CN112652780B - Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst - Google Patents
Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst Download PDFInfo
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Abstract
The invention discloses Fe/Fe 3 The preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst, which uses SiO 2 As a hard template, a novel Fe/Fe is prepared by the polymerization reaction of hydroxymethylated melamine and ferric acetylacetonate 3 The C nano-particles load the porous nitrogen-doped carbon-based oxygen reduction catalyst. The invention utilizes the polymerization reaction of hydroxymethylated melamine and iron acetylacetonate to synthesize polymer containing iron, nitrogen and carbon, and Fe/Fe formed in the process of pyrolysis 3 The C species can effectively improve the graphitization degree of carbon, enhance the conductivity of the material and further improve the catalytic activity of the catalytic material, and the Fe/Fe prepared by the method 3 The specific surface area of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst is 1084m 2 g ‑1 The average pore diameter is 7nm, and the oxygen reduction performance is excellent.
Description
Technical Field
The invention belongs to the technical field of synthesis of non-noble metal doped carbon-based oxygen reduction catalytic materials, and particularly relates to Fe/Fe 3 A preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst.
Background
The rapid development of the industry brings great social changes and a series of problems, such as energy crisis, environmental pollution and the like. Therefore, exploring the development of clean and efficient energy conversion devices and energy storage devices is a necessary approach to solve the above problems. Fuel cells, which are a new type of energy conversion device, are considered to be one of the most promising technologies due to their advantages of environmental friendliness, low cost, high energy conversion efficiency, and the like. The Oxygen Reduction Reaction (ORR) plays an important role in the conversion of chemical energy to electrical energy as a key reaction of the cathode of the fuel cell, but the slow kinetic process and the excessively high reaction energy barrier thereof greatly reduce the energy conversion efficiency of the fuel cell, so that the development of an electrocatalyst with high activity to accelerate the reaction rate and improve the reaction selectivity is the focus of current research. The carbon-supported platinum-based catalyst (Pt/C) has excellent oxygen reduction catalytic activity and is the most commonly used catalyst for the current fuel cell, but due to the factors of high price, scarce resources, poor stability and the like of the Pt/C catalyst, the application of the Pt/C catalyst in the commercial fuel cell is limited to a great extent. Therefore, the development of non-noble metal catalysts which are economical and environmentally friendly and have high catalytic activity and high durability is urgent.
Currently, researchers have developed a series of non-noble metal materials as oxygen reduction catalysts, including transition metal (iron, cobalt, nickel, etc.) oxides, transition metal nitrides, transition metal and heteroatom doped carbon materials, and the like. The transition metal oxide and the transition metal nitride have the advantages of rich raw material sources, good electrocatalytic activity and the like, have the characteristic of replacing noble metals, and are favored by researchers. However, the oxygen reduction activity is far lower than expected due to problems such as poor conductivity, easy agglomeration and the like. The carbon carrier is modified by the transition metal and the heteroatom, so that the catalytic activity of the transition metal/heteroatom can be retained, rich active sites can be created on the surface of the material, the transition metal/heteroatom modified carbon material and the rich active sites play a role together, the ultrahigh conductivity and the catalytic activity are endowed to the transition metal/heteroatom modified carbon material, and the oxygen reduction activity of the catalyst is improved theoretically. Transition metal and heteroatom doped carbon materials are therefore currently the most promising non-noble metal catalysts.
In recent years, iron carbide (Fe) 3 C) Have been widely studied in ORR due to their good conductivity and specific electronic structure. Mixing Fe nanoparticles (such as Fe and Fe) 3 C, etc.) coated inside the carbon layer, and the iron and nitrogen co-doped carbon-based catalytic material further shows excellent oxygen reduction activity. Wei Zidong topic group (J. Am. chem. Soc. 2016, 138, 3570-3578) reported a compound containing Fe-Nx active sites and Fe/Fe 3 C nano-particle non-noble metal catalyst, which is found to contain Fe/Fe at the same time 3 The catalyst of C nano-particles and Fe-Nx has higher activity when removing Fe/Fe 3 The activity of the catalyst is obviously reduced when C is nano-particles. Theoretical calculation shows that when the metal iron atoms are contained near the active sites of Fe-Nx, the adsorption behavior of oxygen is facilitated, and the oxygen reduction process is accelerated. Fe. Fe 3 The nanoparticles such as C can provide free electrons, change the electronic structure of the outer carbon shell, promote the adsorption and electron transfer of oxygen molecules and contribute to enhancing the ORR activity. However, fe appear during the preparation process 3 The self-aggregation phenomenon of the nanoparticles such as C can cause the loss of catalytic active sites. Therefore, finding a suitable substrate material to uniformly distribute active sites is an important issue in designing an electrocatalytically active material. When the porous carbon material with rich pore structure and higher effective specific surface area is used as an iron-based catalyst carrier, active species in the catalyst can be dispersed and anchored, and meanwhile, a convenient channel is provided for substances participating in reaction, so that the porous carbon material is widely concerned by researchers in the field of catalysis. Based on this, the invention uses SiO 2 As a hard template, a novel Fe/Fe compound is prepared by polymerization reaction of hydroxymethylated melamine and ferric acetylacetonate 3 The C nano-particles load the porous nitrogen-doped carbon-based oxygen reduction catalyst.
Disclosure of Invention
The technical problems solved by the invention are as follows: first, use of SiO 2 Is a hard template agent, and the hydroxymethylated melamine is a nitrogen-containing carbon precursor synthesized into the porous nitrogen-doped carbon material. The porous carbon material has excellent conductivity andthe catalyst has a special pore channel structure, and active species in the catalyst can be dispersed and anchored by using the catalyst as a carrier of an iron-based catalyst. In addition, the abundant pore structure and the higher effective specific surface area of the porous carbon material can provide convenient channels for substances participating in reaction, so that the substance transmission is accelerated, and the catalytic performance is improved. Secondly, through the development of the work, a novel Fe/Fe preparation method is provided 3 A method of C nanoparticle-supported porous nitrogen-doped carbon-based oxygen reduction catalysts. Firstly, synthesizing a polymer containing iron, nitrogen and carbon by using polymerization reaction of hydroxymethylated melamine and ferric acetylacetonate, and then obtaining Fe/Fe through high-temperature pyrolysis and acid leaching processes 3 The C nano-particles support a porous nitrogen-doped carbon material. Fe/Fe formed during pyrolysis 3 The C species can effectively improve the graphitization degree of the catalyst, enhance the conductivity of the material and further improve the catalytic activity of the catalytic material.
The invention adopts the following technical scheme to solve the technical problems 3 The preparation method of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following specific steps:
step S1: dissolving melamine and formaldehyde in deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring and mixing the mixture evenly, and then sequentially adding a hard template agent SiO 2 Adding a metal precursor of iron acetylacetonate, dropwise adding glacial acetic acid, stirring, uniformly mixing, centrifuging and drying to obtain a material A;
step S2: transferring the material A obtained in the step S1 to a nickel boat, placing the nickel boat in a tube furnace, heating the material A to 300 ℃ from room temperature within 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material A to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material A to room temperature to obtain a material B;
and step S3: transferring the material B obtained in the step S2 into 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to neutrality, and drying in an oven at 80 ℃ for 12h to obtain Fe/Fe 3 And C nano particles load the porous nitrogen-doped carbon-based oxygen reduction catalyst C.
Preferably, the melamine and the hard template agent SiO in the step S1 2 And the mass ratio of the metal precursor of the iron acetylacetonate is 3: 0.5-1, and the feeding molar ratio of the melamine to the formaldehyde is 1:3.
Preferably, the inert gas in step S2 is one or more of nitrogen or argon.
Preferably, the Fe/Fe 3 The preparation method of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following specific steps of:
step S1: dissolving 5g of melamine and 5mL of formaldehyde in 50mL of deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring for 30min, uniformly mixing, and then adding 1g of hard template agent SiO 2 0.7g of metal precursor ferric acetylacetonate and 2mL of glacial acetic acid, stirring for 1h at 60 ℃, then stirring overnight at room temperature, centrifuging and drying to obtain a material A3:
step S2: transferring the material A3 obtained in the step S1 to a nickel boat, placing the nickel boat in a tube furnace, heating the material A to 300 ℃ from room temperature within 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material A to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material A to room temperature to obtain a material B3;
and step S3: transferring the material B3 obtained in the step S2 into 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to neutrality, and drying in an oven at 80 ℃ for 12h to obtain Fe/Fe 3 C nano-particles load a porous nitrogen-doped carbon-based oxygen reduction catalyst C3, the Fe/Fe 3 The specific surface area of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst C3 is 1084m 2 g -1 The average pore diameter is 7nm, and the oxygen reduction performance is excellent.
Compared with the prior art, the invention has the following excellent effects:
1. the invention introduces SiO 2 As a hard template agent, hydroxymethylated melamine is used as a nitrogen-containing carbon precursor to synthesize the mesoporous nitrogen-doped carbon material. The catalyst has excellent conductivity and a unique pore channel structure, and can disperse and anchor active species in the catalyst when being used as a carrier of an iron-based catalyst. In addition, rich pore canal structure and higher effective specific surface area can provide convenient channels for substances participating in the reaction,thereby accelerating the material transmission and improving the catalytic performance.
2. The invention utilizes the polymerization reaction of hydroxymethylated melamine and iron acetylacetonate to synthesize polymer containing iron, nitrogen and carbon, and Fe/Fe formed in the process of pyrolysis 3 The C species can effectively improve the graphitization degree of carbon, enhance the conductivity of the material and further improve the catalytic activity of the catalytic material.
3. Fe/Fe prepared by the invention 3 The specific surface area of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst is 1084m 2 g -1 The average pore diameter is 7nm, and the oxygen reduction performance is excellent.
Drawings
FIG. 1 is a scanning electron micrograph of a target product C3 prepared in example 3;
FIG. 2 is a graph showing a nitrogen adsorption and desorption curve and a pore size distribution of a target product C3 prepared in example 3;
FIG. 3 is an X-ray diffraction pattern of the target product C3 prepared in example 3;
FIG. 4 is a cyclic voltammogram of the target product prepared in examples 1, 3 and 5.
FIG. 5 is a graph showing the electron transfer numbers of the objective product C3 prepared in example 3.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be understood that the scope of the subject matter of the present invention is limited to the examples below, and any technique realized based on the above contents of the present invention falls within the scope of the present invention.
Example 1
Step S1: dissolving 5g of melamine and 5mL of formaldehyde in 50mL of deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring for 30min, uniformly mixing, and then adding 1g of SiO 2 And 2mL of glacial acetic acid, stirring at the temperature for 1h, then stirring at room temperature overnight, centrifuging and drying to obtain a material A1;
step S2: transferring the material A1 to a nickel boat, placing the nickel boat in a tube furnace, heating the material to 300 ℃ from room temperature for 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material to room temperature to obtain a material B1;
and step S3: and transferring the material B1 into a 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to be neutral, and then drying in an oven at 80 ℃ for 12h to obtain a target product C1.
Example 2
Step S1: dissolving 5g of melamine and 5mL of formaldehyde in 50mL of deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring for 30min, uniformly mixing, and then adding 1g of SiO 2 0.5g of iron acetylacetonate and 2mL of glacial acetic acid, stirring is continued at this temperature for 1h and subsequently overnight at room temperature, and material A2:
step S2: transferring the material A2 to a nickel boat, placing the nickel boat in a tube furnace, heating the material A2 to 300 ℃ from room temperature for 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material A to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material A to room temperature to obtain a material B2;
and step S3: and transferring the material B2 into a 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to be neutral, and then drying in an oven at 80 ℃ for 12h to obtain a target product C2.
Example 3
Step S1: dissolving 5g of melamine and 5mL of formaldehyde in 50mL of deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring for 30min, uniformly mixing, and then adding 1g of SiO 2 0.7g of iron acetylacetonate and 2mL of glacial acetic acid, stirring at this temperature is continued for 1h, immediately overnight at room temperature, and centrifugation and drying give material A3:
step S2: transferring the material A3 to a nickel boat, placing the nickel boat in a tube furnace, heating the material to 300 ℃ from room temperature for 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material to room temperature to obtain a material B3;
and step S3: and transferring the material B3 into a 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to be neutral, and then drying in an oven at 80 ℃ for 12h to obtain a target product C3.
Example 4
Step S1: will be provided withDissolving 5g of melamine and 5mL of formaldehyde in 50mL of deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring for 30min, uniformly mixing, and then adding 1g of SiO 2 1g of iron acetylacetonate and 2mL of glacial acetic acid, stirring at this temperature for 1h being continued, and subsequently overnight at room temperature, and centrifugation and drying giving A4:
step S2: transferring the material A4 to a nickel boat, placing the nickel boat in a tube furnace, heating the material A4 to 300 ℃ from room temperature for 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material A to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material A to room temperature to obtain a material B4;
and step S3: and transferring the material B4 into a 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to be neutral, and then drying in an oven at 80 ℃ for 12h to obtain a target product C4.
Example 5
Step S1: dissolving 5g of melamine and 5mL of formaldehyde in 50mL of deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring for 30min, uniformly mixing, adding 0.7g of ferric acetylacetonate and 2mL of glacial acetic acid, continuously stirring for 1h at the temperature, then stirring overnight at room temperature, centrifuging and drying to obtain a material A5;
step S2: transferring the material A5 to a nickel boat, placing the nickel boat in a tube furnace, heating the material to 300 ℃ from room temperature for 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material to room temperature to obtain a material B5;
and step S3: and transferring the material B5 into a 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to be neutral, and then drying in an oven at 80 ℃ for 12h to obtain a target product C5.
Example 6
Weighing a certain amount of Fe/Fe ground into powder by using an electronic balance 3 C nano particles load a porous nitrogen-doped carbon-based oxygen reduction catalyst C3 sample, the sample is uniformly mixed with 5wt% of Nafion and high-purity water, and ultrasonic treatment is carried out for several minutes to obtain uniform ink-shaped dispersion liquid; and (3) using a liquid transfer gun to transfer a proper amount of the ultrasonically-good ink-like dispersion liquid to be dropped on the cleaned glassy carbon electrode, and then naturally drying at room temperature to prepare the working electrode. Using the sameMethod working electrodes for C1, C2, C4, C5 samples were prepared and compared to the C3 sample. All electrochemical tests used a three-electrode system. In the Linear Sweep Voltammetry (LSV) test, glassy carbon is used as a working electrode (with a diameter of 5 mm), and the surface of the working electrode is coated with a certain volume and a certain concentration of active substances (namely, a prepared ink-like dispersion liquid), hg/HgO and a platinum sheet (1 cm) 2 ) Respectively used as a reference electrode and a counter electrode, and the electrolyte is N 2 /O 2 Saturated 0.1mol L -1 With an aqueous KOH solution, the scanning speed in the test was 10mV s -1 The rotation speed is 1600rpm, and the scanning range is-0.8V to 0.4V. In the Cyclic Voltammetry (CV) test, the reference electrode, counter electrode, electrolyte, and test conditions were the same as the above LSV conditions except that the working electrode was a glassy carbon electrode having a diameter of 3mm and coated with a certain volume and a certain concentration of an active material (the above prepared ink dispersion).
While the foregoing embodiments have described the principles, principal features and advantages of the invention, it will be understood by those skilled in the art that the invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but is susceptible to various changes and modifications without departing from the scope thereof, which fall within the scope of the appended claims.
Claims (4)
1. Fe/Fe 3 The preparation method of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following specific steps:
step S1: dissolving melamine and formaldehyde in deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring and mixing the mixture evenly, and then sequentially adding a hard template agent SiO 2 Adding a metal precursor of iron acetylacetonate, dropwise adding glacial acetic acid, stirring, uniformly mixing, centrifuging and drying to obtain a material A;
step S2: transferring the material A obtained in the step S1 to a nickel boat, placing the nickel boat in a tube furnace, heating the material A to 300 ℃ from room temperature for 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material A to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material A to room temperature to obtain a material B;
and step S3: transferring the material B obtained in the step S2 into 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to neutrality, and drying in an oven at 80 ℃ for 12h to obtain Fe/Fe 3 And C nano particles load the porous nitrogen-doped carbon-based oxygen reduction catalyst C.
2. Fe/Fe according to claim 1 3 The preparation method of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following steps: the melamine and the hard template agent SiO in the step S1 2 And the mass ratio of the metal precursor of the iron acetylacetonate is 3.5-1, and the feeding molar ratio of the melamine to the formaldehyde is 1:3.
3. Fe/Fe according to claim 1 3 The preparation method of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following steps: and in the step S2, the inert gas is one or more of nitrogen or argon.
4. Fe/Fe according to claim 1 3 The preparation method of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst is characterized by comprising the following specific steps of:
step S1: dissolving 5g of melamine and 5mL of formaldehyde in 50mL of deionized water, placing the mixture in a water bath kettle at 60 ℃, stirring for 30min, uniformly mixing, and then adding 1g of hard template agent SiO 2 0.7g of metal precursor ferric acetylacetonate and 2mL of glacial acetic acid, continuously stirring for 1h at 60 ℃, then stirring overnight at room temperature, and obtaining a material A3 through centrifugation and drying processes:
step S2: transferring the material A3 obtained in the step S1 to a nickel boat, placing the nickel boat in a tube furnace, heating the material to 300 ℃ from room temperature for 55min in an inert gas atmosphere, keeping the temperature for 60min, heating the material to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, and naturally cooling the material to room temperature to obtain a material B3;
and step S3: transferring the material B3 obtained in the step S2 into 20wt% hydrofluoric acid solution, soaking for 24h, washing with high-purity water to neutrality, and drying in an oven at 80 ℃ for 12h to obtain the productFe/Fe 3 C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst C3, the Fe/Fe 3 The specific surface area of the C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst C3 is 1084m 2 g -1 The average pore diameter is 7nm, and the oxygen reduction performance is excellent.
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