CN114284515B - Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation method and application of composite material - Google Patents
Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation method and application of composite material Download PDFInfo
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Abstract
The invention relates to a ternary heterostructure FePc/Ti 3 C 2 /g‑C 3 N 4 A preparation method and application of the composite material. The method firstly prepares single-layer Ti 3 C 2 Combining it with FePC to form a composite material, and combining it with g-C 3 N 4 The ternary heterostructure FePc/Ti3C2/g-C3N4 composite material is formed by combination. The invention applies it to Oxygen Reduction Reaction (ORR) and is carried out by reacting FePc, ti 3 C 2 And g-C 3 N 4 The advantages of the platinum-carbon composite material are more outstanding by utilizing intermolecular force combination, the defects are mutually complemented, and the excellent oxygen reduction activity far exceeding that of the current commercial platinum-carbon is obtained, so that the platinum-carbon composite material has a wide application prospect.
Description
Technical Field
The invention belongs to Ti 3 C 2 The technical field of composite materials, in particular to a single-layer Ti 3 C 2 More particularly relates to a ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 A method for preparing a composite material and application for oxygen reduction reaction.
Background
With the advent of global energy crisis and the increasing environmental pollution and greenhouse effect caused by fossil fuel combustion, development of clean energy is urgent. There is increasing interest in the storage and conversion of sustainable energy, and fuel cells have high research value as one of the most promising clean energy converters at present. In a fuel cell, fuel is oxidized at the anode and the released electrons are transferred to the cathode through an external circuit, where oxygen is reduced. However, the kinetics are very slow due to the reduction of oxygen to four electrons, which greatly limits the energy output efficiency of the fuel cell. ORR is a very important reaction for fuel cells. The best ORR catalysts at present are well known to be Pt-based catalysts. Although the platinum-based catalyst has the most outstanding catalytic activity, it is not only poor in stability but also scarce in platinum, less in reserves and expensive. It is therefore necessary to develop a highly efficient, highly stable non-platinum based catalyst.
In recent years, a novel 2D material Ti 3 C 2 Transition metal carbides/nitrides, having unique structural and electronic properties, have attracted considerable attention from researchers. Ti (Ti) 3 C 2 As an emerging two-dimensional material, they exhibit high conductivity, surface hydrophilicity and good stability. In addition, as a class of materials with ultra-low work function and electronegative surfaces, ti 3 C 2 Is a potential support material that may alter the electrophilicity of the active center of the catalyst. Thereby adjusting the catalytic performance in the multicomponent catalyst system, and being applicable to various other clean energy reactions so as to realize sustainable energy future. Ti (Ti) 3 C 2 The materials are developed for a short time, and most of researches are currently applied to the field of energy storage as electrode materials, and the application of the materials in the field of electrocatalysts is still in a primary stage. Therefore, there is great prospect in the design of novel high-efficiency electrocatalysts by studying their structure and electronic properties.
Since 1964After first finding that cobalt phthalocyanine (CoPC) has oxygen reduction catalytic activity, researchers found that a large number of transition metal macrocyclic compounds have oxygen reduction catalytic activity, the most representative of which is iron phthalocyanine (FePC). The transition metal macrocyclic compound is typically a metal-nitrogen-carbon (M-N 4 -C) catalysts, the M-N4 structure formed by the central metal atom with the surrounding nitrogen atoms is generally the active center of such catalysts. However, the transition metal macrocyclic compound is easily oxidized in the air, so that serious aggregation phenomenon occurs, and the conductivity and catalytic activity of molecules are reduced.
Carbon nitride is used as a nonmetallic semiconductor material and is provided with 5 allotropes, and graphite phase carbon nitride (g-C 3 N 4 ) Is the most stable crystal form. g-C 3 N 4 Has excellent physicochemical and thermal stability, and g-C when the temperature is raised to 750 DEG C 3 N 4 It is completely decomposed and is not dissolved in acid-base or organic solvent. Economical and green, easy to synthesize, and has certain defects on the surface, rich-NH 2 group and PAI co-track system, and convenient to modify, thereby controllably adjusting g-C 3 N 4 Is an electronic structure of (a). But for g-C 3 N 4 The low conductivity of the oxygen reduction reaction is the greatest disadvantage limiting it.
Disclosure of Invention
The invention aims at providing a ternary heterostructure FePc/Ti aiming at the defects existing in the prior art 3 C 2 /g-C 3 N 4 Preparation of composite materials and application thereof as oxygen reduction catalysts. The method firstly prepares single-layer Ti 3 C 2 Combining it with FePC to form a composite material, and combining it with g-C 3 N 4 The ternary heterostructure FePc/Ti3C2/g-C3N4 composite material is formed by combination. Most of them are made of Ti 3 C 2 The material is used as a substrate material in the field of photocatalysis, and is applied to Oxygen Reduction Reaction (ORR) by using FePc and Ti 3 C 2 And g-C 3 N 4 The advantages of the molecular combination are more outstanding, the defects are mutually complemented, and the molecular combination far exceeds the current commercial valueThe excellent oxygen reduction activity of platinum carbon has wide application prospect.
The invention provides the following specific technical scheme:
ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 A method of preparing a composite material, the method comprising the steps of:
first, ti is prepared 3 C 2 :
Putting titanium aluminum carbide into a container, adding hydrofluoric acid, stirring for 24-36h, centrifugally washing with deionized water at 3200-4000rpm to neutrality, suction filtering, and drying in a drying oven at 60-80deg.C to obtain titanium carbide (Ti) 3 C 2 )；
Wherein, each gram of titanium aluminum carbide is put into 5-15mL of hydrofluoric acid; the mass percentage concentration of the hydrofluoric acid is 40% -60%;
second step, preparing monolayer Ti 3 C 2 :
Then the treated Ti is 3 C 2 Soaking in dimethyl sulfoxide (DMSO), standing for 24-48 hr, ultrasonic treating under nitrogen for 7-10 hr, suction filtering, and drying in a drying oven at 60-80deg.C for 10-15 hr to obtain single-layer Ti 3 C 2 ；
Preferably every 0.1g of Ti 3 C 2 Placing 20-40 mM LDMSO.
Third step, fePc/Ti is prepared 3 C 2 Precursor body
The single-layer Ti obtained in the last step is used for 3 C 2 Adding into N, N-Dimethylformamide (DMF), and performing ultrasonic treatment for 20-40min; iron phthalocyanine (FePC) is dissolved in DMF and is uniformly dispersed by ultrasonic for half an hour; mixing the two solutions, ultrasonically treating for 40-70min, suction filtering, and drying in a drying oven at 60-80deg.C for 10-15 hr to obtain FePc/Ti 3 C 2 A precursor;
wherein, every 0.02g of Ti 3 C 2 Placing into 9-12mLDMF, and placing FePC of 0.02g into 9-12 mLDMF; the mass ratio of FePc to Ti3C2 is FePc: t3c2=1: 1-2.5;
fourth step, g-C is prepared 3 N 4 :
After grinding melamine, placing the melamine into a porcelain boat, and calcining the melamine for 3 to 4 hours at the temperature of between 500 and 600 ℃ by using a muffle furnace to obtain yellow solid g-C 3 N 4 Grinding into fine powder.
Fifth step, preparing ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Composite material
And then g-C obtained in the fourth step 3 N 4 Placing in deionized water, ultrasonic treating for 40-70min, adding FePc/Ti 3 C 2 Pouring the precursor into a container containing g-C 3 N 4 In the solution of (2), placing the mixture in a water bath kettle, stirring and heating at 60-80 ℃ for 10-15h, suction-filtering, and then placing the mixture in a drying oven at 60-80 ℃ for drying for 10-15h to obtain the black composite material FePc/Ti 3 C 2 /g-C 3 N 4
Wherein, g-C is 0.1g each 3 N 4 Dissolving in 30-40mL deionized water, fePc/Ti 3 C 2 Precursor and g-C 3 N 4 The mass ratio of (C) is FePc/Ti3C2: g-c3n4=1: 5-10.
The ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 The application of the composite material is that the composite material is loaded on the cathode of the fuel cell to be used as a catalyst.
The invention has the substantial characteristics that:
the invention selects novel two-dimensional material Ti 3 C 2 The titanium aluminum carbide is etched and then intercalated to obtain single-layer Ti 3 C 2 And combining it with carbon-based metal macrocyclic compounds FePc and g-C 3 N 4 Combining to obtain ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Composite materials, and the synthesized materials are first applied to the oxygen reduction reaction ORR.
Compared with the known preparation method of the two-dimensional composite material loaded by other carbon-based metal macrocyclic compounds, the method provided by the invention has the advantages that firstly, the titanium aluminum carbide is etched and then intercalated to obtain a single-layer Ti 3 C 2 Monolayer Ti 3 C 2 The conductive material has extremely strong conductivity, and has larger defect degree and specific surface area, and can absorb oxygen better; and FePc, ti 3 C 2 And g-C 3 N 4 All have lamellar structures, so that the combination of the three can generate a synergistic effect, and the synergistic effect can greatly improve the catalytic reduction effect on oxygen.
The beneficial effects of the invention are as follows:
the invention prepares a ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Compared with other metal catalysts, the catalyst adopts the combination of the transition metal carbon-based macrocyclic compound and the non-metal material, avoids the use of noble metal, reduces the cost, has mild preparation conditions and basically low-temperature experimental conditions, and can effectively save energy. Simultaneous single layer of Ti 3 C 2 Compared with stacked Ti 3 C 2 Possessing stronger conductivity, exposing higher proportion of end groups, higher defect degree and more active sites, and reacting FePc with monolayer Ti by intermolecular forces 3 C 2 The pi-pi bond is used for bonding, so that the stability of FePc can be enhanced, agglomeration and metal center site falling are not easy to occur, and the FePc is formed in a single-layer Ti 3 C 2 FePc and Ti under the action of charged end group 3 C 2 Producing a synergistic effect which is beneficial for ORR activity; subsequently add g-C 3 N 4 Further enhances the stability of FePc and increases the synergistic effect, so that the catalytic performance of the catalyst is further improved, the electron transfer rate is increased, the charge transfer resistance is reduced, and the catalytic active sites are effectively increased. And in the vast majority with Ti 3 C 2 Materials with a substrate are used in the field of photocatalysis, and are applied to Oxygen Reduction Reactions (ORR). Through electrochemical performance test, the synthesized electrocatalytic composite material has excellent oxygen reduction catalytic activity. The initial potential and the half-wave potential are respectively: 1.00V and 0.92V, which are significantly better than 0.95V and 0.81V of commercial platinum carbon, and has higher limiting current density.
Description of the drawings:
FIG. 1 shows the single layer Ti as obtained in example 1 3 C 2 Atomic Force Microscope (AFM) images of atomic force microscopy topography of the material;
FIG. 2 shows the single layer Ti as obtained in example 1 3 C 2 Atomic Force Microscope (AFM) images of roughness curves of materials;
FIG. 3 shows a ternary heterostructure FePc/Ti obtained in example 1 3 C 2 /g-C 3 N 4 TEM image of the composite material;
FIG. 4 shows a ternary heterostructure FePc/Ti obtained in example 1 3 C 2 /g-C 3 N 4 Composite material, fePc, ti 3 C 2 And g-C 3 N 4 An XRD pattern of (a);
FIG. 5 shows a ternary heterostructure FePc/Ti obtained in example 1 3 C 2 /g-C 3 N 4 Linear voltammetric scan curves (sweep rate 10mv/s, rotational speed 1600 rpm) of the composite, fePc and commercial platinum carbon catalyst in 0.1mol/L oxygen saturated KOH solution.
FIG. 6 shows FePc and Ti obtained in example 1 3 C 2 And g-C 3 N 4 Linear voltammogram in 0.1mol/L oxygen saturated KOH solution (sweep speed 10mv/s, rotational speed 1600 rpm).
FIG. 7 shows FePc/Ti obtained in example 1 3 C 2 Precursor, fePc/g-C 3 N 4 、Ti 3 C 2 /g-C 3 N 4 And ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 The composite material was scanned in a linear voltammogram (sweep rate 10mv/s, rotational speed 1600 rpm) in 0.1mol/L oxygen saturated KOH solution.
The specific embodiment is as follows:
the ternary heterostructure FePc/Ti is described below by a specific example 3 C 2 /g-C 3 N 4 The preparation of the composite material and its use as an oxygen reduction catalyst are further described.
Example 1:
1. single layer Ti 3 C 2 Is prepared from
1g of titanium aluminum carbide powder is put into a clean beaker, 10mL of hydrofluoric acid with the mass percentage of 49% is added, and a preservative film is covered and dried in shadeStirring the mixture for 24 hours; then filtering to obtain solid precipitate, taking down the solid on the filter paper, putting the solid into a centrifuge tube, adding deionized water, washing at 3500rpm for 6 times until the PH of the deionized water in the centrifuge tube is 7, filtering, putting into a drying oven at 60 ℃ for drying for 10 hours, and etching the aluminum in the titanium aluminum carbide to obtain Ti 3 C 2 . Then 0.1g of treated Ti 3 C 2 Immersing in a beaker filled with 30mL of dimethyl sulfoxide, covering with a preservative film, keeping the preservative film at a dark and dry place for 24h, pouring into a Monte Carlo bottle, performing ultrasonic treatment under the protection of nitrogen for 7h, suction filtering, and drying in a drying oven at 60 ℃ for 10h to obtain single-layer Ti 3 C 2 。
2.FePc/Ti 3 C 2 Preparation of the precursor
0.02g of the single-layer Ti prepared in step 1 was reacted 3 C 2 Dissolving in beaker with 10 mM MF, and transferring into ultrasonic cleaner for half an hour to disperse uniformly; simultaneously dissolving 0.02g FePC in a beaker with 10mLDMF, moving the beaker into an ultrasonic cleaner for half an hour to uniformly disperse the FePC and the solution, mixing the two solutions, moving the mixed solution into the ultrasonic cleaner for ultrasonic treatment for one hour, carrying out suction filtration, and then drying the mixed solution in a drying oven at 60 ℃ for 10 hours to obtain FePc/Ti 3 C 2 A precursor.
3. Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation of composite materials
Grinding 1g melamine into fine powder in an agate mortar, placing into a cleaned porcelain boat, placing into a muffle furnace, heating to 500 ℃ at a temperature rising rate of 5 DEG/min under the protection of nitrogen, maintaining for 120min, cooling to room temperature, taking out yellow solid, grinding into fine powder in an agate mortar, and taking 0.1 g-C 3 N 4 Put into a beaker containing 30mL of deionized water, moved into an ultrasonic cleaner for half an hour to be dispersed evenly, and 0.02g of FePc/Ti is added 3 C 2 Pouring the precursor into a container containing g-C 3 N 4 Heating the solution in a beaker in a water bath at 60 ℃ for 10 hours, filtering, and drying in a drying oven at 60 ℃ for 10 hours to obtain ternary heterogeneous materialsStructure FePc/Ti 3 C 2 /g-C 3 N 4 A composite material.
Example 2:
1. single layer Ti 3 C 2 Is prepared from
2g of titanium aluminum carbide is put into a clean beaker, then 20mL of hydrofluoric acid with the concentration of 49% is added, a preservative film is covered, and the mixture is kept stirring for 36 hours at a dark and dry place; then filtering to obtain solid precipitate, taking down the solid on the filter paper, putting the solid into a centrifuge tube, adding deionized water, washing at 3500rpm for 6 times until the PH of the deionized water in the centrifuge tube is 7, putting the centrifuge tube into a vacuum drying oven at 80 ℃ for drying for 15 hours after the suction filtration, and etching the aluminum in the titanium aluminum carbide to obtain Ti 3 C 2 . Then 0.2g of treated Ti 3 C 2 Immersing in a beaker filled with 60mL of dimethyl sulfoxide, covering with a preservative film, keeping the preservative film at a dark and dry place for 36h, pouring into a Monte Carlo bottle, performing ultrasonic treatment under the protection of nitrogen for 12h, performing suction filtration, and drying in a vacuum drying oven at 80 ℃ for 15h to obtain single-layer Ti 3 C 2 。
2.FePc/Ti 3 C 2 Preparation of the precursor
Monolayer Ti prepared from 0.04g1 3 C 2 Dissolving in beaker with 20 mM MF, and transferring into ultrasonic cleaner for half an hour to disperse uniformly; simultaneously dissolving 0.06g FePC in a beaker with 20mLDMF, moving the beaker into an ultrasonic cleaner for half an hour to uniformly disperse the FePC and the solution, mixing the two solutions, moving the mixed solution into the ultrasonic cleaner for ultrasonic treatment for one hour, carrying out suction filtration, and then drying the mixed solution in a vacuum drying oven with 80 ℃ for 15 hours to obtain FePc/Ti 3 C 2 A precursor.
3. Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation of composite materials
Grinding 2g melamine into fine powder in an agate mortar, placing into a cleaned porcelain boat, placing into a muffle furnace, heating to 600 ℃ at a heating rate of 5 DEG/min under the protection of nitrogen, maintaining for 180min, cooling to room temperature, taking out yellow solid, and grinding into fine powder in an agate mortarAfter the powder, 0.28g of g-C was taken 3 N 4 Put into a beaker containing 30mL of deionized water, moved into an ultrasonic cleaner for half an hour to be dispersed evenly, and 0.04g of FePc/Ti is added 3 C 2 Pouring the precursor into a container containing g-C 3 N 4 Placing the solution in a beaker, placing the beaker in a water bath kettle at 80 ℃ for water bath heating for 15 hours, filtering, placing the beaker in a vacuum drying oven at 80 ℃ for drying for 15 hours, and obtaining the ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 A composite material.
Application examples
To be synthesized into ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 The composite materials were tested for use as oxygen reduction catalysts in ORR.
The electrocatalytic performance test was performed using an electrochemical workstation and an RDE rotating disk electrode, using a three-electrode system (auxiliary electrode is a platinum electrode; reference electrode is a platinum electrode, and the composite material obtained in example 1 is a working electrode), and under oxygen saturation, placing the composite material into 0.1mol/L KOH solution to perform LSV test at 1600rpm (as a catalyst, the catalytic reaction is O2+2H2O+4e-. Fwdarw.4OH- (i.e., oxygen reduction reaction)). In practical application, the catalyst is loaded on the cathode of the fuel cell to serve as a catalyst. The potentials herein were all converted to standard hydrogen electrodes, the electrolyte was saturated by oxygen for 20 minutes prior to testing, the electrode material was activated by voltammetric cycling at 1600rp and a sweep rate of 50mv/s for 20 cycles, and then linear voltammetric testing was performed 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.
FIGS. 1 and 2 show a single layer of Ti prepared according to the present invention 3 C 2 Atomic force microscopy of the precursor, from which we can see the monolayer Ti we have prepared 3 C 2 Is about 1-2nm, which is comparable to the single layer Ti reported in the prior literature 3 C 2 Demonstrating our monolayer Ti 3 C 2 Successfully prepared.
FIG. 3 shows a ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Of composite materialTransmission electron microscope scan, from which we can see a single layer of Ti respectively 3 C 2 FePC and g-C 3 N 4 Morphology of FePc/Ti is shown 3 C 2 /g-C 3 N 4 Structure of composite material
FIG. 4 shows a ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Composite material, fePc, ti 3 C 2 And g-C 3 N 4 Is a XRD pattern of (C). From the figure we can see that the diffraction peaks at 8.4 °, 18.1 °, 27.2 ° and 61 ° are due to Ti 3 C 2 The (002), (004), (006) and (110) planes of (C) confirm Ti 3 C 2 Is a successful synthesis of (a). (002) And (004) the lower basal peak displacement of the plane is due to the fact that the peak is displaced from Ti 3 AlC 2 Wherein Al is removed and Ti is introduced 3 C 2 Tx surface termination, e.g., -F, -O, and-OH. By analysis of g-C 3 N 4 The XRD patterns of (C) can be seen to correspond to g-C at peaks at 13.1℃and 27.4℃ 3 N 4 The (100) and (002) planes of (C) indicate the formation of g-C 3 N 4 . Furthermore, fePc/Ti 3 C 2 /g-C 3 N 4 The XRD spectrum of (C) containing peaks of three precursors can prove FePc/Ti 3 C 2 /g-C 3 N 4 Is a successful combination of (a) and (b). The FePc transitions from highly ordered to disordered due to the coupling of the dispersed FePc on the substrate. Thus, compared with pure FePc, fePc/Ti 3 C 2 /g-C 3 N 4 The characteristic peak of FePc is reduced. Furthermore, the characteristic peaks of the hybrids show a slight shift to lower angles compared to FePc due to extended delocalization of pi electrons, which is FePc versus Ti 3 C 2 Results of pi-pi interactions between. FePc/Ti compared to graphite carbon nitride 3 C 2 /g-C 3 N 4 The XRD pattern of (B) has no obvious change, which indicates FePc/Ti 3 C 2 In g-C 3 N 4 The nano-sheet has good dispersibility.
Weighing 6mg of ternary heterostructure FePc/Ti obtained in example 1 3 C 2 /g-C 3 N 4 The composite material is added into 1mL of perfluorosulfonic acid type polymer with the mass fraction of 0.2 percentAnd (3) performing ultrasonic dispersion on the solution (nafion solution) for 30min to form uniform dispersion liquid, thus obtaining the catalyst ink. The electrochemical workstation and the RDE rotary disk electrode are used for carrying out the electrocatalytic performance test, the working electrode is polished before the test, 10 mu L of catalyst ink is dripped on the surface of the working electrode, the catalyst ink is naturally dried at room temperature, and the electrode surface loading capacity is 0.32mg/cm 2 。
A three-electrode system (an auxiliary electrode is a platinum electrode; a reference electrode is a platinum electrode, and a working electrode is an electrode with catalyst ink dropwise added) is adopted. Under the condition of oxygen saturation, the LSV test is carried out in 0.1mol/L KOH solution at 1600rpm (the catalyst is catalyzed by O 2 +2H 2 O+4e - →4OH - (i.e., oxygen reduction reaction)). In practical application, the catalyst is loaded on the cathode of the fuel cell to serve as a catalyst. The potentials herein were all converted to standard hydrogen electrodes, the electrolyte was saturated by oxygen for 20 minutes prior to testing, the electrode material was activated by voltammetric cycling at 1600rpm and a sweep rate of 50mV/s for 20 cycles, and then linear voltammetric testing was performed 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. 5 shows the results of performance tests, the initial potential and the half-wave potential are important indicators for evaluating ORR performance, and the larger the values of the initial potential and the half-wave potential are, the better the values of the initial potential and the half-wave potential are in the LSV curve, and the platinum carbon electrode has the optimal effect as the evaluation standard of ORR, namely, the initial potential of 0.95V and the half-wave potential of 0.81V. The ternary heterostructure FePc/Ti prepared by the patent 3 C 2 /g-C 3 N 4 The composite catalyst was used in ORR with an initial potential and half-wave potential of 1.00V and 0.92V, respectively. And the manufacturing cost of the catalyst is far lower than that of a platinum carbon electrode. In addition ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 The final limiting current density of the composite catalyst is-6.18 mA/cm -2 Limiting current Density with platinum carbon-5.495 mA/cm -2 The catalyst prepared by the invention has excellent performance compared with the catalyst prepared by the invention.
FIG. 6 is FePc, ti 3 C 2 And g-C 3 N 4 Performance test results of FePc, ti 3 C 2 And g-C 3 N 4 The initial potential and the half-wave potential are lower than those of platinum carbon and the ternary heterostructure FePc/Ti prepared in example 1 3 C 2 /g-C 3 N 4 The initial potential and half-wave potential of the composite material indicate that our catalyst has catalytic activity far exceeding that of single raw material.
FIG. 7 is FePc/Ti 3 C5 precursor, fePc/g-C 3 N 4 、Ti 3 C 2 /g-C 3 N 4 And ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 The performance test result of the composite material, namely a comparison sample prepared by combining the ternary heterostructures in pairs, shows that the ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Three raw materials of the composite material are indispensable, and the side surface reaction of FePc and single-layer Ti by intermolecular force 3 C 2 By combining, the stability of FePc can be enhanced, so that the FePc is not easy to agglomerate and the metal center site is not easy to fall off, and the FePc is prepared in a single layer of Ti 3 C 2 FePc and Ti under the action of charged end group 3 C 2 Producing a synergistic effect which is beneficial for ORR activity; subsequently add g-C 3 N 4 Further enhances the stability of FePc and increases the synergistic effect, so that the catalytic performance of the catalyst is further improved, the electron transfer rate is increased, the charge transfer resistance is reduced, and the catalytic active sites are effectively increased.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will understand that various changes in form and details may be made therein without departing from the scope of the invention defined by the appended claims.
The invention is not a matter of the known technology.
Claims (6)
1. Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Of composite materialThe preparation method is characterized by comprising the following steps:
first, ti is prepared 3 C 2 ：
Putting titanium aluminum carbide into a container, adding hydrofluoric acid, stirring for 24-36h, centrifugally washing with deionized water to neutrality, suction filtering, and drying to obtain titanium carbide (Ti) 3 C 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein, each gram of titanium aluminum carbide is put into 5-15mL of hydrofluoric acid;
second step, preparing monolayer Ti 3 C 2 ：
Then the treated Ti is 3 C 2 Soaking in dimethyl sulfoxide (DMSO), standing for 24-48 hr, ultrasonic treating under nitrogen for 7-10 hr, suction filtering, and drying in a drying oven at 60-80deg.C for 10-15 hr to obtain single-layer Ti 3 C 2 ；
Third step, fePc/Ti is prepared 3 C 2 Precursor:
the single-layer Ti obtained in the last step is used for 3 C 2 Adding into N, N-Dimethylformamide (DMF) for ultrasonic dispersion; additionally, dissolving iron phthalocyanine (FePC) in DMF and performing ultrasonic dispersion; mixing the two solutions, ultrasonically treating for 40-70min, suction filtering, and drying in a drying oven at 60-80deg.C for 10-15 hr to obtain FePc/Ti 3 C 2 A precursor;
wherein, every 0.02g of Ti 3 C 2 Placing into 9-12mLDMF, and placing FePC of 0.02g into 9-12 mLDMF; the mass ratio is FePc: t3c2=1: 1-2.5;
fourth step, g-C is prepared 3 N 4 ：
After grinding melamine, placing the melamine into a porcelain boat, and calcining the melamine for 3 to 4 hours at the temperature of between 500 and 600 ℃ by using a muffle furnace to obtain yellow solid g-C 3 N 4 Grinding into fine powder;
fifth step, preparing ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Composite material:
and then g-C obtained in the fourth step 3 N 4 Placing in deionized water, ultrasonic treating for 40-70min, adding FePc/Ti 3 C 2 Pouring the precursor into a container containing g-C 3 N 4 Is placed in a water bath kettle 6Stirring and heating at 0-80 ℃ for 10-15h, suction filtering and drying to obtain black composite FePc/Ti 3 C 2 /g-C 3 N 4 ；
Wherein, g-C is 0.1g each 3 N 4 Dissolving in 30-40mL deionized water, fePc/Ti 3 C 2 Precursor and g-C 3 N 4 The mass ratio of (C) is FePc/Ti3C2: g-c3n4=1: 5-10.
2. The ternary heterostructure FePc/Ti according to claim 1 3 C 2 /g-C 3 N 4 The preparation method of the composite material is characterized in that in the first step, the revolution number of centrifugal washing is 3200-4000rpm; the mass percentage concentration of the hydrofluoric acid is 40% -60%.
3. The ternary heterostructure FePc/Ti according to claim 1 3 C 2 /g-C 3 N 4 The preparation method of the composite material is characterized in that the drying temperature in the first step, the second step, the third step and the fifth step is 60-80 ℃; the drying time is 10-15h.
4. The ternary heterostructure FePc/Ti according to claim 1 3 C 2 /g-C 3 N 4 A process for the preparation of a composite material, characterized in that in said second step, preferably every 0.1g of Ti 3 C 2 Placing 20-40 mM LDMSO.
5. The ternary heterostructure FePc/Ti according to claim 1 3 C 2 /g-C 3 N 4 The preparation method of the composite material is characterized in that in the third step, the ultrasonic dispersion time for the two times is 20-40min.
6. The ternary heterostructure FePc/Ti prepared by the method of claim 1 3 C 2 /g-C 3 N 4 A composite material application, characterized in that the composite material is supported on a cathode of a fuel cell as a catalyst.
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