1100 ℃ at a speed of 1-5 ℃/min under the protection of inert gas, preserving heat for 0.5-5 h, and naturally cooling to room temperature. The solid powder can be used to obtain single-site metal electrocatalysts without acid treatment.
In some embodiments, the purity of the zinc nitrate is 90-99.999%.
In some embodiments, the 2-methylimidazole has a purity of 90-99.999%.
In some embodiments, the purity of the ferric nitrate is 90-99.999%.
In some embodiments, the solvent may be one or more of methanol, dimethylsulfoxide, and N, N-dimethylformamide.
In some embodiments, the inert gas may be one or a mixture of nitrogen and argon.
In some embodiments, the molar ratio of the ferric nitrate in the mixture of zinc nitrate and ferric nitrate is 0-20%.
In some embodiments, the metal phthalocyanine-based molecule can be iron phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine or a derivative (including nitro iron phthalocyanine, nitro nickel phthalocyanine, nitro cobalt phthalocyanine, nitro zinc phthalocyanine, nitro manganese phthalocyanine, nitro copper phthalocyanine, cyano iron phthalocyanine, cyano nickel phthalocyanine, cyano cobalt phthalocyanine, cyano zinc phthalocyanine, cyano manganese phthalocyanine, cyano copper phthalocyanine, amino iron phthalocyanine, amino nickel phthalocyanine, amino cobalt phthalocyanine, amino zinc phthalocyanine, amino manganese phthalocyanine, amino copper phthalocyanine, fluoro substituted iron phthalocyanine, fluoro substituted nickel phthalocyanine, fluoro substituted cobalt phthalocyanine, fluoro substituted zinc phthalocyanine, fluoro substituted manganese phthalocyanine, fluoro substituted copper phthalocyanine, fluoro substituted chloro substituted nickel phthalocyanine, chloro substituted cobalt phthalocyanine, chloro substituted iron phthalocyanine, chloro substituted zinc phthalocyanine, chloro substituted manganese phthalocyanine, chloro substituted copper phthalocyanine) or a mixture of more thereof, wherein the structural formula is shown in formula (I).
In the formula (I), R is respectively and independently H, CN, NO2、NH2F, Cl, OMe or COOMe, M is Fe, Co, Ni, Cu, Zn or Mn.
The invention has the following excellent effects:
(1) the metal phthalocyanine molecules or derivatives are coordinated with metal in a phthalocyanine center through imidazole or a substituent group in the metal phthalocyanine molecule derivatives and zinc ions at the same time, so that the metal phthalocyanine molecules or derivatives are introduced into a framework (coordination bonding and non-coating) of ZIFs (zinc ion exchange resins), and further pyrolyzed to obtain different metal single-site electrocatalysts.
(2) The single-site electrocatalyst obtained by the invention has excellent electrocatalytic oxygen reduction performance, and especially the loading of single-site Fe-N can be increased by further using ferric nitrate in a cyanoferriphthalocyanine/ZIFs system. And the catalyst (example 3) had an activity of 0.811V (half-wave potential) for oxygen reduction in 0.1M perchloric acid electrolyte and 0.910V (half-wave potential) in 0.1M potassium hydroxide electrolyte.
The invention will be further explained with reference to specific examples.
In the formula of the single-site electrocatalyst, Pc represents phthalocyanine; control catalyst C-Fe (AcAc)3ZIF-8 denotes a compound of Fe (AcAc) acetylacetonate under the same conditions3A catalyst prepared for the precursor; control catalyst C-Fe (NO)3)3ZIF-8 denotes the reaction of iron nitrate Fe (NO) under the same conditions3)3Catalyst prepared as precursor.
Example 1
Zinc nitrate (6mmol) and 2-methylimidazole (24mmol) were weighed out in a molar ratio of 1:4, respectively, and dissolved in 75mL of anhydrous methanol with the aid of ultrasound, respectively. Then 72.4mg of iron phthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the action of ultrasound. The 2-methylimidazole solution was added to the zinc nitrate solution. Then, the iron phthalocyanine solution was slowly dropped into the aforementioned mixed solution, and stirred at room temperature for 18 hours under magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 1000 ℃ at the temperature of 5 ℃ per minute under the protection of argon, preserving the heat for 3 hours, and naturally cooling to room temperature. The solid powder can obtain the single-site electrocatalyst C-FePc/ZIF-8 without acid treatment.
The polarization curve of the single-site electrocatalyst C-FePc/ZIF-8 in 0.1M oxygen-saturated KOH solution is shown in FIG. 2.
Results of property testing:
1. activity of oxygen reduction of 0.761V (half-wave potential) in 0.1M perchloric acid electrolyte and 0.881V (half-wave potential) in 0.1M potassium hydroxide electrolyte;
2. the metal loading was 2.2% (mass fraction).
Example 2
Zinc nitrate (6mmol) and 2-methylimidazole (24mmol) were weighed out in a molar ratio of 1:4, respectively, and dissolved in 75mL of anhydrous methanol with the aid of ultrasound, respectively. Then 72.4mg of octacyanoferriphthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide under the action of ultrasound. The 2-methylimidazole solution was added to the zinc nitrate solution. Then, the cyanoiron phthalocyanine solution was slowly added dropwise to the aforementioned mixed solution, and stirred at room temperature for 18 hours under magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 1000 ℃ at the temperature of 5 ℃ per minute under the protection of argon, preserving the heat for 3 hours, and naturally cooling to room temperature. The solid powder can be used for obtaining the single-site electrocatalyst C-FePc (CN) without acid treatment8/ZIF-8。
Single site electrocatalyst C-FePc (CN)8The transmission electron microscope dark field of/ZIF-8 is shown in figure 1; single site electrocatalyst C-FePc (CN)8FIG. 2 shows the polarization diagram of/ZIF-8 in 0.1M oxygen saturated KOH solution; single site electrocatalyst C-FePc (CN)8ZIF-8 HClO saturated with oxygen at 0.1M4The polarization profile in solution is shown in figure 3.
Results of property testing:
1. activity of oxygen reduction of 0.792V (half-wave potential) in 0.1M perchloric acid electrolyte and 0.901V (half-wave potential) in 0.1M potassium hydroxide electrolyte;
2. the metal loading was 2.6% (mass fraction).
3. After 10000 times of cyclic voltammetry tests, the catalyst lost only 23mV for the half-wave potential in 0.1M perchloric acid electrolyte and only 11mV for the half-wave potential in 0.1M potassium hydroxide electrolyte.
Example 3
Zinc nitrate (5.88mmol), ferric nitrate (0.12mmol) and 2-methylimidazole (24mmol) were weighed out in a molar ratio of 1:4, respectively, and dissolved in 75mL of anhydrous methanol with the aid of ultrasound, respectively. Then 72.4mg of octacyanoferriphthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide under the action of ultrasound. The 2-methylimidazole solution was added to the mixed solution of zinc nitrate and ferric nitrate. Then, the cyanoiron phthalocyanine solution was slowly added dropwise to the mixed solution of 2-methylimidazole, zinc nitrate and iron nitrate, and stirred at room temperature for 18 hours under magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 1000 ℃ at the temperature of 5 ℃ per minute under the protection of argon, preserving the heat for 3 hours, and naturally cooling to room temperature. The solid powder can be used for preparing single-site electrocatalyst C- (Fe (NO) without acid treatment3)3+FePc(CN)8)/ZIF-8。
Single site electrocatalyst C- (Fe (NO)3)3+FePc(CN)8) ZIF-8 HClO saturated with oxygen at 0.1M4The polarization profile in solution is shown in figure 3.
Results of property testing:
1. activity of oxygen reduction at 0.811V (half-wave potential) in 0.1M perchloric acid electrolyte and 0.910V (half-wave potential) in 0.1M potassium hydroxide electrolyte;
2. the metal loading was 2.8% (mass fraction).
3. After 10000 cyclic voltammetry tests, the catalyst lost only 21mV for the half-wave potential in 0.1M perchloric acid electrolyte and 9mV for the half-wave potential in 0.1M potassium hydroxide electrolyte.
Example 4
Zinc nitrate (6mmol) and 2-methylimidazole (24mmol) were weighed out in a molar ratio of 1:4, respectively, and dissolved in 75mL of anhydrous methanol with the aid of ultrasound, respectively. Then 72.4mg of nickel phthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the action of ultrasound. The 2-methylimidazole solution was added to the zinc nitrate solution. Then, the nickel phthalocyanine solution was slowly added dropwise to the aforementioned mixed solution, and stirred at room temperature for 18 hours under magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 1000 ℃ at the temperature of 5 ℃ per minute under the protection of argon, preserving the heat for 3 hours, and naturally cooling to room temperature. The solid powder can obtain the single-site electrocatalyst C-NiPc/ZIF-8 without acid treatment.
Example 5
Zinc nitrate (6mmol) and 2-methylimidazole (48mmol) were weighed out in a molar ratio of 1:8, respectively, and dissolved in 75mL of anhydrous methanol with the aid of ultrasound, respectively. Then, 10.0mg of iron phthalocyanine, 11.0mg of cobalt phthalocyanine and 8.5mg of nickel phthalocyanine were weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the ultrasonic action. The 2-methylimidazole solution was added to the zinc nitrate solution. Then, the iron phthalocyanine, cobalt phthalocyanine and nickel phthalocyanine solution is slowly dripped into the mixed solution, and is stirred for 18 hours at room temperature under the action of magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 900 ℃ at the temperature of 5 ℃ per minute under the protection of argon, preserving the heat for 2 hours, and naturally cooling to room temperature. The solid powder can obtain the single-site electrocatalyst C- (FePc + CoPc + NiPc)/ZIF-8 without acid treatment.
Example 6
According to a molar ratio of 0.98: 0.02: 4 Zinc nitrate (5.88mmol), ferric nitrate (0.12mmol) and 2-methylimidazole (24mmol) were weighed out separately and dissolved in 75mL of anhydrous methanol with the aid of ultrasound, respectively. Then 24.1mg of iron phthalocyanine, cobalt phthalocyanine and nickel phthalocyanine are weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the action of ultrasonic waves. The 2-methylimidazole solution was added to the mixed solution of zinc nitrate and ferric nitrate. Then slowly dripping the iron phthalocyanine, cobalt phthalocyanine and nickel phthalocyanine solution into the mixed solution of 2-methylimidazole, zinc nitrate and ferric nitrate, and stirring for 18 hours at room temperature under the action of magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 1000 ℃ at the temperature of 2 ℃ per minute under the protection of mixed gas of argon and nitrogen, preserving the heat for 2 hours, and naturally cooling to room temperature. The solid powder can obtain the single-site electrocatalyst C- (FePc + CoPc + NiPc)/ZIF-8 without acid treatment.
Example 7
According to a molar ratio of 0.96: 0.04: 4 Zinc nitrate (5.76mmol), ferric nitrate (0.24mmol) and 2-methylimidazole (24mmol) were weighed out separately and dissolved in 75mL of anhydrous methanol with the aid of ultrasound. Then 72.4mg of nitro iron phthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the action of ultrasound. The 2-methylimidazole solution was added to the mixed solution of zinc nitrate and ferric nitrate. Then the nitro iron phthalocyanine solution is slowly added into the mixed solution of 2-methylimidazole, zinc nitrate and ferric nitrate dropwise, and stirred for 18 hours at room temperature under the action of magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. Finally, the dried solid powder is placed in a tube furnace under the protection of a mixed gas of argon and nitrogen for each timeHeating to 1100 ℃ in 2 minutes, preserving the heat for 2 hours, and naturally cooling to room temperature. The solid powder can obtain the single-site electrocatalyst C-FePc (NO) without acid treatment2)4/ZIF-8。
Example 8
According to a molar ratio of 1:4 Zinc nitrate (6mmol) and 2-methylimidazole (24mmol) were weighed out separately and dissolved in 75mL of anhydrous methanol with the aid of ultrasound. Then 72.4mg of copper phthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the action of ultrasound. The 2-methylimidazole solution was added to the zinc nitrate solution. Then the copper phthalocyanine solution is slowly dropped into the mixed solution and stirred for 18 hours at room temperature under the action of magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tube furnace, heating to 1100 ℃ at the temperature of 5 ℃ per minute under the protection of mixed gas of argon and nitrogen, preserving the heat for 2 hours, and naturally cooling to room temperature. The solid powder can obtain the single-site electrocatalyst C-CuPc/ZIF-8 without acid treatment.
Example 9
According to a molar ratio of 1:4 Zinc nitrate (6mmol) and 2-methylimidazole (24mmol) were weighed out separately and dissolved in 75mL of anhydrous methanol with the aid of ultrasound. Then 72.4mg of aminocobalt phthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide under the action of ultrasound. The 2-methylimidazole solution was added to the zinc nitrate solution. Then, the amino cobalt phthalocyanine solution was slowly added dropwise to the aforementioned mixed solution, and stirred at room temperature for 18 hours under magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 900 ℃ at the temperature of 5 ℃ per minute under the protection of mixed gas of argon and nitrogen, preserving the heat for 3 hours, and naturally cooling to room temperature. The solid powder can be obtained without acid treatmentElectrocatalyst C-CoPc (NH)2)4/ZIF-8。
Example 10
According to a molar ratio of 1:4 Zinc nitrate (6mmol) and 2-methylimidazole (24mmol) were weighed out separately and dissolved in 75mL of anhydrous methanol with the aid of ultrasound. Then 72.4mg of fluorine substituted cobalt phthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the action of ultrasound. The 2-methylimidazole solution was added to the zinc nitrate solution. Then, the fluorine substituted cobalt phthalocyanine solution is slowly dripped into the mixed solution and stirred for 18 hours at room temperature under the action of magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 1000 ℃ at the temperature of 5 ℃ per minute under the protection of mixed gas of argon and nitrogen, preserving the heat for 3 hours, and naturally cooling to room temperature. The solid powder can be used to obtain single-site electrocatalyst C-CoPcF without acid treatment8/ZIF-8。
Example 11
According to a molar ratio of 1:4 Zinc nitrate (6mmol) and 2-methylimidazole (24mmol) were weighed out separately and dissolved in 75mL of anhydrous methanol with the aid of ultrasound. Then 72.4mg of fluorine substituted iron phthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the action of ultrasound. The 2-methylimidazole solution was added to the zinc nitrate solution. Then, the fluorine substituted iron phthalocyanine solution is slowly dropped into the mixed solution and stirred for 18 hours at room temperature under the action of magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 800 ℃ at the temperature of 5 ℃ per minute under the protection of mixed gas of argon and nitrogen, preserving the heat for 1h, and naturally cooling to room temperature. The solid powder can be used for obtaining the single-site electrocatalyst C-FePcF without acid treatment8/ZIF-8。
Example 12
According to a molar ratio of 1: zinc nitrate (6mmol) and 2-methylimidazole (48mmol) were weighed out separately and dissolved in 75mL of anhydrous methanol with the aid of ultrasound. Then 72.4mg of chlorine substituted iron phthalocyanine was weighed out and dissolved in 10mL of N, N-dimethylformamide solution under the action of ultrasound. The 2-methylimidazole solution was added to the zinc nitrate solution. Then, the chlorine-substituted iron phthalocyanine solution was slowly added dropwise to the aforementioned mixed solution, and stirred at room temperature for 18 hours under magnetic stirring. Centrifuging the obtained catalyst precursor at high speed, washing and centrifuging with N, N-dimethylformamide and methanol for three times, quickly freezing the solid in liquid nitrogen, and freeze-drying in a freeze-drying machine for 24 h. And finally, placing the dried solid powder in a tubular furnace, heating to 1000 ℃ at the temperature of 2 ℃ per minute under the protection of mixed gas of argon and nitrogen, preserving the heat for 1h, and naturally cooling to room temperature. The solid powder can be used for obtaining the single-site electrocatalyst C-FePcCl without acid treatment8/ZIF-8。
Results of property testing: the single-site electrocatalysts obtained in examples 4-12 have high single-site metal loading, good stability, and high catalytic activity (in 0.1M perchloric acid electrolyte or 0.1M potassium hydroxide electrolyte).
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (7)
1. A method of preparing an electrocatalyst, comprising:
carrying out coordination reaction on a zeolite imidazole ester framework material and a metal phthalocyanine molecule, and carrying out high-temperature cracking on a coordination reaction product so as to obtain the electrocatalyst, wherein the zeolite imidazole ester framework material comprises a metal site to be coordinated and an imidazole nitrogen site to be coordinated;
the method comprises the following specific steps:
dripping 2-methylimidazole solution into a mixture solution of zinc nitrate and ferric nitrate to obtain a mixed solution;
adding a metal phthalocyanine molecular solution into the mixed solution for coordination reaction to obtain a coordination reaction product;
carrying out high-temperature cracking on the coordination reaction product to obtain a single-site electrocatalyst;
the mole fraction of the ferric nitrate in the mixture of the zinc nitrate and the ferric nitrate is 0-20%;
the molar ratio of the mixture of the zinc nitrate and the ferric nitrate to the 2-methylimidazole is 1: 4-1: 8;
the concentration of the metal phthalocyanine molecular solution is 0-49 mg/mL;
the metal phthalocyanine molecule is dissolved in dimethyl sulfoxide or N, N-dimethylformamide.
2. The method according to claim 1, wherein the metal phthalocyanine molecule is a compound of formula (I) or a mixture of compounds of formula (I),
wherein:
each R is independently HF, Cl, Br, I, hydroxyl, cyano, amino, mercapto, nitro, carboxyl, C1-6Alkoxy, -COOC1-6Alkyl or C1-6An alkylamino group(s) of an alkyl group,
m is Fe, Co, Ni, Cu, Zn or Mn.
3. The method of claim 2, wherein each R is independently C1-4Alkoxy, -COO C1-4Alkyl or C1-4An alkylamino group.
4. The method according to claim 1, wherein the metal phthalocyanine-based molecule is a compound represented by one of formulae (1) to (11) or a mixture thereof,
5. the method according to claim 1, wherein the coordination reaction is performed at room temperature for 3-24 hours.
6. The method of claim 1, further comprising, after the coordination reaction, post-treating the coordination reaction product to obtain the electrocatalyst, the post-treating comprising:
1) carrying out centrifugal treatment on the coordination reaction product;
2) carrying out quick freezing treatment on the centrifugal precipitate obtained in the step 1) in liquid nitrogen and carrying out freeze drying treatment in a freeze dryer;
3) heating the freeze-dried product obtained in the step 2) for 0.5-5 hours at the temperature of 700-1100 ℃;
4) naturally cooling the heat-treated product obtained in the step 3) to room temperature so as to obtain the electrocatalyst.
7. A method of catalysing the reduction of oxygen, characterised in that the reduction of oxygen is catalysed by an electrocatalyst obtained by a method as claimed in any one of claims 1 to 6.
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