CN111082075A - Preparation method of transition metal, nitrogen and boron co-doped nano composite electrocatalyst - Google Patents
Preparation method of transition metal, nitrogen and boron co-doped nano composite electrocatalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a transition metal, nitrogen and boron codoped nano composite electrocatalyst, which comprises the steps of firstly utilizing monomers with end groups respectively being catechol groups and phenylboronic acid groups to prepare borate microspheres through condensation reaction, then adding transition metal salt, introducing transition metal ions into the borate microspheres by utilizing the coordination force between the transition metal ions and the catechol groups, then calcining the borate microspheres at high temperature, and reducing the supported transition metal while carbonizing the borate microspheres. And etching by using hydrochloric acid with high concentration, and carbonizing at high temperature for the second time to obtain the transition metal, nitrogen and boron codoped nano composite electrocatalyst. The ORR catalytic activity of the finally obtained nano composite electrocatalyst is similar to that of a commercial Pt/C catalyst, and the catalytic stability and methanol resistance of the nano composite electrocatalyst are superior to those of the Pt/C catalyst.
Description
Technical Field
The invention belongs to the technical field of hybrid nano materials, and particularly relates to a preparation method of a transition metal, nitrogen and boron co-doped nano composite electrocatalyst.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have received considerable attention from researchers as an emerging clean energy source. The cell reaction of PEMFCs consists of both the oxidation of fuel at the anode and the reduction of oxygen at the cathode, the rate of the oxidation-reduction determining the operating efficiency of the fuel cell, and the rate of the reaction being determined by the catalyst. Since the overpotential of the Oxygen Reduction Reaction (ORR) of the cathode is much greater than that of the oxidation reaction of the anode, compared to the electrode reaction of the cathode which is more difficult to perform than the anode, the research on the catalyst of the cathode ORR has profound significance for the development of fuel cells. Because of their excellent activity in catalyzing ORR, the noble metals platinum (Pt) have traditionally been used commercially as ORR catalysts, either pure Pt or carbon black-supported Pt (Pt/C). However, Pt is not stable during use because it is agglomerated during the process of catalyzing ORR and is affected by factors such as fuel crossover. In addition, the high price of Pt itself limits its large-scale commercialization process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a transition metal, nitrogen and boron co-doped nano composite electrocatalyst.
The technical scheme of the invention is as follows:
a preparation method of a transition metal, nitrogen and boron co-doped nano composite electrocatalyst comprises the following steps:
(1) dissolving a catechol group-containing monomer and a phenylboronic acid group-containing monomer in a lower alcohol solvent according to a molar ratio of 1: 0.5-2, stirring and reacting for 6-12h at the temperature of 30-60 ℃ in a protected atmosphere and in a dark place at the rotating speed of 800rpm, then carrying out solid-liquid separation to obtain a solid, and washing and vacuum drying the solid to obtain the borate microsphere;
the catechol group-containing monomer is one of compounds DEC, DC, DFC, TEC, TC and PC shown in the following structural formula:
the monomer containing the phenylboronic acid group is one of compounds DEB, DB, DFB, TEB, TB and PB shown in the following structural formula:
(2) dispersing the borate microspheres in a lower alcohol solvent, dropwise adding the lower alcohol solution of a transition metal salt, keeping out of the sun at 30-60 ℃ in a protective atmosphere, stirring at the rotating speed of 400-800rpm for reaction for 1-6h, carrying out solid-liquid separation to obtain a solid, and washing and vacuum drying the solid to obtain the borate microspheres loaded with the transition metal salt, wherein the molar ratio of the borate microspheres to the transition metal salt is 1: 0.1-10;
(3) under the protective atmosphere, heating the borate microsphere loaded with the transition metal salt to 600-1000 ℃ at the speed of 5-10 ℃/min, calcining at constant temperature for 1-3h, and naturally cooling to room temperature to obtain the nano carbon material loaded with the transition metal;
(4) dispersing the nano carbon material in a 5-7M hydrochloric acid solution, reacting at the room temperature at the stirring speed of 400-800rpm for 6-8h, centrifuging, fully washing, drying in vacuum, heating to 600-1000 ℃ at the speed of 5-10 ℃/min under a protective atmosphere, calcining at a constant temperature for 3-5h, and naturally cooling to the room temperature to obtain the transition metal, nitrogen and boron co-doped nano composite electrocatalyst.
In a preferred embodiment of the present invention, the method for preparing the catechol-group-containing monomer comprises: mixing the polyamino compound and 3, 4-dihydroxy benzaldehyde according to the weight ratio of 1: 2-4, dissolving in a lower alcohol solvent, and stirring and reacting for 12-48h under the conditions of 10-50 ℃, light shielding and a stirring speed of 200-600rpm to obtain the catechol group-containing monomer.
Further preferably, the polyamino compound is ethylenediamine, p-phenylenediamine, 2- [4- (4-aminophenoxy) phenyl ] hexafluoropropane, tris (2-aminoethyl) amine, tris (4-aminophenyl) amine or 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin.
In a preferred embodiment of the present invention, the method for preparing the monomer containing a phenylboronic acid group comprises: dissolving a polyamino compound and 4-formylphenylboronic acid in a lower alcohol solvent according to a molar ratio of 1: 2-4, and stirring and reacting for 12-48h under the conditions of 10-50 ℃, light shielding and a stirring speed of 200-600rpm to obtain the monomer containing the phenylboronic acid group.
Further preferably, the polyamino compound is ethylenediamine, p-phenylenediamine, 2- [4- (4-aminophenoxy) phenyl ] hexafluoropropane, tris (2-aminoethyl) amine, tris (4-aminophenyl) amine or 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin.
In a preferred embodiment of the present invention, the transition metal salt includes at least one of ferric chloride, cobalt chloride, nickel chloride, copper chloride, ferric acetate, cobalt acetate, nickel acetate, copper acetate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, and copper acetylacetonate.
In a preferred embodiment of the present invention, the catechol group-containing monomer is DC, DFC, TEC, TC or PC; the monomer containing the phenylboronic acid group is DB, DFB, TEB, TB or PB.
In a preferred embodiment of the present invention, the lower alcohol solvent is methanol or ethanol.
In a preferred embodiment of the present invention, the protective atmosphere is an inert gas atmosphere or a nitrogen atmosphere.
Further preferably, the inert gas is argon.
The invention has the beneficial effects that:
1. the invention adopts a template-free in-situ reduction method to synthesize the transition metal loaded nano composite electrocatalyst, the preparation process is simple, and the reaction conditions are mild.
2. According to the invention, nitrogen and boron elements are introduced in the monomer design process, and a transition metal source is introduced by virtue of the coordination force of catechol and transition metal ions, so that the doping of the impurity elements and the transition metal is beneficial to improving the ORR catalytic activity of the material.
3. The activity of the finally obtained nano composite electrocatalyst is close to that of a commercial Pt/C catalyst in the aspect of catalyzing ORR, and the stability and methanol resistance of the catalyst in the aspect of catalyzing ORR are superior to those of the Pt/C catalyst, so that the nano composite electrocatalyst has potential advantages in the aspect of preparing a novel non-noble metal ORR catalyst.
Drawings
FIG. 1 is a scanning electron micrograph of the product of each step of example 1 of the present invention.
Figure 2 is a XRD data pattern of the nanocomposite electrocatalyst prepared in example 1 of the present invention.
FIG. 3 is a graph of XPS data for a nanocomposite electrocatalyst prepared in example 1 of the present invention.
FIG. 4 is one of graphs comparing results of the nanocomposite electrocatalyst prepared in example 1 of the present invention with a commercial Pt/C catalyst.
FIG. 5 is a second graph of the results of a comparison of the nanocomposite electrocatalyst prepared in example 1 according to the present invention and a commercial Pt/C catalyst.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Preparation of borate microspheres:
tris (4-aminophenyl) amine (0.0956g, 0.334mmol) and 3, 4-dihydroxybenzaldehyde (0.138g, 1.0mmol) were dissolved in 20mL of ethanol and the reaction was stirred at 400rpm for 24h at 25 ℃. Kinetic studies samples were taken at set time intervals for GPC and NMR testing. The black solution obtained after the reaction is finished is the catechol group-containing monomer TC, and the reaction formula of the TC is as follows:
tris (4-aminophenyl) amine (0.0956g, 0.334mmol) and 4-formylphenylboronic acid (0.15g, 1.0mmol) were dissolved in 20mL of ethanol and the reaction was stirred at 400rpm at 25 ℃ for 24 h. Kinetic studies samples were taken at set time intervals for GPC and NMR testing. And (3) obtaining a yellow solution after the reaction, namely the yellow solution containing the phenylboronic acid group monomer TB, wherein the reaction formula of the TB is as follows:
the obtained catechol group-containing monomer TC (5mL, 0.0668mmol) and phenylboronic acid group-containing monomer TB (5mL, 0.0668mmol) were dissolved in 40mL of ethanol, and the mixture was stirred at 400rpm under protection of Ar gas and at 60 ℃ in the dark for 6 hours. And in the morphology research, samples are taken at set time intervals for SEM and TEM tests, and a dark red solution is obtained after the reaction is finished. Centrifugally separating to obtain a dark red solid, centrifugally washing the dark red solid for three times by using ethanol, and then carrying out vacuum drying to obtain the dark red solid, namely the borate microsphere.
(2) Preparation of transition metal salt supported borate microspheres:
the borate microspheres obtained above were dispersed in 40mL of ethanol, ferric chloride hexahydrate (0.01084g, 0.0668mmol) dissolved in 10mL of ethanol was added dropwise to the solution of borate microspheres, and the reaction was stirred at 400rpm under protection of Ar gas and at 60 ℃ for 1h in the absence of light. And after the reaction is finished, carrying out solid-liquid separation, washing the solid part with ethanol for three times, and then carrying out vacuum drying for 6h at the temperature of 60 ℃ to obtain a black red solid, namely the iron ion loaded borate microsphere.
(3) Preparation of transition metal, nitrogen and boron co-doped nano composite electrocatalyst:
and (3) placing the obtained iron ion-loaded borate microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of Ar, calcining at constant temperature for 1h, and naturally cooling to room temperature to obtain black powder. The black powder was dispersed in 6M hydrochloric acid solution, reacted at room temperature for 6 hours at a stirring rate of 400rpm, centrifugally washed 3 times with ultrapure water after completion of the reaction, and vacuum dried at 60 ℃ for 12 hours. And (3) placing the black powder treated by hydrochloric acid into a tubular furnace again, heating to 800 ℃ at the heating rate of 5 ℃/min under the protection of Ar, calcining at constant temperature for 3h, and naturally cooling to room temperature to obtain the black powder, namely the iron/nitrogen and boron co-doped nano composite electrocatalyst (Fe-N/B-Cs).
Example 2
(1) Preparation of borate microspheres:
2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane (0.2592g, 0.5mmol) and 3, 4-dihydroxybenzaldehyde (0.138g, 1.0mmol) were dissolved in 20mL of methanol and the reaction was stirred at 25 ℃ at 400rpm for 24 h. Kinetic studies samples were taken at set time intervals for GPC and NMR testing. The black solution obtained after the reaction is the catechol group-containing monomer DFC, and the reaction formula of the DFC is as follows:
2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane (0.2592g, 0.5mmol) and 4-formylphenylboronic acid (0.15g, 1.0mmol) were dissolved in 20mL of methanol and the reaction was stirred at 400rpm for 24h at 25 ℃. Kinetic studies samples were taken at set time intervals for GPC and NMR testing. The yellow solution obtained after the reaction is finished is the monomer DFB containing the phenylboronic acid group, and the reaction formula of the DFB is as follows:
the resulting catechol-group-containing monomer DFC (5mL, 0.125mmol) and phenylboronic acid-group-containing monomer DFB (5mL, 0.125mmol) were dissolved in 40mL of ethanol, and the mixture was stirred at 400rpm under protection of Ar gas and at 40 ℃ for 6 hours. And in the morphology research, samples are taken at set time intervals for SEM and TEM tests, and a dark red solution is obtained after the reaction is finished. Centrifugally separating to obtain a dark red solid, centrifugally washing the dark red solid for three times by using ethanol, and then carrying out vacuum drying to obtain the dark red solid, namely the borate microsphere.
(2) Preparation of transition metal salt supported borate microspheres:
the borate microspheres obtained above were dispersed in 40mL of ethanol, cobalt chloride tetrahydrate (0.022g, 0.125mmol) dissolved in 10mL of ethanol was dropwise added to the solution of borate microspheres, and the reaction was stirred at 400rpm under protection of Ar gas and at 60 ℃ for 1 hour with exclusion of light. And after the reaction is finished, carrying out solid-liquid separation, washing the solid part with ethanol for three times, and then carrying out vacuum drying for 6h at the temperature of 60 ℃ to obtain a black-red solid, namely the cobalt ion loaded borate microsphere.
(3) Preparation of transition metal, nitrogen and boron co-doped nano composite electrocatalyst:
and (3) placing the obtained cobalt ion-loaded borate microspheres in a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of Ar, calcining at constant temperature for 1h, and naturally cooling to room temperature to obtain black powder. The black powder was dispersed in 6M hydrochloric acid solution, reacted at room temperature for 6 hours at a stirring rate of 400rpm, centrifugally washed 3 times with ultrapure water after completion of the reaction, and vacuum dried at 60 ℃ for 12 hours. And (3) placing the black powder treated by hydrochloric acid into a tubular furnace again, heating to 800 ℃ at the heating rate of 5 ℃/min under the protection of Ar, calcining at the constant temperature for 3h, and naturally cooling to room temperature to obtain the black powder, namely the cobalt/nitrogen and boron Co-doped nano composite electrocatalyst (Co-N/B-Cs).
Examples 3 to 5:
with the same process conditions as in example 1, when the borate microspheres were prepared, the catechol group-containing monomer and the phenylboronic acid group-containing monomer were changed to synthesize different transition metal, nitrogen, and boron co-doped nanocomposite electrocatalysts, and the results are shown in table 1.
TABLE 1
Examples 6 to 9:
with the same process conditions as in example 1, the types of transition metal salts were changed when preparing the transition metal salt supported borate microspheres, and different transition metal, nitrogen, and boron co-doped nanocomposite electrocatalysts were synthesized, and the results are shown in table 2.
TABLE 2
Examples 10 to 12:
with the same process conditions as in example 1, different transition metal, nitrogen and boron co-doped nanocomposite electrocatalysts were synthesized by changing the calcination temperature during the preparation of the transition metal, nitrogen and boron co-doped nanocomposite electrocatalysts, and the results are shown in table 3.
TABLE 3
In fig. 1, a is a TEM picture of the borate microsphere without ferric chloride introduced before sintering in example 1 at an amplification factor of 40K, and it can be seen that the microsphere has a good morphology and a particle size of about 200 nm; in fig. 1, b is a TEM image of the borate microsphere with an amplification factor of 40K after the ferric chloride is introduced before sintering in example 1, after the ferric chloride is introduced, the particle size of the microsphere is not changed, but a plurality of holes are etched on the surface, which is a result of iron ions entering the borate network to replace phenylboronic acid groups; in fig. 1, c is a TEM picture of the nanocomposite electrocatalyst at an amplification factor of 40K in example 1, after carbonization, many micropores appear on the surface of the carbon spheres, and the particle size is slightly reduced, about 160 nm.
Figure 2 is XRD data for the nanocomposite electrocatalyst of example 1. After comparing PDF cards, Fe contained in the electrocatalyst can be seen3C result, and Fe can not be found in the electrocatalyst due to the etching effect of the hydrochloric acid2O3And (4) components.
FIG. 3 shows the nano-composite electrocatalyst prepared in example 1XPS data of (2). The element in graph a is N1 s, and its high resolution XPS can be divided into 6 peaks respectively at 403.2eV, 401.3eV, 400.3eV, 399.4eV, 398.3eV and 397.7eV, corresponding to the N oxide, graphite N, pyrrole N, amino group, pyridine N and N-B bond. The element in the graph B is B1 s, and the high resolution XPS can be divided into 3 peaks at 192.1eV, 190.8eV and 189.2eV, which correspond to B-O, B-N and B-C. The element in graph c is Fe 2p, and its high resolution XPS can be divided into two pairs of two peaks and one satellite peak, which are located at 725.7eV, 723.5eV, 719.8eV, 714.4eV and 710.0eV, respectively, corresponding to Fe3+2p1/2，Fe2+2p1/2Satellite peak, Fe3+2p3/2，Fe3+2p3/2。
Fig. 4a is a comparison of CV curves of the nanocomposite electrocatalyst and the commercial Pt/C catalyst in example 1, the dashed and solid line portions correspond to argon saturation conditions and oxygen saturation conditions, respectively, and it can be seen that the CV curve of the nanocomposite electrocatalyst shows a peak for oxygen reduction at 0.779V under the oxygen saturation conditions, indicating the occurrence of oxygen reduction reaction. The CV curve oxygen reduction peak of the commercial Pt/C catalyst was at 0.835V, indicating that the oxygen reduction catalytic performance of the nanocomposite electrocatalyst was similar to the commercial Pt/C catalyst. Fig. 4b is a comparison of LSV curves of the nanocomposite electrocatalyst and the commercial Pt/C catalyst in example 1, the peak and half-wave potentials of the nanocomposite electrocatalyst are at 0.929V and 0.798V, respectively, and it can be seen that the catalytic performance is excellent, compared to the commercial Pt/C catalyst, the peak and half-wave potentials are at 0.964V and 0.836V, respectively.
Fig. 5a is a comparison of the chronoamperometric curves of the nanocomposite electrocatalyst and the commercial Pt/C catalyst of example 1, and the relative activities of the nanocomposite electrocatalyst and the commercial Pt/C catalyst remained at the initial 93.2% and 87.9% respectively after 20000s of testing, indicating that the electrochemical stability of the nanocomposite electrocatalyst is superior to that of the commercial Pt/C catalyst. FIG. 5b is a comparison of the methanol tolerance test of the nanocomposite electrocatalyst and the commercial Pt/C catalyst of example 1, wherein the reduction current of the nanocomposite electrocatalyst is maintained substantially constant after the methanol addition at 200s, while the oxidation current of methanol occurs immediately with the commercial Pt/C catalyst, indicating that the prepared nanocomposite electrocatalyst has high selectivity and better methanol tolerance in the catalytic oxygen reduction reaction.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A preparation method of a transition metal, nitrogen and boron co-doped nano composite electrocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving a catechol group-containing monomer and a phenylboronic acid group-containing monomer in a lower alcohol solvent according to a molar ratio of 1: 0.5-2, stirring and reacting for 6-12h at the temperature of 30-60 ℃ in a protected atmosphere and in a dark place at the rotating speed of 800rpm, then carrying out solid-liquid separation to obtain a solid, and washing and vacuum drying the solid to obtain the borate microsphere;
the catechol group-containing monomer is one of compounds DEC, DC, DFC, TEC, TC and PC shown in the following structural formula:
the monomer containing the phenylboronic acid group is one of compounds DEB, DB, DFB, TEB, TB and PB shown in the following structural formula:
(2) dispersing the borate microspheres in a lower alcohol solvent, dropwise adding the lower alcohol solution of a transition metal salt, keeping out of the sun at 30-60 ℃ in a protective atmosphere, stirring at the rotating speed of 400-800rpm for reaction for 1-6h, carrying out solid-liquid separation to obtain a solid, and washing and vacuum drying the solid to obtain the borate microspheres loaded with the transition metal salt, wherein the molar ratio of the borate microspheres to the transition metal salt is 1: 0.1-10;
(3) under the protective atmosphere, heating the borate microsphere loaded with the transition metal salt to 600-1000 ℃ at the speed of 5-10 ℃/min, calcining at constant temperature for 1-3h, and naturally cooling to room temperature to obtain the nano carbon material loaded with the transition metal;
(4) dispersing the nano carbon material in a 5-7M hydrochloric acid solution, reacting at the room temperature at the stirring speed of 400-800rpm for 6-8h, centrifuging, fully washing, drying in vacuum, heating to 600-1000 ℃ at the speed of 5-10 ℃/min under a protective atmosphere, calcining at a constant temperature for 3-5h, and naturally cooling to the room temperature to obtain the transition metal, nitrogen and boron co-doped nano composite electrocatalyst.
2. The method of claim 1, wherein: the preparation method of the catechol group-containing monomer comprises the following steps: dissolving polyamino compound and 3, 4-dihydroxy benzaldehyde in a lower alcohol solvent according to a molar ratio of 1: 2-4, and stirring and reacting for 12-48h under the conditions of 10-50 ℃, light shielding and a stirring speed of 200-.
3. The method of claim 2, wherein: the polyamino compound is ethylenediamine, p-phenylenediamine, 2- [4- (4-aminophenoxy) phenyl ] hexafluoropropane, tri (2-aminoethyl) amine, tri (4-aminophenyl) amine or 5,10,15, 20-tetra (4-aminophenyl) porphyrin.
4. The method of claim 1, wherein: the preparation method of the monomer containing the phenylboronic acid group comprises the following steps: dissolving a polyamino compound and 4-formylphenylboronic acid in a lower alcohol solvent according to a molar ratio of 1: 2-4, and stirring and reacting for 12-48h under the conditions of 10-50 ℃, light shielding and a stirring speed of 200-600rpm to obtain the monomer containing the phenylboronic acid group.
5. The method of claim 4, wherein: the polyamino compound is ethylenediamine, p-phenylenediamine, 2- [4- (4-aminophenoxy) phenyl ] hexafluoropropane, tri (2-aminoethyl) amine, tri (4-aminophenyl) amine or 5,10,15, 20-tetra (4-aminophenyl) porphyrin.
6. The method of claim 1, wherein: the transition metal salt comprises at least one of ferric chloride, cobalt chloride, nickel chloride, copper chloride, ferric acetate, cobalt acetate, nickel acetate, copper acetate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, ferric acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and copper acetylacetonate.
7. The production method according to any one of claims 1 to 6, characterized in that: the catechol group-containing monomer is DC, DFC, TEC, TC or PC; the monomer containing the phenylboronic acid group is DB, DFB, TEB, TB or PB.
8. The production method according to any one of claims 1 to 6, characterized in that: the lower alcohol solvent is methanol or ethanol.
9. The production method according to any one of claims 1 to 6, characterized in that: the protective atmosphere is inert gas atmosphere or nitrogen atmosphere.
10. The method of claim 9, wherein: the inert gas is argon.
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| CN116003806A (en) * | 2022-07-19 | 2023-04-25 | 厦门大学 | Boron-linked borate supermolecule, modified nanoparticle thereof, preparation method and application |
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