CN114361470B - Preparation method and application of nitrogen-doped MXene-loaded cobalt phthalocyanine composite material - Google Patents

Preparation method and application of nitrogen-doped MXene-loaded cobalt phthalocyanine composite material Download PDF

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CN114361470B
CN114361470B CN202210009098.1A CN202210009098A CN114361470B CN 114361470 B CN114361470 B CN 114361470B CN 202210009098 A CN202210009098 A CN 202210009098A CN 114361470 B CN114361470 B CN 114361470B
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nitrogen
mxene
cobalt phthalocyanine
doped
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CN114361470A (en
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张文林
何婷婷
杨德新
刘仕萌
余文杰
段艳菊
于丰收
李春利
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Hebei University of Technology
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a preparation method and application of a nitrogen-doped MXene-loaded cobalt phthalocyanine composite material. The method comprises the steps of firstly chemically etching Ti by hydrofluoric acid solution 3 AlC 2 Preparation of MXene (i.e. Ti) with F end groups adsorbed on surface 3 C 2 F 2 ) And then, selecting urea as a nitrogen dopant, loading nitrogen element on MXene by a one-step hydrothermal method, and then combining cobalt phthalocyanine and the nitrogen-doped MXene to prepare the catalyst. The invention applies the catalyst in ORR, and the obtained catalytic material has good oxygen reduction catalytic activity and wide application prospect.

Description

Preparation method and application of nitrogen-doped MXene-loaded cobalt phthalocyanine composite material
Technical Field
The invention belongs to the technical field of MXene composite materials, particularly relates to a nitrogen-doped MXene functionalized composite material, and more particularly relates to a preparation method of the nitrogen-doped MXene-loaded cobalt phthalocyanine composite material and application of the nitrogen-doped MXene-loaded cobalt phthalocyanine composite material in oxygen reduction reaction.
Background
With the coming of global energy crisis and the increasing environmental pollution and greenhouse effect caused by the combustion of fossil fuels, the development of clean energy is urgently needed. There is an increasing concern about the storage and conversion of sustainable energy, and fuel cells are currently of high research value as one of the most promising clean energy converters. In a fuel cell, fuel is oxidized at the anode, the liberated electrons are transferred through an external circuit to the cathode, and oxygen is reduced at the cathode. However, since the oxygen reduction reaction is a four-electron reaction, the kinetics thereof are very slow, which greatly limits the energy output efficiency of the fuel cell. ORR is a very important reaction for fuel cells. It is well known that the best ORR catalyst at present is the Pt-based catalyst. Although the platinum-based catalyst has the most outstanding catalytic activity, the platinum-based catalyst has poor stability, and platinum is scarce, has low reserves and is expensive. Therefore, it is necessary to develop a high-efficiency and high-stability catalyst of non-platinum group.
In recent years, two-dimensional nanomaterials are gaining increasing popularity due to their ultra-thin thickness, large surface area and high surface-to-volume atomic ratio. Transition metal carbide (MXenes) is an emerging 2D material, and rapidly becomes a research hotspot since being discovered in 2011, and the molecular formula of the transition metal carbide (MXenes) is M n+1 X n T x (n =1,2,3) wherein M is a transition metal, X is carbon or nitrogen, T x Is a terminal functional group (-O, -F, -OH). With the intensive research on MXene, the electrocatalytic performance is increasingly highlighted. The catalyst carrier for catalyzing fuel combustion has the characteristics of unique two-dimensional layered structure, better surface chemical property, excellent conductivity, good structural stability and the like. MXene is used as a novel two-dimensional layered material, the high stability of MXene is beneficial to the overall stability of the catalyst, the large specific surface area can increase catalytic activity sites, and the catalyst preparation process is simple, convenient to operate, excellent in conductivity and the like. However, when the MXene is used for independently preparing the electrocatalyst for the electrocatalysis reaction, the catalytic activity is lower; it is necessary to combine transition metals or non-metals with them, but most bimetallic catalysts still have poor catalytic activity and are still under investigation.
Nitrogen doping has proven to be a simple modification strategy to improve the electrochemical performance of two-dimensional MXene, which is a promising candidate for energy storage applications. Chemical doping of nitrogen atoms is an effective method for improving the electrochemical performance of many two-dimensional MXene by manipulating the electron transfer process. The nitrogen-doped MXene has the characteristics of high surface area, large pore volume and further increased interlayer spacing, and has excellent electrochemical performance in ORR application. Although nitrogen doping has been widely studied to improve the electrochemical performance of MXene materials, its underlying mechanism remains controversial, particularly with respect to the existing forms of nitrogen dopants. The nitrogen dopant directly affects the kinetics of the ORR reaction, thereby affecting the catalytic activity of the ORR. It is important with respect to the choice of nitrogen dopant. In addition, a high-temperature calcination mode is generally adopted when the nitrogen-doped MXene is prepared, so that the energy consumption is high, the operation is complex, and harmful gases are easily generated. The catalyst is in a carbonization state during preparation, the carbonization degree is not easy to determine, the material is deformed, and the carbon defect is reduced, so that the catalytic activity of the catalyst is influenced, and the catalyst has certain limitations.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen-doped MXene-loaded cobalt phthalocyanine composite material and application of the composite material as an oxygen reduction reaction catalyst aiming at the defects in the prior art. The invention firstly chemically etches Ti by hydrofluoric acid solution 3 AlC 2 Preparation of MXene (i.e. Ti) with F end groups adsorbed on surface 3 C 2 F 2 ) And then, selecting urea as a nitrogen dopant, loading nitrogen element on MXene by a one-step hydrothermal method, and then combining cobalt phthalocyanine and the nitrogen-doped MXene to prepare the catalyst. The invention applies the catalyst in ORR, and the obtained catalytic material has good oxygen reduction catalytic activity and wide application prospect.
The invention provides the following specific technical scheme:
a preparation method of a nitrogen-doped MXene-loaded cobalt phthalocyanine composite material comprises the following steps:
in the first step, chemical etching is used to etch Ti 3 AlC 2 Etching to obtain MXene with F end groups adsorbed on the surface:
mixing Ti 3 AlC 2 Adding the powder into HF solution, stirring at 25-45 deg.C for 12-48 hr, centrifuging with deionized water, filtering, and drying for 12-24 hr to obtain MXene;
wherein 1-3g Ti is added into every 10-20ml HF solution 3 AlC 2 ；
The concentration of the HF solution is40～49％，Ti 3 AlC 2 The powder size is 200-400 meshes;
secondly, loading nitrogen element on MXene by adopting a one-step hydrothermal method:
dissolving urea in deionized water, adding MXene, stirring the solution, mixing, pouring into a polytetrafluoroethylene high-pressure reaction kettle, and keeping at 150-200 ℃ for 8-32 hours; after the reaction is finished, washing, filtering and drying to obtain the nitrogen-doped MXene;
wherein, 2 to 3g of urea and 0.005 to 0.01g of MXene are added into each 5ml of water;
thirdly, loading cobalt phthalocyanine on the nitrogen-doped MXene by adopting a solvent method:
and then pouring the cobalt phthalocyanine solution into the nitrogen-doped MXene solution, stirring at room temperature for 12-24 hours, filtering, washing, and drying for 10-12 hours to obtain the cobalt phthalocyanine-loaded nitrogen-doped MXene composite material.
Wherein the mass ratio of cobalt phthalocyanine to nitrogen-doped MXene is 1:0.5 to 6;
the solvent of the cobalt phthalocyanine solution and the nitrogen-doped MXene solution is DMF; 0.005-0.5 g of cobalt phthalocyanine is added into every 10ml of DMF; 0.0025 to 3.0g of nitrogen-doped MXene is added per 10ml of DMF.
The application of the nitrogen-doped MXene-supported cobalt phthalocyanine composite material is that the composite material is supported on a cathode of a fuel cell to serve as a catalyst.
The invention has the substantive characteristics that:
according to the invention, a hydrothermal method is adopted to load nitrogen element on MXene, and the nitrogen element is combined with cobalt phthalocyanine, and the synthesized material is applied to oxygen reduction reaction for the first time.
Compared with the known preparation method of the MXene composite material loaded by other metals and nonmetal, the method selects two substances of cobalt phthalocyanine and urea as the loading bodies, and Ti is added before loading 3 AlC 2 Etching to obtain MXene with F end groups adsorbed on the surface; MXene with F end groups adsorbed on the surface has certain electrocatalytic activity and higher ionic conductivity, and the good interlayer spacing and rich chemical composition of the N-doped MXene can better promote electron transfer; MXene itself is a two-dimensional layered structure, negativeAfter carrying nitrogen element, the carrier is combined with cobalt phthalocyanine through pi-pi bond to generate axial coordination, and the combined action of the two can have better catalytic reduction effect on oxygen.
The invention has the beneficial effects that:
compared with other metal catalysts, the nitrogen-doped MXene supported cobalt phthalocyanine composite material prepared by a solvent method is added with a certain amount of nonmetal and metal; the cost is reduced, the operation is simple, and the preparation condition is mild. Meanwhile, due to the addition of cobalt and nitrogen elements, the electron transfer rate is increased, the charge transfer resistance is reduced, and the catalytic active sites are effectively increased; and in the case where most MXene is used in a supercapacitor, it is used in an oxygen reduction reaction. Through electrochemical performance tests, the synthesized electro-catalytic composite material has good oxygen reduction catalytic activity. The initial potential and the half-wave potential are respectively as follows: 0.989V and 0.836V, close to 1.0V and 0.85V of commercial platinum carbon, and has a higher limiting current density; compared with the cost of the two, the cost of 1g of commercial platinum-carbon catalyst is 192.2 yuan, and the cost of the material serving as the oxygen reduction reaction catalyst is only 42 yuan.
Description of the drawings:
fig. 1 is an SEM image of nitrogen-doped MXene obtained in example 1.
Fig. 2 is an SEM image of the nitrogen-doped MXene-supported cobalt phthalocyanine composite obtained in example 1.
FIG. 3 is a linear voltammetry scan curve (sweep rate is 10mv/s, rotation speed is 1600 rpm) of the nitrogen-doped MXene-supported cobalt phthalocyanine composite, the nitrogen-doped MXene, cobalt phthalocyanine and platinum carbon obtained in example 1 in 0.1mol/L oxygen saturated KOH solution.
Detailed Description
The preparation method of the nitrogen-doped MXene-supported cobalt phthalocyanine composite material and the application of the composite material as an oxygen reducing agent are further described by specific examples.
The chemical etching method is to etch Ti 3 AlC 2 Etching to MXene and Ti with F end group adsorbed on surface 3 AlC 2 The specific reaction process for known materials is as follows:
Ti 3 AlC 2 (s)+3HF(l)→Ti 3 C 2 (s)+AlF 3 (s)+(3/2)H 2 (g)；
Ti 3 C 2 (s)+2HF(l)→Ti 3 C 2 F 2 (s)+H 2 (g)。
example 1:
1. synthesis of MXene containing F end groups
10ml of a 40% HF solution was poured into a beaker, and 1g of Ti was added 3 AlC 2 Powder (200 mesh), stirred at 25 ℃ for 24 hours, washed centrifugally with deionized water, filtered and dried for 12 hours to obtain MXene.
2. Preparation of nitrogen-doped MXene
Dissolving 20g of urea in 50ml of deionized water, adding 0.05g of MXene, stirring to obtain a uniform solution, pouring the uniform solution into a sealed polytetrafluoroethylene high-pressure reaction kettle, transferring the reaction kettle into a drying box, and keeping the reaction kettle at 150 ℃ for 24 hours. And after the reaction is finished, centrifugally washing the reactant by using deionized water and ethanol, filtering and drying the reactant to obtain the nitrogen-doped MXene.
3. Preparation of nitrogen-doped MXene-loaded cobalt phthalocyanine composite material
0.02g of cobalt phthalocyanine is poured into 10ml of DMF solvent, and ultrasonic treatment is carried out for 0.5 hour; 0.02g of nitrogen-doped MXene was poured into 10ml of DMF solvent and sonicated for 0.5 hours. And then pouring the cobalt phthalocyanine solution into the nitrogen-doped MXene solution, stirring at room temperature for 12 hours, filtering, washing and drying for 10 hours to obtain the cobalt phthalocyanine-loaded nitrogen-doped MXene composite material.
Example 2:
1. synthesis of MXene containing F end groups
2 ml of 49% HF solution was poured into a beaker, and 2g of Ti was added 3 AlC 2 The powder was stirred at 35 ℃ for 24 hours, washed centrifugally with deionized water, filtered and dried for 24 hours to obtain MXene.
2. Preparation of nitrogen-doped MXene
30g of urea is dissolved in 50ml of deionized water, 0.1g of MXene is added, the mixture is stirred into a uniform solution, and then the uniform solution is poured into a polytetrafluoroethylene high-pressure reaction kettle and is moved into a drying box to be kept for 12 hours at 180 ℃. And after the reaction is finished, centrifugally washing the reactant by using deionized water and ethanol, filtering and drying the reactant to obtain the nitrogen-doped MXene.
3. Preparation of nitrogen-doped MXene-loaded cobalt phthalocyanine composite material
0.005g of cobalt phthalocyanine is poured into 10ml of DMF solvent, and ultrasonic treatment is carried out for 1 hour; 0.02g of nitrogen-doped MXene was poured into 10ml of DMF solvent and sonicated for 1 hour. And then pouring the cobalt phthalocyanine solution into the nitrogen-doped MXene solution, stirring for 24 hours at room temperature, filtering, washing and drying for 12 hours to obtain the cobalt phthalocyanine-loaded nitrogen-doped MXene composite material.
Example 3
The application of the synthesized nitrogen-doped MXene-supported cobalt phthalocyanine composite material as an oxygen reduction catalyst in ORR (organic reduction) is tested.
An electrochemical workstation and an RDE rotating disk electrode are used for carrying out electrocatalysis performance test, a three-electrode system (an auxiliary electrode is a platinum electrode; a reference electrode is a calomel electrode, and the composite material obtained in example 1 is used as a working electrode) is placed into 0.1mol/L KOH solution under the condition of oxygen saturation, and an LSV test is carried out at the rotating speed of 1600rpm (as a catalyst, the catalytic reaction is O 2 +2H 2 O+4e - →4OH - (i.e., oxygen reduction reaction)). When in actual application, the catalyst is loaded on the cathode of the fuel cell to be used as a catalyst. The potentials herein were converted to standard hydrogen electrodes, oxygen was applied for 20 minutes prior to testing, the electrolyte was saturated, voltammetric cycling was performed at 1600rpm for 20 cycles of electrode material at a sweep rate of 50mv/s, followed by linear voltammetric testing at a sweep rate of 10mv/s in the range of 1-0.2V. Each experiment was repeated 3 times to ensure the reliability of the experimental data.
Fig. 3 shows the results of performance tests, where the starting potential and the half-wave potential are important indicators for evaluating the performance of ORR, and the larger the value of the two potentials in the LSV curve, the better, and the platinum carbon electrode has the best effect as the evaluation standard of ORR, i.e., the starting potential of 1.0V and the half-wave potential of 0.85V. The catalyst prepared by the patent is used in ORR, and the initial potential and the half-wave potential are 0.989V and 0.836V respectively. And the manufacturing cost of the catalyst is far lower than that of a platinum carbon catalyst. The final limiting current density is 9.45mA/cm 2 Much higher than platinum carbon.
The material obtained in example 2, according to the test method of example 3, has a half-wave potential of 0.823V, which is slightly lower than that of example 1.
Example 4
The other steps are the same as example 1, except that the amount of cobalt phthalocyanine in step 3 (preparation of the nitrogen-doped MXene supported cobalt phthalocyanine composite material) is changed from 0.02g to 0.1g (namely, the mass ratio of cobalt phthalocyanine to nitrogen-doped MXene is 5;
the product obtained was tested for properties in the same manner as in example 3.
Example 5
The other steps are the same as example 1, except that the amount of cobalt phthalocyanine in step 3 (preparation of the nitrogen-doped MXene supported cobalt phthalocyanine composite material) is changed from 0.02g to 0.002g (namely the mass ratio of cobalt phthalocyanine to nitrogen-doped MXene is 1;
the product obtained was tested for properties in the same manner as in example 3.
The performance of the materials obtained in examples 4-5 was tested, and when the mass ratio of cobalt phthalocyanine to nitrogen-doped MXene was 5. When the mass ratio of cobalt phthalocyanine to nitrogen-doped MXene is 1. This shows that the mass of cobalt phthalocyanine is too much, and the phenomenon of cobalt phthalocyanine molecule aggregation is generated because the redundant cobalt phthalocyanine molecules cannot generate axial coordination with nitrogen, so that the ORR catalytic effect is poor; and the ORR catalytic effect is not good because the excessive nitrogen element cannot be coordinated with cobalt phthalocyanine molecules, so that the nitrogen element and the residual lone electrons are caused, and only few active sites can be obtained.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
The invention is not the best known technology.

Claims (2)

1. A preparation method of a nitrogen-doped MXene-loaded cobalt phthalocyanine composite material is characterized by comprising the following steps:
in the first step, chemical etching is used to etch Ti 3 AlC 2 Etching MXene with F end groups adsorbed on the surface:
mixing Ti 3 AlC 2 Adding the powder into HF solution, stirring at 25-45 deg.C for 12-48 hr, centrifuging with deionized water, filtering, and drying for 12-24 hr to obtain MXene;
wherein 1-3g of Ti is added into every 10-20ml of HF solution 3 AlC 2 ；
Secondly, loading nitrogen element on MXene by adopting a one-step hydrothermal method:
dissolving urea in deionized water, adding MXene, stirring the solution, mixing, pouring into a polytetrafluoroethylene high-pressure reaction kettle, and keeping at 150-200 ℃ for 8-32 hours; after the reaction is finished, washing, filtering and drying to obtain the nitrogen-doped MXene;
wherein, 2 to 3g of urea and 0.005 to 0.01g of MXene are added into each 5ml of water;
thirdly, loading cobalt phthalocyanine on the nitrogen-doped MXene by adopting a solvent method:
then pouring a cobalt phthalocyanine solution into the nitrogen-doped MXene solution, stirring at room temperature for 12-24 hours, filtering, washing, and drying for 10-12 hours to obtain the cobalt phthalocyanine-loaded nitrogen-doped MXene composite material;
wherein the mass ratio of cobalt phthalocyanine to nitrogen-doped MXene is 1:0.5 to 6;
the concentration of the HF solution in the first step is 40-49%, and Ti is added 3 AlC 2 The powder size is 200-400 meshes;
the solvent of the cobalt phthalocyanine solution and the nitrogen-doped MXene solution in the third step is DMF; adding 0.005-0.5 g of cobalt phthalocyanine into every 10ml of DMF; 0.0025 to 3.0g of nitrogen-doped MXene is added into every 10ml of DMF.
2. The application of the nitrogen-doped MXene-supported cobalt phthalocyanine composite prepared by the method according to claim 1, wherein the composite is supported on a cathode of a fuel cell as a catalyst.
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