CN115786962B - Metal and nonmetal double-doped amorphous carbon material and preparation method and application thereof - Google Patents
Metal and nonmetal double-doped amorphous carbon material and preparation method and application thereof Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 45
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- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
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- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
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Abstract
The invention discloses a metal and nonmetal double-doped amorphous carbon material, a preparation method and application thereof. The amorphous carbon material of metal and nonmetal double doping is prepared by the following steps: step 1, mixing metal Mo salt, a dispersing agent and a carbon source in a preset proportion, and continuously stirring to obtain an intermediate product; step 2, stirring and mixing the intermediate product and a fluorine source serving as a soft template uniformly, performing ultrasonic treatment, naturally airing the mixture, and curing to obtain the mixture; step 3, carbonizing the mixture in a tube furnace filled with inert atmosphere, and grinding the obtained powder to obtain solid powder; and 4, washing the solid powder, and then drying to obtain the metal and nonmetal double-doped amorphous carbon material. Can be used for preparing hydrogen peroxide economically, efficiently and in a small scale.
Description
Technical Field
The invention relates to the technical field of material chemistry, in particular to a metal and nonmetal double-doped amorphous carbon material, and a preparation method and application thereof.
Background
Hydrogen peroxide, an essential chemical and environmental-friendly oxidizer, has been widely used in the fields of disinfection, sewage treatment, bleaching, etc. At present, the preparation of hydrogen peroxide is mainly based on an anthraquinone method, and the method adopts noble metal catalysis and has the problems of high cost, high risk, complex process and the like. In addition, the high concentration hydrogen peroxide produced by this method has a certain instability, which makes it a certain safety hazard during storage and transportation. Meanwhile, the use of the high-concentration hydrogen peroxide often needs dilution treatment, because the low-concentration hydrogen peroxide can basically meet most of industrial and living demands of people at home and abroad, so that the use cost of the low-concentration hydrogen peroxide is increased. Therefore, it is very attractive to develop a green, economical, distributed hydrogen peroxide production technology. Among them, the electrochemical oxygen reduction reaction and the direct binding of H 2/O2 both take place under milder conditions, and are considered as promising alternatives to the anthraquinone process. Compared with H 2/O2 directly combined to synthesize H 2O2, the preparation of H 2O2 by electrocatalytic two-electron oxygen reduction reaction (2 e - -ORR) has the advantages of low cost, strong sustainability, high safety and the like, and therefore, has been attracting attention in recent years.
2E - -ORR is a promising, environmentally friendly hydrogen peroxide production route. Among them, monoatomic catalysts (SACs) generally show good selectivity to 2e - -ORR due to their unique electronic structure and geometry. However, since the free energy of the metal in the form of monoatoms is significantly higher than that of the metal in the form of bulk, as the loading of the metal monoatoms on the substrate increases, the metal atoms are liable to agglomerate to form large clusters or nanoparticles, which greatly reduces its catalytic ability. Thus SACs typically have very low metal loadings, which makes the number of surface active sites in the catalyst very limited. Therefore, there is no delay in developing a two-electron oxygen reduction electrocatalyst having both high activity, high selectivity and multiple active sites. At present, people find that a plurality of nonmetallic hetero elements are doped on a carbon framework, so that a remote coordination effect can be generated, and the charge/spin density of carbon atoms can be effectively regulated, so that the carbon framework has good catalytic performance. However, the development of such catalysts is limited by the fact that nonmetallic heteroatoms and metallic heteroatoms tend to coordinate directly in the typical carbon framework, rather than forming the desired remote coordination structure.
Disclosure of Invention
The invention aims to provide a metal and nonmetal double-doped amorphous carbon material aiming at the problems of few active sites of a catalyst and the like in the prior art.
Another object of the present invention is to provide a method for preparing the amorphous carbon material.
It is another object of the present invention to provide the use of the amorphous carbon material in the electrocatalytic oxygen reduction to hydrogen peroxide.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a metal and nonmetal double-doped amorphous carbon material comprises an amorphous carbon substrate, metal atoms and nonmetal atoms, wherein the metal atoms are Mo atoms, and the nonmetal atoms are F atoms, and the metal atoms are uniformly dispersed and supported on the amorphous carbon substrate in a single-atom form.
In the above technical scheme, the metal and nonmetal double-doped amorphous carbon material is prepared by the following steps:
Step 1, mixing metal Mo salt, a dispersing agent and a carbon source in a preset proportion, and continuously stirring to obtain an intermediate product;
Step 2, stirring and mixing the intermediate product prepared in the step 1 and a fluorine source serving as a soft template uniformly, performing ultrasonic treatment, naturally airing the mixture, and curing to obtain the mixture;
step 3, carbonizing the mixture prepared in the step 2 in a tube furnace filled with inert atmosphere, and grinding the obtained powder to obtain solid powder;
And 4, washing the solid powder prepared in the step 3, and then drying to obtain the metal and nonmetal double-doped amorphous carbon material.
In the above technical scheme, in the step 1, the metal Mo salt is anhydrous MoCl 5, the carbon source is phenolic resin, and the dispersant is acetylacetone.
In the above technical solution, in the step 1, the mass ratio of Mo in the carbon source and the metal Mo salt is 0.5: (0.2-0.5).
In the above technical scheme, in the step 2, the fluorine source used as the soft template is an aqueous dispersion of polytetrafluoroethylene with the mass ratio of 20-60 wt%, and the mass ratio of polytetrafluoroethylene to phenolic resin is (10-15): 1.
In the technical scheme, the curing method in the step 2 is to be placed in an electrothermal drying oven for curing, the curing temperature is 100-120 ℃, and the curing time is 24-36h.
In the technical scheme, the inert gas in the step 3 is N 2, the carbonization temperature is 800-1000 ℃, and the carbonization time is 1-2h.
In the above technical solution, the washing method in step 4 is to wash the heat-treated material with a hydrochloric acid aqueous solution and deionized water in sequence;
the drying method in the step 4 is that the materials are placed in an electric heating drying oven for drying, the drying temperature is 80 ℃, the drying time is 6-24 hours, and the concentration of the hydrochloric acid aqueous solution in the step 4 is 2-3M;
in another aspect of the invention, the use of the metallic and non-metallic bi-doped amorphous carbon material as a catalyst in the electrocatalytic oxygen reduction to hydrogen peroxide is included.
In the technical scheme, dispersing the metal and nonmetal double-doped amorphous carbon material in a mixed solution containing nafion, isopropanol and water to obtain slurry with the concentration of 2-4mg/mL, dripping the slurry on hydrophobic carbon paper, airing the slurry at room temperature to obtain a hydrophobic carbon paper electrode loaded with the metal and nonmetal double-doped amorphous carbon material, preparing 0.1M KOH aqueous solution as electrolyte, taking the hydrophobic carbon paper electrode loaded with the metal and nonmetal double-doped amorphous carbon material as a working electrode, taking a Pt sheet as a counter electrode, taking an Ag/AgCl electrode as a reference electrode, and preparing H 2O2 by electrolysis under the voltage of-0.223-0.227V (vs. RHE);
the volume ratio of nafion, isopropanol and water is 3-5:20-30:77-65.
Compared with the prior art, the invention has the beneficial effects that:
1. Compared with a cluster or metal particle catalyst, the metal and nonmetal double-doped amorphous carbon material has larger atomic utilization rate, and has great potential in reasonable utilization of metal resources and atomic economy.
2. Compared with a single-atom catalyst, the metal and nonmetal double-doped amorphous carbon material is prepared by directly introducing fluorine serving as a second phase doping element onto a uniformly dispersed Mo metal carbon skeleton, and the material has a larger specific surface area and a multistage pore structure, and can be used for preparing hydrogen peroxide economically, efficiently and in a small scale.
3. The fluorine in the metal and nonmetal double-doped amorphous carbon material effectively activates surrounding carbon atoms, so that the amorphous carbon material has a plurality of active sites and good conductivity, and can show excellent reactivity, yield, selectivity and stability in the process of preparing hydrogen peroxide by electrocatalytic two-electron oxygen reduction.
4. The invention obtains the metal and nonmetal double-doped amorphous carbon material by using a soft template method and a subsequent pyrolysis process, and the preparation method has simple process and low equipment cost and meets the actual production requirement.
Drawings
FIG. 1 is a surface SEM image of the material prepared in example 1.
Fig. 2 is an SEM magnified of the material prepared in example 1.
Fig. 3 is a surface TEM image of the material prepared in example 1.
Fig. 4 is a TEM magnified image of the material prepared in example 1.
FIG. 5 is a nitrogen isothermal adsorption/desorption curve of the material prepared in example 1.
FIG. 6 is a HAADF-STEM diagram of the material prepared in example 1.
FIG. 7 is a Cyclic Voltammetry (CV) curve of electrocatalytic oxygen reduction in Ar, O 2 saturated electrolyte to hydrogen peroxide at a scan rate of 10mV s -1 using the material prepared in example 1 as a catalyst.
FIG. 8 is a Linear Scanning Voltage (LSV) curve for electrocatalytic oxygen reduction to hydrogen peroxide using the material prepared in example 1 as a catalyst at a scan rate of 5mV s -1 and O 2 saturated electrolyte.
FIG. 9 is a plot of selectivity and electron transfer number for hydrogen peroxide prepared using the material prepared in example 1 as a catalyst.
FIG. 10 is a plot of current density change at 0V for the material prepared in example 1. Wherein the slope represents the capacitance of the electrochemical bilayer.
FIG. 11 is a graph of H 2O2 RR performance of the material prepared in example 1 in Ar saturated 0.1M KOH solution at a scan rate of 10mVs-1,1mM H 2O2.
FIG. 12 is a graph showing the amperometric curve and the hydrogen peroxide concentration change at-0.023V vs. RHE for the material prepared in example 1.
Fig. 13 is a surface SEM image of the material prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
a metal and non-metal bi-doped amorphous carbon material prepared by the steps of:
Step 1, adding 1.08g of MoCl 5 and 2.5g of 20wt.% phenolic resin ethanol solution into a 50mL beaker, adding acetylacetone serving as a dispersing agent, and placing the mixture on a magnetic stirrer for stirring for 30min to obtain an intermediate product.
And 2, uniformly stirring and mixing the intermediate product obtained by the preparation with 12.5g of 60wt.% Polytetrafluoroethylene (PTFE) dispersion, performing ultrasonic treatment for 1 hour, naturally airing the mixture, and placing the mixture in an electric heating drying oven at 100 ℃ for curing for 24 hours to obtain the mixture.
And 3, carbonizing the prepared mixture in a tube furnace filled with nitrogen (N 2) for 2 hours at the carbonization temperature of 900 ℃, collecting the obtained powder, and grinding the powder into fine powder to obtain solid powder.
And 4, washing the prepared solid powder with 2M hydrochloric acid aqueous solution and deionized water in sequence to remove metal nano particles and other residues, putting the obtained substances into an electric heating drying oven, and drying at 80 ℃ for 6 hours to remove water in the material, thereby obtaining the metal and nonmetal double-doped amorphous carbon material, and marking as Mo-F-C.
The prepared Mo-F-C catalytic material was subjected to surface morphology observation by Scanning Electron Microscopy (SEM), transmission Electron Microscopy (TEM) and high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), and as shown in fig. 1 to 4, the average pore diameter of the material surface was about 100nm due to the pore structure generated by 60wt.% polytetrafluoroethylene dispersion as pore-forming template. As shown in FIG. 3, mo in Mo-F-C after removal of the metal compound by acid washing is distributed in the form of single atom. As shown in fig. 5, the specific surface area of the material measured by the low temperature nitrogen adsorption method reaches 773.6m 2 g-1. As shown in fig. 6, mo is uniformly located on the carbon substrate in the form of single atoms.
Example 2
The Mo-F-C composite material prepared in the example 1 is subjected to catalytic performance test, wherein the specific test method comprises the steps of preparing an aqueous solution of 0.1M KOH as electrolyte for the catalytic performance test, and uniformly dispersing the Mo-F-C composite material in a volume ratio of 3:20:77, obtaining slurry with the concentration of 4mg/mL, dripping the slurry on a commercial hydrophobic carbon paper electrode, and airing the slurry at room temperature to obtain a hydrophobic carbon paper electrode loaded with a Mo-F-C composite material; and (3) dripping the slurry on the glassy carbon part of the rotary disc electrode, and airing at room temperature to obtain the glassy carbon electrode loaded with the Mo-F-C composite material. The hydrophobic carbon paper electrode loaded with the Mo-F-C composite material is used as a working electrode, a Pt sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the yield and the long-term stability of hydrogen peroxide prepared by electrocatalytic oxygen reduction are tested. The activity, the selectivity and the double-layer capacitance of the electrocatalytic oxygen reduction preparation hydrogen peroxide are tested by taking the glassy carbon electrode loaded with the Mo-F-C composite material as a working electrode, taking a carbon rod as a counter electrode and taking an Ag/AgCl electrode as a reference electrode.
As shown in FIG. 7, in the O 2 saturated electrolyte, the Mo-F-C composite showed a significant ORR current at an initial reaction potential of 0.60V vs. RHE, but not in the Ar saturated electrolyte, indicating good ORR activity of Mo-F-C.
As shown in FIGS. 8-9, the Mo-F-C composite material was found to have higher ring current and medium disk current, approaching the theoretical value of 2e - -ORR, by evaluating the selectivity of Mo-F-C on a rotating disk electrode (RRDE) with a predetermined collection efficiency, indicating that Mo-F-C has higher H 2O2 activity and selectivity (80%).
As shown in fig. 10-11, electrochemical double layer capacitance (C dl) was measured proportional to the electrochemical surface area (ECSA) of the material, and it was found that the Mo-F-C composite material had a C dl of 9.97mF cm -2, indicating a large specific surface area and multiple active sites for Mo-F-C, such that Mo-F-C exhibited high H 2O2 activity and selectivity.
As shown in FIG. 12, the Mo-F-C composite material can continuously work for more than 12 hours under the condition of-0.023V vs RHE, and the stable hydrogen peroxide yield is maintained, which indicates that the material has good stability.
Example 3
Based on example 1, the pyrolysis temperature in this example was controlled to 1000℃and the pyrolysis time was 2 hours, with the remaining conditions being the same as in example 1. The SEM diagram of the surface morphology of the finally obtained Mo-F-C composite material is shown in FIG. 13. As can be seen from the figure, the Mo-F-C composite still has a large amount of pore structure due to 60wt.% polytetrafluoroethylene dispersion as pore-forming template. Tests show that the performance of the Mo-F-C composite material for preparing hydrogen peroxide by electrocatalytic oxygen reduction is similar to that of the embodiment 1.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The application of a metal and nonmetal double-doped amorphous carbon material as a catalyst in preparing hydrogen peroxide by electrocatalytic oxygen reduction is characterized by comprising an amorphous carbon substrate, metal atoms and nonmetal atoms, wherein the metal atoms are Mo atoms, and the nonmetal atoms are F atoms, and the metal atoms are uniformly dispersed and supported on the amorphous carbon substrate in a single atom form;
The amorphous carbon material doped with metal and nonmetal is prepared by the following steps:
Step 1, mixing metal Mo salt, a dispersing agent and a carbon source in a preset proportion, and continuously stirring to obtain an intermediate product;
Step 2, stirring and mixing the intermediate product prepared in the step 1 and a fluorine source serving as a soft template uniformly, performing ultrasonic treatment, naturally airing the mixture, and curing to obtain the mixture;
step 3, carbonizing the mixture prepared in the step 2 in a tube furnace filled with inert atmosphere, and grinding the obtained powder to obtain solid powder;
And 4, washing the solid powder prepared in the step 3, and then drying to obtain the metal and nonmetal double-doped amorphous carbon material.
2. The use according to claim 1, wherein in step 1, the metal Mo salt is anhydrous moci 5, the carbon source is phenolic resin, the dispersant is acetylacetone, and in step 1, the mass ratio of Mo in the carbon source and metal Mo salt is 0.5: (0.2-0.5).
3. The use according to claim 2, wherein in step 2 the fluorine source as soft template is an aqueous dispersion of 20-60 wt% polytetrafluoroethylene, the mass ratio of polytetrafluoroethylene to phenolic resin being (10-15): 1.
4. The use according to claim 1, wherein the curing in step 2 is carried out by placing in an electrothermal drying oven at a temperature of 100-120 ℃ for 24-36 hours.
5. The use according to claim 1, wherein the inert gas in step 3 is N 2, the carbonization temperature is 800-1000 ℃, and the carbonization time is 1-2h.
6. The use according to claim 1, wherein the washing in step 4 is performed by washing the heat-treated material with a hydrochloric acid aqueous solution of a predetermined concentration and deionized water in that order.
7. The use according to claim 6, wherein the aqueous hydrochloric acid has a concentration of 2-3M.
8. The use according to claim 1, wherein the drying in step 4 is carried out by placing in an electrothermal drying oven at 80 ℃, and the drying time is 6-24 hours.
9. The use according to claim 1, wherein the amorphous carbon material doped with both metals and non-metals is dispersed in a mixed solution containing nafion, isopropanol and water to obtain a slurry with a concentration of 2-4 mg/mL, which is dripped on the hydrophobic carbon paper and dried at room temperature to obtain a hydrophobic carbon paper electrode loaded with the amorphous carbon material doped with both metals and non-metals, 0.1M of KOH aqueous solution is prepared as an electrolyte, the hydrophobic carbon paper electrode loaded with the amorphous carbon material doped with both metals and non-metals is used as a working electrode, a Pt sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and H 2O2 is prepared by electrolysis at a voltage of-0.223-0.227V vs. RHE.
10. The use according to claim 9, wherein the volume ratio of nafion, isopropanol to water is 3-5:20-30:77-65.
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| CN115108545A (en) * | 2022-05-10 | 2022-09-27 | 华南理工大学 | Nitrogen-doped porous carbon-loaded monatomic molybdenum material and preparation method and application thereof |
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| CN111384407A (en) * | 2020-02-25 | 2020-07-07 | 电子科技大学 | Preparation method of metal monoatomic-dispersed ordered mesoporous carbon spheres |
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