CN115786962A - 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a metal and nonmetal double-doped amorphous carbon material and a preparation method and application thereof. The amorphous carbon material with double doping of metal and nonmetal is prepared by the following steps: step 1, mixing metal Mo salt, a dispersant and a carbon source in a predetermined ratio, and continuously stirring to obtain an intermediate product; step 2, stirring and mixing the intermediate product and a fluorine source which is simultaneously used as a soft template uniformly, carrying out ultrasonic treatment, naturally airing the mixture, and solidifying to obtain a 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 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
Peroxy compoundHydrogen hydride, a necessary chemical and environmental oxidant, has been widely used in the fields of disinfection, sewage treatment and bleaching. At present, the preparation of hydrogen peroxide is mainly based on an anthraquinone method, and the method adopts noble metal catalysis, so that the problems of high cost, high risk, complex process and the like exist. In addition, the high concentrations of hydrogen peroxide produced by this method have some instability that presents certain safety hazards during storage and transportation. Meanwhile, the use of the high-concentration hydrogen peroxide often needs dilution treatment, and the low-concentration hydrogen peroxide can basically meet most industrial and living requirements of people at home and abroad, so that the use cost of the hydrogen peroxide is increased. Therefore, it would be very attractive to develop a green, economical, distributed hydrogen peroxide production technology. Wherein the electrochemical oxygen reduction reaction and H 2 /O 2 Direct binding occurs under milder conditions and is considered a promising alternative to the anthraquinone process. Electrocatalytic two-electron oxygen reduction reaction (2 e) - ORR) preparation of H 2 O 2 And H 2 /O 2 Direct binding synthesis of H 2 O 2 In contrast, the method has advantages such as low cost, strong sustainability, and high safety, and therefore has attracted much attention in recent years.
2e - ORR is a promising, environmentally friendly route to hydrogen peroxide production. Among them, the monatomic catalysts (SACs) are generally referred to as 2e catalysts due to their unique electronic structure and geometry - ORR shows good selectivity. However, since the free energy of the metal in monatomic form is significantly higher than that of the metal in bulk form, as the loading of the metal monatomic on the substrate increases, the metal atoms tend to agglomerate to form large clusters or nanoparticles, which greatly reduces their catalytic capacity. Thus, SACs typically have very low metal loadings, which makes the number of surface active sites in the catalyst very limited. Therefore, the development of a two-electron oxygen reduction electrocatalyst with high activity, high selectivity and multiple active sites is not easy. At present, people find that a plurality of non-metallic hetero elements are doped on a carbon framework to generate a remote coordination effect, so that the charge/spin density of carbon atoms is effectively adjusted,so that they have good catalytic performance. However, the development of such catalysts is limited because non-metallic and metallic heteroatoms tend to coordinate directly in the typical carbon framework rather than forming the intended remote coordination structures.
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.
The invention also provides application of the amorphous carbon material in preparing hydrogen peroxide by electrocatalytic oxygen reduction.
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, and metal atoms and nonmetal atoms which are uniformly dispersed and loaded on the amorphous carbon substrate in a monoatomic mode, wherein the metal atoms are Mo atoms, and the nonmetal atoms are F atoms.
In the above technical solution, the metal and nonmetal double-doped amorphous carbon material is prepared by the following steps:
step 2, stirring and mixing the intermediate product obtained in the step 1 and a fluorine source which is simultaneously used as a soft template uniformly, performing ultrasonic treatment, naturally airing the mixture, and curing to obtain a 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 solution, in the step 1, the metal Mo salt is anhydrousMoCl 5 The carbon source is phenolic resin, and the dispersing agent is acetylacetone.
In the above technical scheme, in step 1, the mass ratio of the carbon source to Mo in the metal Mo salt is 0.5: (0.2-0.5).
In the technical scheme, in the step 2, the fluorine source used as the soft template is 20-60wt.% of aqueous dispersion of polytetrafluoroethylene, and the mass ratio of the polytetrafluoroethylene to the phenolic resin is (10-15): 1.
In the technical scheme, the curing method in the step 2 is to place the mixture in an electric heating drying oven for curing, wherein the curing temperature is 100-120 ℃, and the curing time is 24-36h.
In the above technical solution, the inert gas in 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 substance with an aqueous hydrochloric acid solution with a predetermined concentration and deionized water in sequence;
the drying method in the step 4 comprises the steps of placing the mixture in an electric heating drying oven for drying, wherein 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 present invention, the use of said metallic and non-metallic double doped amorphous carbon material as a catalyst in the preparation of hydrogen peroxide by electrocatalytic oxygen reduction is included.
In the technical scheme, the metal and nonmetal double-doped amorphous carbon material is dispersed in a mixed solution containing nafion, isopropanol and water to obtain slurry with the concentration of 2-4mg/mL, the slurry is dripped on hydrophobic carbon paper and dried at room temperature to obtain a hydrophobic carbon paper electrode loaded with the metal and nonmetal double-doped amorphous carbon material, 0.1M KOH aqueous solution is prepared as electrolyte, the hydrophobic carbon paper electrode loaded with the metal and nonmetal double-doped amorphous carbon 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 H is prepared by electrolysis under the voltage of-0.223-0.227V (vs 2 O 2 ；
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 cluster or metal particle catalysts, the metal and nonmetal double-doped amorphous carbon material has higher atom utilization rate as the catalyst, and has great potential in reasonable utilization of metal resources and atom economy.
2. Compared with a single-atom catalyst, the metal and nonmetal double-doped amorphous carbon material provided by the invention is used as the catalyst, and fluorine is directly introduced into a uniformly dispersed Mo metal carbon skeleton as a second-phase doping element to obtain the Mo-F-C catalytic material, and the material has a large specific surface area and a hierarchical pore structure, and can be used for economically, efficiently and massively preparing hydrogen peroxide.
3. The introduction of fluorine in the metal and nonmetal double-doped amorphous carbon material effectively activates surrounding carbon atoms, so that the material has a plurality of active sites and good conductivity, and can show excellent reaction activity, yield, selectivity and stability in the process of preparing hydrogen peroxide by electrocatalysis and two-electron oxygen reduction.
4. The invention obtains the amorphous carbon material with double doping of metal and nonmetal by utilizing the soft template method and the 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 photograph of the material prepared in example 1.
Fig. 2 is an SEM magnified view of the material prepared in example 1.
Fig. 3 is a TEM image of the surface of the material prepared in example 1.
Fig. 4 is a TEM magnified view of the material prepared in example 1.
Fig. 5 is a nitrogen isothermal sorption and desorption curve for the material prepared in example 1.
FIG. 6 is a HAADF-STEM diagram of the material prepared in example 1.
FIG. 7 shows the material prepared in example 1 as a catalyst at 10mV s -1 At scanning rate of Ar, O 2 Cyclic Voltammetry (CV) curves for the preparation of hydrogen peroxide by electrocatalytic oxygen reduction in saturated electrolyte.
FIG. 8 shows the material prepared in example 1 as a catalyst at a scan rate of 5mV s -1 And O 2 Linear Sweep Voltage (LSV) curve for the preparation of hydrogen peroxide by electrocatalytic oxygen reduction in saturated electrolyte.
FIG. 9 is a graph showing the selectivity and the number of electron transfers in the production of hydrogen peroxide using the material prepared in example 1 as a catalyst.
FIG. 10 is a graph of the current density at 0V for the material prepared in example 1. Where the slope represents the capacitance of the electrochemical double layer.
FIG. 11 shows the material prepared in example 1 at a scan rate of 10mVs-1,1mM H 2 O 2 Ar saturated 0.1MKOH solution of (2) 2 O 2 RR performance curve.
Figure 12 is a graph of the amperometric curve and 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 merely illustrative of the invention and are not intended to limit the invention.
Example 1:
a metal and nonmetal double-doped amorphous carbon material is prepared by the following steps:
And 2, uniformly stirring and mixing the prepared intermediate product and 12.5g of 60wt.% Polytetrafluoroethylene (PTFE) dispersion liquid, carrying out ultrasonic treatment for 1 hour, naturally airing the mixture, and placing the mixture in an electrothermal drying oven at 100 ℃ for curing for 24 hours to obtain a mixture.
Step 3, filling the mixture obtained in the preparation process into nitrogen (N) 2 ) Carbonizing for 2h in a tube furnace at 900 deg.C, collecting the obtained powder, and grinding 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 substance into an electric heating drying box, and drying at 80 ℃ for 6 hours to remove moisture in the material to obtain the metal and nonmetal double-doped amorphous carbon material, which is named as Mo-F-C.
The prepared Mo-F-C catalytic material is observed for surface morphology through a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM) and a high-angle annular dark field-scanning transmission electron microscope (HAADF-STEM), and as shown in FIGS. 1 to 4, the average pore diameter of the surface of the material is about 100nm, which is the pore structure generated by using 60wt.% of polytetrafluoroethylene dispersion as a pore-forming template. As shown in FIG. 3, mo in Mo-F-C was distributed in the form of a single atom after the removal of the metal compound by acid washing. 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 present on the carbon substrate in the form of a single atom.
Example 2
The Mo-F-C composite material prepared in example 1 was subjected to a catalytic performance test, wherein the specific test method comprises the steps of preparing a 0.1M KOH aqueous solution as an electrolyte for the catalytic performance test, and uniformly dispersing the Mo-F-C composite material in a dispersion medium at 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 at room temperature to obtain a hydrophobic carbon paper electrode loaded with the Mo-F-C composite material; and (3) dripping the slurry on the glassy carbon part on the rotating disk electrode, and airing at room temperature to obtain the glassy carbon electrode loaded with the Mo-F-C composite material. The yield and long-term stability of hydrogen peroxide prepared by electrocatalytic oxygen reduction are tested by taking the hydrophobic carbon paper electrode loaded with the Mo-F-C composite material as a working electrode, a Pt sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode. The glassy carbon electrode loaded with the Mo-F-C composite material is used as a working electrode, a carbon rod is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the activity, selectivity and double electric layer capacitance of hydrogen peroxide prepared by electrocatalytic oxygen reduction are tested.
As shown in FIG. 7, at O 2 In the saturated electrolyte, the Mo-F-C composite material shows obvious ORR current at the initial reaction potential of 0.60V vs. RHE, but does not exist in the Ar saturated electrolyte, which indicates that the Mo-F-C has good ORR activity.
As shown in FIGS. 8-9, evaluation of Mo-F-C selectivity on a rotating disk electrode (RRDE) with a predetermined collection efficiency revealed that the Mo-F-C composite had a high ring current and a moderate disk current, approaching 2e - Theoretical value of ORR, indicating that Mo-F-C has a higher H 2 O 2 Activity and selectivity (80%).
As shown in FIGS. 10-11, the electrochemical double layer capacitance (C) proportional to the electrochemical surface area (ECSA) of the material was measured dl ) Discovery of C of Mo-F-C composite Material dl Is 9.97mF cm -2 Shows that the Mo-F-C has large specific surface area and a plurality of active sites, so that the Mo-F-C shows high H 2 O 2 Activity and selectivity.
As shown in FIG. 12, under the condition of-0.023V vs RHE, the Mo-F-C composite material can continuously work for more than 12h, and the stable yield of hydrogen peroxide is kept, which shows that the material has good stability.
Example 3
Based on example 1, the pyrolysis temperature was controlled to 1000 ℃ and the pyrolysis time was 2 hours in this example, and the rest of the conditions were the same as example 1. The surface topography SEM image 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 significant amount of pore structure due to the 60wt.% polytetrafluoroethylene dispersion acting as pore-forming template. The performance of the Mo-F-C composite material for preparing hydrogen peroxide by electrocatalytic oxygen reduction is found to be similar to that shown in example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The amorphous carbon material is characterized by comprising an amorphous carbon substrate, and metal atoms and non-metal atoms which are uniformly dispersed and loaded on the amorphous carbon substrate in a monoatomic mode, wherein the metal atoms are Mo atoms, and the non-metal atoms are F atoms.
2. The metallic and non-metallic double doped amorphous carbon material of claim 1, prepared by the steps of:
step 1, mixing metal Mo salt, a dispersant and a carbon source in a predetermined ratio, and continuously stirring to obtain an intermediate product;
step 2, stirring and mixing the intermediate product obtained in the step 1 and a fluorine source which is simultaneously used as a soft template uniformly, performing ultrasonic treatment, naturally airing the mixture, and curing to obtain a 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.
3. The metallic and non-metallic double doped amorphous carbon material of claim 2, wherein in step 1, the metallic Mo salt is anhydrous MoCl 5 The carbon source is phenolic resin, the dispersing agent is acetylacetone, and the mass ratio of the carbon source to Mo in the metal Mo salt in the step 1 is 0.5: (0.2-0.5).
4. The metallic and non-metallic double doped amorphous carbon material according to claim 2, wherein said fluorine source as a soft template in step 2 is an aqueous dispersion of 20-60wt.% polytetrafluoroethylene, and the mass ratio of said polytetrafluoroethylene to said phenolic resin is (10-15): 1.
5. The metallic and non-metallic double doped amorphous carbon material according to claim 2, wherein the curing in step 2 is performed by placing in an electrothermal dry oven for curing at 100-120 ℃ for 24-36h.
6. The metallic and non-metallic double doped amorphous carbon material of claim 2, wherein the inert gas in step 3 is N 2 The carbonization temperature is 800-1000 ℃, and the carbonization time is 1-2h.
7. The metallic and non-metallic double doped amorphous carbon material according to claim 2, wherein the washing in step 4 is performed by sequentially washing the heat-treated material with a hydrochloric acid aqueous solution of a predetermined concentration and deionized water; preferably, the concentration of the aqueous hydrochloric acid solution is 2 to 3M.
8. The metallic and non-metallic double doped amorphous carbon material of claim 2, wherein the drying in step 4 is performed by drying in an electrothermal drying oven at 80 ℃ for 6-24h.
9. Use of the metallic and non-metallic double doped amorphous carbon material of claim 1 as a catalyst in the preparation of hydrogen peroxide by electrocatalytic oxygen reduction.
10. The use according to claim 8, wherein the metallic and non-metallic double doped amorphous carbon material is dispersed in a mixed solution containing nafion, isopropanol and water to obtain a slurry with a concentration of 2-4mg/mL, drop-coated on hydrophobic carbon paper, and air-dried at room temperatureObtaining 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 and an Ag/AgCl electrode as a reference electrode, and preparing H through electrolysis under the voltage of-0.223-0.227V (vs 2 O 2 (ii) a Preferably, the volume ratio of nafion, isopropanol and water is 3-5:20-30:77-65.
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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 |
| CN112382768A (en) * | 2020-11-17 | 2021-02-19 | 中国科学院新疆理化技术研究所 | Preparation method and application of iron and nitrogen co-doped hierarchical ordered porous carbon catalyst |
| 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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| CN108686693A (en) * | 2018-04-19 | 2018-10-23 | 重庆大学 | A kind of preparation method of monatomic cobalt-based nitrogen sulphur codope carbon material catalyst |
| CN111384407A (en) * | 2020-02-25 | 2020-07-07 | 电子科技大学 | Preparation method of metal monoatomic-dispersed ordered mesoporous carbon spheres |
| CN112382768A (en) * | 2020-11-17 | 2021-02-19 | 中国科学院新疆理化技术研究所 | Preparation method and application of iron and nitrogen co-doped hierarchical ordered porous carbon catalyst |
| 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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