CN111068661A - Nonmetal co-doped carbon-loaded metal nanoparticle catalyst and preparation method and application thereof - Google Patents

Nonmetal co-doped carbon-loaded metal nanoparticle catalyst and preparation method and application thereof Download PDF

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CN111068661A
CN111068661A CN201911275690.0A CN201911275690A CN111068661A CN 111068661 A CN111068661 A CN 111068661A CN 201911275690 A CN201911275690 A CN 201911275690A CN 111068661 A CN111068661 A CN 111068661A
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doped carbon
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李成飞
李高仁
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Sun Yat Sen University
National Sun Yat Sen University
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Abstract

The invention discloses a non-metal co-doped carbon-supported metal nanoparticle catalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, mixing 1-20 parts by mass: 0.5-15: 0.1-5: dissolving 0.1-10 parts of one or more than two polymerized monomers of aniline, pyrrole or thiophene, a complexing agent, an oxidant and a metal salt in a solvent, and simultaneously carrying out polymerization and complex reaction at 0-5 ℃; and S2, drying the sample prepared in the step S1, and sintering, washing and drying the dried sample in the protective gas atmosphere to prepare the non-metal co-doped carbon-supported metal nanoparticle catalyst. The method simultaneously carries out polymerization and complexation reactions, highly disperses the metal salt to form ultra-small nano particles, and obtains high specific surface area so as to improve the catalytic activity. The catalyst prepared by the invention is applied to electrocatalytic hydrogen evolution reaction, and has higher catalytic activity and excellent cycle stability.

Description

Nonmetal co-doped carbon-loaded metal nanoparticle catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrolytic water catalysis, in particular to a non-metal co-doped carbon-loaded metal nanoparticle catalyst and a preparation method and application thereof.
Background
The electrocatalysts currently used for hydrogen evolution are mainly platinum-based catalysts, and although they have excellent hydrogen evolution properties, their large-scale use is limited by the cyclic stability and complexity of the preparation process and the high cost. Therefore, the search for a simple preparation method which is suitable for large-scale production, reduces the use amount of precious metals and further improves the catalytic activity is still urgent.
Chinese patent CN201210330852.8 discloses a electrocatalyst for a cathode of a fuel cell and preparation and application thereof, wherein the electrocatalyst is prepared by taking a conductive polymer as a reaction precursor, polymerizing under acidic and oxidizing conditions to obtain polyaniline, adding a transition metal salt, a phosphorus-containing compound and/or a boron-containing compound, and sintering, wherein the molar ratio of metal to the conductive polymer is 1: 100-1: 10. The preparation method reduces the use amount of noble metals, but the polyaniline obtained by polymerization reacts with metal salt to obtain the electrocatalyst, the polymer does not have a three-dimensional loose structure, the metal salt ions are agglomerated in the sintering process, and the improvement of the catalytic activity is not facilitated. Therefore, there is a need to find a hydrogen evolution electrocatalyst with further improved catalytic activity.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defect and the defect of poor catalytic activity of the existing hydrogen evolution electrocatalyst, and provides a preparation method of a non-metal co-doped carbon-loaded metal nanoparticle catalyst.
It is another object of the present invention to provide a non-metal co-doped carbon-supported metal nanoparticle catalyst.
Still another object of the present invention is to provide an application of the non-metal co-doped carbon supported metal nanoparticle catalyst.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a non-metal co-doped carbon-supported metal nanoparticle catalyst comprises the following steps:
s1, mixing 1-20 parts by mass: 0.5-15: 0.1-5: dissolving 0.1-10 parts of one or more than two polymerized monomers of aniline, pyrrole or thiophene, a complexing agent, an oxidant and a metal salt in a solvent, and simultaneously carrying out polymerization and complex reaction at 0-5 ℃;
and S2, drying the sample prepared in the step S1, and sintering, washing and drying the dried sample in the protective gas atmosphere to prepare the non-metal co-doped carbon-supported metal nanoparticle catalyst.
The invention takes one or more than two polymerized monomers of aniline, pyrrole or thiophene as organic polymer precursors, and firstly uniformly mixes the organic polymer precursors with a complexing agent in order to ensure that a negative charge group (such as a phosphate group and a carboxylic acid group) in the complexing agent and a positive charge group (such as-N) in the polymerized monomers+H-) is positively charged. After the oxidant is added, the polymerization monomer is subjected to polycondensation reaction, the complexing agent is embedded into the molecular layer of the organic polymer due to electrostatic adsorption, the three-dimensional loose organic polymer is formed, and meanwhile, metal salt ions and the complexing agent can be highly dispersed in the inner layer and the outer layer of the organic polymer after the complexation reaction, so that more ion agglomeration caused in the subsequent sintering process is avoided. In addition, the three-dimensional organic polymer and the oxygen-containing group of the complexing agent are subjected to chemical reaction to form CO in the sintering process2The gas promotes the formation of a loose porous structure, so that the resulting catalyst has a high specific surface area, thereby exposing more catalytic sites.
Preferably, the specific operation of step S1 is:
adding one or more than two polymeric monomers of aniline, pyrrole or thiophene and a complexing agent into a solvent, stirring and mixing to form a uniform solution, then adding an oxidant and a metal salt solution into the solution, and simultaneously putting the solution at a temperature of 0-5 ℃ and stirring at a certain speed for 2-10 hours to obtain a mixed material.
Preferably, in the step S1, the mass part ratio of the polymerized monomer, the complexing agent, the oxidant and the metal salt is 5-20: 5-12: 1-3: 1 to 8.
More preferably, in the step S1, the mass part ratio of the polymerized monomer, the complexing agent, the oxidant and the metal salt is 10-20: 8-10: 2-3: 1.5 to 5.
Preferably, the polymerized monomer in step S1 is aniline.
The non-metal doping species is related to the species of the complexing agent and the oxidizing agent, so that different types of non-metal doping catalysts can be obtained by the preparation method of the invention. Of course, the final product formed is also related to the content of complexing agent and oxidizing agent, and when they are too high, the corresponding phosphide, nitride, sulfide or oxide is formed.
Preferably, the complexing agent in step S1 is one or a combination of two or more of histidine, phytic acid, tannic acid, and malic acid.
More preferably, the complexing agent in step S1 is phytic acid.
Preferably, the solvent in step S1 is one of deionized water, alcohols, and ethers.
More preferably, the solvent in step S1 is one or more of deionized water, methanol, ethanol, n-butanol, ethylene glycol, or isopropanol.
Preferably, the stirring speed in the step S1 is 200-800 r/min.
More preferably, the stirring speed in step S1 is 300-500 rpm.
Preferably, the oxidant in step S1 is ammonium persulfate.
Preferably, the metal salt in step S1 is one or more of Ni, Co, Ru, Pt and Ir.
Preferably, the specific operation of step S2 is:
drying the mixed material obtained in the step S1; and (3) putting the dried sample into a sintering furnace, heating to 600-1300 ℃ at a heating rate of 0.5-10 ℃/min under the atmosphere of protective gas, keeping the temperature for 1-5 h, naturally cooling to room temperature, taking out the sample, crushing, sieving, washing and drying at 80 ℃ to obtain the non-metal co-doped carbon-supported metal nanoparticle catalyst.
The heating rate, the sintering temperature and the heat preservation time affect the size of the metal nano particles, and when the heating rate is too high, the sintering temperature is too high, and the heat preservation time is too long, the particle size of the metal nano particles is increased. Of course, the amount of C, P, O, N, S remaining is also dependent on the sintering temperature, and the higher the sintering temperature, the lower the non-metal doping content, so the temperature is adjusted appropriately.
Preferably, the drying temperature in the step S2 is 50-130 ℃, and the drying time is 0.5-10 h.
Preferably, the drying method in step S2 is one of freeze drying, vacuum drying, heat drying or spray drying.
Preferably, the protective gas in step S2 is nitrogen or argon.
Preferably, the temperature rise rate in step S2 is 3-8 ℃/min.
More preferably, the temperature rise rate in step S2 is 4-6 ℃/min.
Preferably, the sintering temperature in step S2 is 600-1300 ℃.
More preferably, the sintering temperature in step S2 is 700-1100 ℃.
Further preferably, the sintering temperature in step S2 is 800-1000 ℃.
Preferably, the sintering heat preservation time in the step S2 is 2-3 h.
The invention protects the prepared nonmetal-codoped carbon-supported metal nanoparticle catalyst.
Preferably, the nonmetal is N, P, S, O, and the metal nanoparticles are composed of one or more nanoparticles of Ni, Co, Ru, Pt and Ir, and the metal nanoparticles are highly dispersed in the carbon material in a combined form of embedding, semi-embedding or anchoring on the surface.
Preferably, the particle size of the metal nanoparticles is 0.5-20 nm.
More preferably, the metal nanoparticles have a particle size of 0.5 to 5 nm.
Preferably, the mass content of the metal nanoparticles is 0.2-50%.
More preferably, the metal nanoparticles are contained in an amount of 1% to 25% by mass.
Preferably, the specific surface area of the non-metal co-doped carbon-loaded metal nano-particles is 50-800 m2/g。
The invention also protects the application of the non-metal co-doped carbon-supported metal nanoparticle catalyst in hydrogen production by water electrolysis.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a non-metal co-doped carbon-supported metal nanoparticle catalyst, which comprises the following steps: dissolving one or more than two polymerization monomers of aniline, pyrrole or thiophene, a complexing agent, an oxidant and a metal salt in a certain mass part ratio in a solvent, and simultaneously carrying out polymerization and complex reaction; and drying the prepared sample, and sintering, washing and drying the dried sample in the protective gas atmosphere to obtain the non-metal co-doped carbon-supported metal nanoparticle catalyst. The method realizes the design idea of a one-pot method, and the complexing reaction is carried out while the polymerization reaction is carried out, so that not only can metal salt ions be highly dispersed, but also metal nano particles are highly dispersed in the carbon material in a combined form of embedding, semi-embedding or anchoring on the surface, and the method plays a space confinement role in the sintering process, is favorable for forming ultra-small nano particles, and simultaneously the complexing agent also plays a pore-forming role to obtain a high specific surface area, and the special space structure is favorable for improving the catalytic activity. Compared with the existing method of firstly preparing the polymer and then mixing the polymer with the metal salt, the preparation process is simpler, intermediate filtration and multiple sintering are not needed, the catalytic activity is improved, and the method is environment-friendly, low in cost and suitable for industrialization.
The nonmetal-codoped carbon-supported metal nanoparticle catalyst obtained by the preparation method has excellent cycle performance and catalytic activity, which are derived from the regulation and control of electronic structures and special space structures of the catalyst by virtue of various nonmetal doping. The catalyst prepared by the invention is applied to electrocatalytic hydrogen evolution reaction, and has higher catalytic activity and excellent cycle stability.
Drawings
Fig. 1 is a schematic structural diagram of the non-metal co-doped carbon-supported metal nanoparticle catalyst of the present invention.
Fig. 2 is an XPS spectrum of the non-metal co-doped carbon supported metal nanoparticle catalyst of example 1 sintered at 900 ℃.
Fig. 3 is a TEM image of the non-metal co-doped carbon supported metal nanoparticle catalyst of example 1 sintered at 900 ℃.
Fig. 4 is a TEM image of the non-metal co-doped carbon supported metal nanoparticle catalyst of example 2 sintered at 900 ℃.
Fig. 5 is a TEM image of example 3 non-metal co-doped carbon supported metal nanoparticle catalyst sintered at 900 ℃.
FIG. 6 is a graph showing the catalytic performance of the nonmetal-codoped carbon-supported metal nanoparticle catalysts obtained in examples 1-3 and comparative example 1.
Fig. 7 is a graph of cycle life performance of the non-metal co-doped carbon-supported metal nanoparticle catalysts obtained in example 1 and comparative example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The invention provides a non-metal co-doped carbon-supported metal nanoparticle catalyst, and a preparation method and application thereof. The following examples are specifically illustrative.
Example 1
A preparation method of a non-metal co-doped carbon-supported metal nanoparticle catalyst comprises the following steps:
dissolving 100g of histidine and 200g of aniline in a mixed solution of 300mL of deionized water and 100mL of ethanol, stirring for 1h in a water bath at 0-5 ℃, then adding 20g of ammonium persulfate dissolved in 100mL of water and 15g of ruthenium chloride dissolved in 100mL of water, continuously stirring for 4 h, directly spray-drying to obtain a powder solid, placing the powder solid in a tubular furnace constant-temperature area, heating to 900 ℃ at a heating rate of 3 ℃/min under the protection of argon, keeping the temperature for 2h, naturally cooling to room temperature, taking out a sample, crushing, sieving, washing, and drying at 80 ℃ to obtain the non-metal co-doped metal nanoparticle catalyst.
Example 2
A preparation method of a non-metal co-doped carbon-supported metal nanoparticle catalyst comprises the following steps:
dissolving 100g of histidine and 200g of aniline in a mixed solution of 300mL of deionized water and 100mL of ethanol, stirring for 1h in a water bath at 0-5 ℃, adding 20g of ammonium persulfate dissolved in 100mL of water and 15g of sodium chloroplatinate dissolved in 100mL of water, continuously stirring for 4 h, directly spray-drying to obtain a powder solid, placing the powder solid in a tubular furnace constant-temperature area, heating to 900 ℃ at a heating rate of 3 ℃/min under the protection of argon, keeping the temperature for 2h, naturally cooling to room temperature, taking out a sample, crushing, sieving, washing, and drying at 80 ℃ to obtain the non-metal co-doped metal nanoparticle catalyst.
Example 3
A preparation method of a non-metal co-doped carbon-supported metal nanoparticle catalyst comprises the following steps:
dissolving 100g of phytic acid and 200g of aniline in 300mL of deionized water and 100mL of ethanol mixed solution, stirring for 1h in a water bath at 0-5 ℃, adding 20g of ammonium persulfate dissolved in 100mL of water, 7.5g of ruthenium chloride and 7.5g of cobalt chloride, continuously stirring for 4 h, directly spray-drying to obtain a powder solid, placing the powder solid in a tubular furnace constant-temperature area, heating to 900 ℃ at a heating rate of 3 ℃/min under the protection of argon, keeping the temperature for 2h, naturally cooling to room temperature, taking out a sample, crushing, sieving, washing, and drying at 80 ℃ to obtain the non-metal co-doped metal nanoparticle catalyst.
Comparative example 1
Dissolving 200g of aniline in 300mL of deionized water, stirring for 1h in a water bath at 0-5 ℃, then dropwise adding 20g of ammonium persulfate dissolved in 100mL of water, reacting for 6h, centrifuging, filtering, washing, and drying at 80 ℃ to obtain a dried sample; and ultrasonically stirring and dispersing the obtained sample into 200mL of water, adding 15g of ruthenium chloride dissolved in 100mL of water, continuously ultrasonically stirring for 2h, centrifuging and filtering, drying at 80 ℃ to obtain a solid, placing the solid in a tubular furnace constant-temperature area, heating to 900 ℃ at a heating rate of 3 ℃/min under the protection of argon, preserving heat for 2h, naturally cooling to room temperature, taking out the sample, crushing and sieving the sample to obtain the nonmetal co-doped metal nanoparticle catalyst.
As shown in fig. 1, which is a schematic structural diagram of the non-metal co-doped carbon-supported metal nanoparticle catalyst of the present invention, the metal nanoparticles are highly dispersed in the carbon material in a combined form of embedding, semi-embedding or anchoring on the surface, and this special spatial structure is favorable for improving the catalytic activity.
From the XPS spectrum of fig. 2, it can be seen that N/S is co-doped in the carbon-supported ruthenium catalyst.
Performance testing
1. Test method
The nonmetal co-doped metal nanoparticle catalyst prepared in the embodiments 1 to 3 and the comparative example 1 is subjected to electrochemical catalysis performance test, and the electrochemical catalysis performance test method comprises the following specific steps: 2mg of the catalyst prepared in examples 1 to 3 and comparative example 1 was ultrasonically dispersed in 1mL of ethanol and 10. mu.L of 5% Nafion solution, and 10. mu.L of the solution was applied to a thickness of 0.07cm2On a glassy carbon electrode (working electrode), a carbon rod is used as a counter electrode, and saturated mercuric chloride is used as a reference electrode to test in a 1mol/L KOH solution. The used test instrument is a test system of CHI760E Chenghua, and the scanning speed is 5mV/s at normal temperature.
2. Test results
TABLE 1 results of electrochemical tests on catalysts prepared in examples 1-3 and comparative example 1
Figure BDA0002315502030000071
The electrochemical test results of the catalysts prepared in the embodiments 1 to 3 and the comparative example 1 are shown in table 1, and it can be seen from the results in table 1 that the catalyst prepared by the method of the present invention has more excellent catalytic activity compared with the comparative example 1, which is mainly derived from co-doping of various non-metal elements to control an electronic structure and a special spatial structure of the catalyst, so that the adsorption and desorption properties of an intermediate product are optimized, and more active sites are exposed by ultra-small metal nanoparticles. Meanwhile, as can be seen from fig. 6, the catalysts prepared in the embodiments 1 to 3 of the present invention can satisfy the requirement of obtaining a lower overpotential at a large current density in practical applications, i.e., have excellent catalytic performance, compared to the catalyst prepared in the comparative example 1.
As can be seen from the transmission electron microscope images shown in the figures 3 to 5, the ultra-small nanoparticles obtained by the preparation method have the average diameter of 0.5-10 nm, and are derived from the fact that the phytic acid ligand plays a role in spatial confinement in the calcination process, and other ligands are easy to decompose at low temperature, so that the limited confinement capability is realized.
As can be seen from the cycle life performance graph of fig. 7, the voltage of the sample of comparative example 1 is continuously increased with the increase of the cycle time, which means that the catalyst is continuously deactivated, while the voltage of the catalyst prepared by the example 1 of the present invention is relatively stable during the cycle, so that the catalyst prepared by the example 1 has a better cycle life. It is worth mentioning that the step-shaped curve is caused by the problem of the Nafion solution as the binder, and the performance is reduced due to the falling of the catalyst caused by the precipitation of a large amount of bubbles in the catalytic process, but the curve is not the cause of the deactivation of the catalyst.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A preparation method of a non-metal co-doped carbon-supported metal nanoparticle catalyst is characterized by comprising the following steps:
s1, mixing 1-20 parts by mass: 0.5-15: 0.1-5: dissolving 0.1-10 parts of one or more than two polymerized monomers of aniline, pyrrole or thiophene, a complexing agent, an oxidant and a metal salt in a solvent, and simultaneously carrying out polymerization and complex reaction at 0-5 ℃;
and S2, drying the sample prepared in the step S1, and sintering, washing and drying the dried sample in the protective gas atmosphere to prepare the non-metal co-doped carbon-supported metal nanoparticle catalyst.
2. The preparation method according to claim 1, wherein the mass part ratio of the polymerized monomer, the complexing agent, the oxidizing agent and the metal salt in step S1 is 5-20: 5-12: 1-3: 1 to 8.
3. The preparation method according to claim 2, wherein the mass parts ratio of the polymerized monomer, the complexing agent, the oxidizing agent and the metal salt in step S1 is 10-20: 8-10: 2-3: 1.5 to 5.
4. The method according to claim 3, wherein the polymerizable monomer in step S1 is aniline.
5. The method according to claim 4, wherein the complexing agent in step S1 is one or more of histidine, phytic acid, tannic acid, and malic acid.
6. The method according to claim 5, wherein the oxidant in step S1 is ammonium persulfate.
7. The method according to claim 6, wherein the metal salt in step S1 is one or more metal salts selected from Ni, Co, Ru, Pt and Ir.
8. The non-metal co-doped carbon-supported metal nanoparticle catalyst prepared by the preparation method of any one of claims 1 to 7.
9. The non-metal Co-doped carbon-supported metal nanoparticle catalyst according to claim 8, wherein the non-metal is N, P, S, O, the metal nanoparticle is composed of one or more nanoparticles of Ni, Co, Ru, Pt or Ir, and the metal nanoparticle is highly dispersed in the carbon material in a combined form of embedding, semi-embedding or anchoring on the surface.
10. Use of the non-metal co-doped carbon-supported metal nanoparticle catalyst of claim 8 or 9 in the electrolysis of water to produce hydrogen.
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