CN112151817A - Copper-based anode catalyst for direct methanol fuel cell and preparation method thereof - Google Patents
Copper-based anode catalyst for direct methanol fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a copper-based anode catalyst for a direct methanol fuel cell and a preparation method thereof, and the copper-based anode catalyst is a composite material which is loaded by a nitrogen-containing carbon material and contains 60-80 wt% of simple substance copper nanocrystals, is obtained by taking polyvinyl alcohol-polyaniline conductive hydrogel subjected to freeze thawing as a carrier, loading transition metal copper by electrodeposition and calcining in an inert atmosphere. The invention adopts a brand new catalyst carrier to load transition metal copper by electrodeposition to replace noble metal, and regulates the electronic structure of the catalyst by doping heteroatom, thereby improving the catalytic activity and electrode conductivity of the catalyst, and the catalyst can be directly used as the anode of a direct methanol fuel cell and has excellent electrochemical reaction activity.
Description
Technical Field
The invention relates to a fuel cell anode catalyst, in particular to a non-noble metal-based carbon material anode catalyst for a direct methanol fuel cell in an alkaline system and a preparation method thereof. The catalyst prepared by the invention can be used for electrocatalytic oxidation of methanol.
Background
In order to meet the increasing energy demand of human beings and solve the increasingly serious environmental problems, green and alternative novel energy research is increasingly gaining attention.
The Direct Methanol Fuel Cell (DMFC) as a fuel cell using methanol as fuel has the advantages of wide fuel source, convenient use, low price, and the like, and the transportation and storage of methanol are more convenient and safer. Methanol of DMFC is directly oxidized at the electrode to convert chemical energy into electrical energy, and the product is mainly H2O and CO2Does not generate NOx、SOxAnd the like, and has wide application prospect in the fields of portable electronic equipment, energy automobiles and the like.
In order to achieve a wider range of commercial applications, it is desirable to obtain highly active methanol oxidation electrocatalysts. Such as Pt [ M. Huang, J. Zhang, C. Wu, L. Guan, J. Power Sources 342(2017) 273; H. huang, s. Yang, r. Vajtai, x. Wang, p.m. Ajayan, adv. mater. 26(2014) 5160 ], Ru [ t.r. Garrick, w. Diao, j.m. Tengco, e.a. Stach, s.d. senayake, d.a. Chen, j.r. Monnier, j.w. Weidner, electrochim. Acta 195(2016) 106; noble metal elements such as Z, Bo, D, Hu, J, Kong, J, Yan, K, Cen, J, Power Sources 273(2015) 530- < - > and Pd [ C, Wen, Y, Wei, D, Tang, B, Sa, T, Zhang, C, Chen, Sci, Rep.7 (2017) 4907 > ] are well known electrocatalysts and have excellent electrochemical activity when used in DMFC.
To date, the Pt-Ru alloy catalyst has been considered to be the most active direct methanol fuel cell anode catalyst among all catalysts.
However, Pt-based catalysts are also easily poisoned by methanol and reaction intermediates (CO, etc.) in addition to high cost, high cost of catalysts [ w. Huang, h. Wang, j. Zhou, j. Wang, p.n. Duchesne, d. Muir, p. Zhang, n. Han, f. Zhao, m. Zeng, j. Zhong, c. Jin, y. Li, s.t. Lee, h. Dai, nat. commun. 6 (2015)) 10035 ] and poisoning effects [ s. Lu, h. Li, j. Sun, z. Zhuang, Nano res. 11 (2018)) 2058 ], which limit their commercialization. Therefore, there is significant practical interest in the development of alternative non-noble metal electrocatalysts.
In recent years, as one of the substitutes for noble metals, transition metal oxides have shown remarkable progress in electrocatalytic oxidation of methanol. Wherein, the copper-based catalyst [ S. Ananthraj, H. Sugime, S. Noda, ACS appl. mater. Interfaces, 12(2020) 27327 and 27338.; s.m. Pawar, j. Kim, a.i. Inamdar, h.woo, y. Jo, b.s. Pawar, s.cho, h.kim, h.im, sci. rep.6 (2016) 21310; D. wu, W, Zhang, D, Cheng, ACS appl. Mater. Interfaces, 9(2017) 19843-19851 ] have been used as electrocatalytic oxidation catalysts for methanol, and have attracted more attention in methanol oxidation applications.
Generally, in order to prepare a high-efficiency catalyst, carbon materials such as carbon black, carbon nanotubes, and graphene are generally used as a conductive framework of the catalyst, and a copper active component is used as an active site for catalyzing a methanol reaction. However, the traditional copper-based catalyst has a complex preparation method, and the dispersion of the active component copper is uneven, so that the electrocatalytic performance of methanol oxidation is influenced, and the wide application of the catalyst is limited.
For example, in the above-mentioned documents, Cu (OH)2Methanol oxidation current density of the-CuO/Cu catalyst at 0.65V (vs SCE) voltage of only 70mA ∙ cm−2，Cu(OH)2The current density of the catalyst for methanol oxidation under the voltage of 0.6V (vs SCE) is only 52mA ∙ cm−2Whereas the methanol oxidation current density of the Cu/NiCu NWs-220/C catalyst at a voltage of 0.5V (vs SCE) is only 34.9mA ∙ cm−2. Therefore, it is required to find a simple method for organically combining the active component copper with the carbon material having excellent conductivity so as to prepare a copper-based composite having high electrocatalytic oxidation performance of methanol.
Disclosure of Invention
The invention aims to provide a copper-based anode catalyst for a direct methanol fuel cell and a preparation method of the copper-based anode catalyst, which can improve the catalytic activity of the catalyst and the electrical conductivity of an electrode by doping heteroatom to regulate the electronic structure of the catalyst.
The copper-based anode catalyst for the direct methanol fuel cell is an elemental copper nanocrystalline composite material loaded by a nitrogen-containing carbon material, which is obtained by taking polyvinyl alcohol-polyaniline conductive hydrogel subjected to freeze thawing as a carrier, loading transition metal copper through electrodeposition and calcining in an inert atmosphere, wherein the elemental copper content is 60-80 wt%.
The polyvinyl alcohol-polyaniline conductive hydrogel subjected to freeze-thaw treatment is a hydrogel product obtained by performing polymerization reaction on triaminophenylboronic acid hydrochloride (ABA), Aniline (AN) and polyvinyl alcohol (PVA) serving as raw materials in AN aqueous solution system containing initiator Ammonium Persulfate (APS), freezing the polyvinyl alcohol-polyaniline conductive hydrogel at low temperature, then thawing the frozen polyvinyl alcohol-polyaniline conductive hydrogel at normal temperature, and performing freeze-thaw treatment for at least 1 time.
According to the polyvinyl alcohol-polyaniline conductive hydrogel subjected to freeze thawing treatment, polyaniline nanoparticles gathered during freeze thawing are converted into the compact nanosheets with the honeycomb structures through internal mechanical pressure, and the hydrogel treated in such a way has a large specific surface area and more active sites.
Specifically, the freeze-thaw treatment is to freeze at a low temperature of-20 ℃ for not less than 8 hours and then place the frozen.
The invention further provides a preparation method of the copper-based anode catalyst for the direct methanol fuel cell, which comprises the steps of adding hydrochloric acid solution of triaminobenzene borate and aniline into polyvinyl alcohol aqueous solution, uniformly dissolving, cooling to 0 ℃, dropwise adding ammonium persulfate solution, carrying out polymerization reaction to obtain polyvinyl alcohol-polyaniline conductive hydrogel as a carrier, carrying out freeze-thaw treatment for at least 1 time, placing the polyvinyl alcohol-polyaniline conductive hydrogel as a working electrode in copper electroplating solution, carrying out electrodeposition in a three-electrode system of a platinum wire counter electrode and a calomel reference electrode to deposit metal copper on the surface of the carrier, taking out, cleaning, drying, and calcining at 400-800 ℃ under inert atmosphere to obtain the Cu-N-C composite catalyst.
Furthermore, the molar ratio of the used triaminophenylboronic acid hydrochloride to the used aniline used as the raw material for the polymerization reaction is 0.01-0.1: 1, and the used amount of the polyvinyl alcohol is 30-600 times of the mass of the triaminophenylboronic acid hydrochloride.
More specifically, the polymerization reaction is carried out at room temperature, and the reaction time is preferably 6-30 h.
In the above preparation method of the present invention, preferably, the mass concentration of the polyvinyl alcohol aqueous solution is 8 to 12 wt%.
More specifically, according to the present invention, after the hydrochloric acid solution of triaminophenylborate hydrochloride and aniline are added to the polyvinyl alcohol aqueous solution, the temperature is raised to 55 ℃, and the mixture is stirred and dissolved, such that a solution with uniform dissolution is obtained.
Preferably, the prepared polyvinyl alcohol-polyaniline conductive hydrogel is subjected to freeze-thaw cycling for 1-5 times.
Further, the polyvinyl alcohol-polyaniline conductive hydrogel subjected to freeze thawing treatment is placed in 0.5-3 mol/L copper electroplating solution for electrodeposition, and the preferable electrodeposition time is 8-12 h.
Furthermore, the electrodeposition voltage is controlled between-0.7 and-1.5V.
The invention preferably adopts a freeze drying mode to dry the polyvinyl alcohol-polyaniline conductive hydrogel deposited with the elemental copper and subjected to freeze thawing treatment. Freeze-drying helps to preserve the characteristic porous nature of the hydrogel so that, after calcination in an inert atmosphere, an elemental copper nanocrystalline composite is obtained that is encapsulated by a nitrogen-containing carbon material.
Wherein the calcination time is preferably 1-5 h.
More specifically, the method comprises the step of heating the polyvinyl alcohol-polyaniline conductive hydrogel deposited with the elemental copper and subjected to freeze thawing treatment from room temperature to 400-800 ℃ at the speed of 1-5 ℃/min for calcination.
The invention adopts the polyvinyl alcohol-polyaniline conductive hydrogel which is subjected to freeze thawing treatment as a brand new catalyst carrier, and the transition metal copper is loaded by an electrodeposition method to replace noble metal, and the nitrogen-containing carbon material wrapped elementary copper nanocrystalline composite material is obtained by calcination. The catalyst is used as an anode catalyst of a direct methanol fuel cell and is directly used as an anode electrode, and has excellent electrochemical reaction activity.
The copper-based anode catalyst for the direct methanol fuel cell, prepared by the invention, can be directly used as an anode electrode, does not use any binder or conductive matrix, can avoid the existence of an inactive area, and enables the working electrode to have better conductivity. According to XRD, the copper is calcined in an inert atmosphere to obtain a simple substance of copper, but the simple substance of copper is not independent copper foil and is loaded on a carbon material to form a Cu-N bond, so that a Cu-N-C structure is formed.
According to the invention, heteroatom N is doped in the catalyst to regulate and control the electronic structure of the catalyst, so that the catalytic activity of the Cu-N-C composite catalyst is further improved. The activity of the electrochemical oxidation reaction of methanol of the Cu-N-C composite catalyst prepared by the method is tested by adopting a cyclic voltammetry, and the peak current density of 0.6V in the mixed electrolyte of 1M potassium hydroxide and 1M methanol solution can reach 189mA ∙ cm under the scanning rate of 50mV/s2Has obvious catalytic effect on methanol. Meanwhile, under the voltage of 0.6V, the current density retention rate is up to 75 percent through a test of a timing current method i-t for 10h, and the stability is far higher than that of a commercial Pt/C electrode.
Drawings
FIG. 1 is an X-ray diffraction pattern of Cu-N-C composite catalyst powder prepared in example 1.
FIG. 2 is a plot of cyclic voltammograms of the catalyst prepared in example 1 in a solution of 1M potassium hydroxide and 1M potassium hydroxide +1M methanol.
FIG. 3 is a graph of amperometric i-t measurements at 0.6V for 10h for the catalyst prepared in example 1.
Detailed Description
The following examples further describe embodiments of the present invention. The following examples are only for more clearly illustrating the technical solutions of the present invention so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the scope of the present invention. The following examples of the present invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Example 1.
0.0303g (0.175mmol) of triaminophenylboronic acid hydrochloride (ABA) is weighed and dissolved in 835 mu L of 6mol/L hydrochloric acid solution to prepare an ABA solution.
Sequentially adding the ABA solution, 0.233g (2.5mmol) of Aniline (AN) and 62 muL of deionized water into 2mL of 10wt% polyvinyl alcohol (PVA) solution, heating and stirring in a water bath at 55 ℃ for 30min, cooling in AN ice water bath to 0 ℃ after the solution is clear, dropwise adding 1.375mL of 2mol/L Ammonium Persulfate (APS) solution, quickly stirring uniformly, pouring into a mold, and standing at normal temperature for 24h to prepare the polyvinyl alcohol-polyaniline conductive hydrogel polymer film.
Placing the formed polyvinyl alcohol-polyaniline conductive hydrogel polymer film in a refrigerator with the temperature of-20 ℃ for 8h, taking out, placing at room temperature for unfreezing, washing with deionized water, and placing in a container containing 0.1mol/L H2SO4In 1mol/L copper sulfate electroplating solution, a polymer film is taken as a working electrode, a calomel electrode is taken as a reference electrode, a Pt wire is taken as a counter electrode to form a three-electrode system, and electrodeposition is carried out for 8 hours under the constant voltage of-1.0V.
Taking out the working electrode, washing with deionized water, freeze drying for 10 hr, placing in a tubular reaction furnace, and reacting in N2Raising the temperature from room temperature to 500 ℃ at the speed of 2 ℃/min for 2h in the atmosphere, and naturally cooling to room temperature to prepare the Cu-N-C catalyst.
FIG. 1 is a powder X-ray diffraction pattern of the catalyst prepared. Comparing the test results with JCPDS card number 04-0836, a standard joint committee on powder diffraction standard, diffraction peaks at diffraction angles 2 theta =43.3 degrees, 50.4 degrees and 74.1 degrees correspond to three different crystal faces (111), (200) and (220) of the elemental copper respectively, and the active substance copper in the catalyst is shown to be present as an elemental substance.
Example 2.
0.0358g (0.21mmol) of triaminophenylboronic acid hydrochloride (ABA) is weighed and dissolved in 835 mu L of 6mol/L hydrochloric acid solution to prepare an ABA solution.
Sequentially adding the ABA solution, 0.264g (2.8mmol) of Aniline (AN) and 234 muL of deionized water into 2mL of 10wt% polyvinyl alcohol (PVA) solution, heating and stirring in a water bath at 55 ℃ for 30min, placing the solution in AN ice water bath to cool to 0 ℃ after the solution is clear, dropwise adding 1.652mL of 2mol/L Ammonium Persulfate (APS) solution, quickly stirring uniformly, pouring the solution into a mold, and standing at normal temperature for 24h to prepare the polyvinyl alcohol-polyaniline conductive hydrogel polymer film.
And placing the formed polyvinyl alcohol-polyaniline conductive hydrogel polymer film in a refrigerator at the temperature of-20 ℃ for 8h, taking out, and placing and unfreezing at room temperature. After the freeze-thaw cycle is performed for 3 times, the mixture is washed with deionized water and placed in a container containing 0.1mol/L H2SO4In the 0.5mol/L copper sulfate electroplating solution, a polymer film is taken as a working electrode, a calomel electrode is taken as a reference electrode, a Pt wire is taken as a counter electrode to form a three-electrode system, and electrodeposition is carried out for 10 hours under the constant voltage of-1.5V.
Taking out the working electrode, washing with deionized water, freeze drying for 10 hr, placing in a tubular reaction furnace, and reacting in N2Raising the temperature from room temperature to 600 ℃ at the speed of 2 ℃/min for 2h in the atmosphere, and naturally cooling to room temperature to prepare the Cu-N-C catalyst.
Example 3.
0.0182g (0.11mmol) of triaminophenylboronic acid hydrochloride (ABA) is weighed and dissolved in 835 mu L of 6mol/L hydrochloric acid solution to prepare an ABA solution.
Sequentially adding the ABA solution, 0.189g (2.0mmol) of Aniline (AN) and 710 mu L of deionized water into 2mL of 10wt% polyvinyl alcohol (PVA) solution, heating and stirring in a water bath at 55 ℃ for 30min, placing the solution in AN ice water bath to cool to 0 ℃ after the solution is clear, dropwise adding 0.937mL of 2mol/L Ammonium Persulfate (APS) solution, quickly and uniformly stirring, pouring the solution into a mold, and standing at normal temperature for 24h to prepare the polyvinyl alcohol-polyaniline conductive hydrogel polymer film.
And placing the formed polyvinyl alcohol-polyaniline conductive hydrogel polymer film in a refrigerator at the temperature of-20 ℃ for 8h, taking out, and placing and unfreezing at room temperature. After 5 times of freeze-thaw cycle, the mixture was washed with deionized water and placed in a container containing 0.1mol/L H2SO4In the copper sulfate electroplating solution of 3mol/L, a polymer film is taken as a working electrode, a calomel electrode is taken as a reference electrode, a Pt wire is taken as a counter electrode to form a three-electrode system, and electrodeposition is carried out for 12 hours under the constant voltage of-0.7V.
Taking out the working electrode, washing with deionized water, and coolingFreeze-drying for 10h, placing in a tubular reaction furnace under N2Raising the temperature from room temperature to 700 ℃ at the speed of 2 ℃/min for 2h in the atmosphere, and naturally cooling to room temperature to prepare the Cu-N-C catalyst.
Example 1 is applied.
The Cu-N-C catalyst prepared in the example 1 is directly used as a working electrode, a 3cm x 4cm stainless steel sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a three-electrode system is adopted, and the electrochemical performance of the prepared Cu-N-C catalyst is characterized by cyclic voltammetry.
Respectively taking 1M potassium hydroxide, 1M potassium hydroxide and 1M methanol mixed solution as electrolyte solution, and performing methanol electrochemical oxidation (MOR) reaction activity test by adopting Shanghai Chenghua CHI 660E electrochemical workstation.
As shown in FIG. 2, in 1M potassium hydroxide solution, the scanning speed is 50mv/s, and the corresponding current density is 64mA ∙ cm under the voltage of 0.6V2(ii) a In the mixed solution of 1M potassium hydroxide and 1M methanol, the scanning speed is 50mv/s, and the corresponding current density is 189mA ∙ cm under the voltage of 0.6V2The catalyst has obvious catalytic effect on methanol.
According to the graph of FIG. 3, in the mixed solution of 1M potassium hydroxide and 1M methanol, the current density after 10h is still maintained at 142mA ∙ cm after 10h by observing the change trend of the current density with time through a chronoamperometric i-t test of 10h, namely, maintaining the voltage at 0.6V-2Starting Current Density (189 mA ∙ cm)-2) And 75% of the total weight of the catalyst, indicating that the catalyst has better stability.
Some literature reports on the performance index comparison of copper-based catalysts are given in table 1 below. The traditional preparation method and preparation process of the copper-based catalyst are complex, and the uniform dispersion degree of the active component copper is not high, so that the electrochemical reaction activity of methanol oxidation is directly influenced.
As can be seen from the data in Table 1, the current density values in the cited documents are all very low in the voltage window of 0.6V (vs SCE), demonstrating that the methanol oxidation activity is not high. In order to improve the activity of the catalyst, the catalyst obtained by combining the active copper component and the carbon material with good conductivity can obviously improve the current density value under fixed voltage, namely the activity of catalyzing and oxidizing the methanol is improved.
[1] S. Anantharaj, H. Sugime, S. Noda, Ultrafast Growth of Cu(OH)2-CuO Nanoneedle Array on Cu Foil for Methanol Oxidation Electrocatalysis, ACS Appl. Mater. Interfaces, 12 (2020) 27327-27338.。
[2] S.M. Pawar, J. Kim, A.I. Inamdar, H. Woo, Y. Jo, B.S. Pawar, S. Cho, H. Kim, H. In-situ synthesis of Cu(OH)2 and CuO nanowire electrocatalysts for methanol electro-oxidation, Materials Letters, 6 (2016) 21310.。
[3] D. Wu, W. Zhang, D. Cheng, Facile Synthesis of Cu/NiCu Electrocatalysts Integrating Alloy, Core−Shell, and One-Dimensional Structures for Efficient Methanol Oxidation Reaction, ACS Appl. Mater. Interfaces, 9 (2017) 19843-19851.。
Claims (10)
1. A copper-based anode catalyst for a direct methanol fuel cell is a simple substance copper nanocrystalline composite material which is obtained by taking polyvinyl alcohol-polyaniline conductive hydrogel subjected to freeze thawing as a carrier, loading transition metal copper through electrodeposition and calcining in an inert atmosphere and loaded by a nitrogen-containing carbon material, wherein the simple substance copper content is 60-80 wt%; the polyvinyl alcohol-polyaniline conductive hydrogel subjected to freeze-thaw treatment is a hydrogel product obtained by taking triaminophenylboronic acid hydrochloride, aniline and polyvinyl alcohol as raw materials, carrying out polymerization reaction in an aqueous solution system containing initiator ammonium persulfate to obtain the polyvinyl alcohol-polyaniline conductive hydrogel, freezing the polyvinyl alcohol-polyaniline conductive hydrogel at low temperature, then thawing the frozen polyvinyl alcohol-polyaniline conductive hydrogel at normal temperature, and carrying out freeze-thaw treatment for at least 1 time.
2. The preparation method of the copper-based anode catalyst for the direct methanol fuel cell as claimed in claim 1, wherein a hydrochloric acid solution of triaminophenylborate hydrochloride and aniline are added into a polyvinyl alcohol aqueous solution, after the hydrochloric acid solution and aniline are dissolved uniformly, the temperature is reduced to 0 ℃, an ammonium persulfate solution is dropwise added, a polyvinyl alcohol-polyaniline conductive hydrogel is obtained through polymerization reaction and serves as a carrier, after at least 1 freeze-thaw treatment, the polyvinyl alcohol-polyaniline conductive hydrogel is placed into a copper electroplating solution and serves as a working electrode, electrodeposition is carried out in a three-electrode system of a platinum wire counter electrode and a calomel reference electrode, metal copper is deposited on the surface of the carrier, the carrier is taken out, cleaned and dried, and calcined at 400-800 ℃ under an inert.
3. The preparation method according to claim 2, wherein the molar ratio of the triaminophenylboronic acid hydrochloride to the aniline is 0.01-0.1: 1, the amount of the polyvinyl alcohol is 30-600 times of the mass of the triaminophenylboronic acid hydrochloride, and the polymerization reaction time is 6-30 h.
4. The method according to claim 2, wherein the polyvinyl alcohol aqueous solution has a mass concentration of 8 to 12 wt%.
5. The preparation method according to claim 2, wherein the freeze-thaw treatment is performed by freezing at a low temperature of-20 ℃ for not less than 8 hours, then standing at room temperature for thawing, and the freeze-thaw treatment is cycled for 1-5 times.
6. The preparation method according to claim 2, wherein the weak base treated polyvinyl alcohol-polyaniline conductive hydrogel is subjected to electrodeposition in 0.5-3 mol/L copper electroplating solution for 8-12 h.
7. The method according to claim 2, wherein the freeze-thaw treated polyvinyl alcohol-polyaniline conductive hydrogel deposited with elemental copper is freeze-dried.
8. The method according to claim 2, wherein the calcination is carried out for 1 to 5 hours.
9. The method according to claim 2, wherein the polyvinyl alcohol-polyaniline conductive hydrogel deposited with elemental copper and subjected to freeze-thaw treatment is calcined by raising the temperature from room temperature to 400-800 ℃ at a rate of 1-5 ℃/min.
10. The use of the copper-based catalyst of claim 1 directly as an alkaline system direct methanol fuel cell anode.
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| CN113224331A (en) * | 2021-05-08 | 2021-08-06 | 中北大学 | Alkaline system direct urea fuel cell anode catalyst and preparation method thereof |
| CN115007203A (en) * | 2022-04-13 | 2022-09-06 | 南京信息工程大学 | Organic amine modified manganese dioxide catalyst and preparation method and application thereof |
| CN115458785A (en) * | 2022-09-28 | 2022-12-09 | 南通大学 | Preparation method of sol-gel electrolyte of direct methanol fuel cell |
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