CN114534766B - Method for preparing carbon-based non-noble metal mesoporous M-N-C catalytic material by gel method and application - Google Patents

Method for preparing carbon-based non-noble metal mesoporous M-N-C catalytic material by gel method and application Download PDF

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CN114534766B
CN114534766B CN202210276521.4A CN202210276521A CN114534766B CN 114534766 B CN114534766 B CN 114534766B CN 202210276521 A CN202210276521 A CN 202210276521A CN 114534766 B CN114534766 B CN 114534766B
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catalytic material
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noble metal
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CN114534766A (en
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王伟
赵凯
陈柯宇
孙燕
韩娟
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Lanzhou Jiaotong University
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Abstract

The invention provides a method for preparing a carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting a gel method, which comprises the steps of selecting different compounds as a metal source, a nitrogen source and a carbon source, adding a template agent, and preparing and forming a catalyst gel precursor under a certain condition under the action of a proper solvent; and carrying out heat treatment, ball milling treatment and impurity removal treatment on the gel precursor at a certain temperature to finally obtain the target mesoporous M-N-C catalyst. The invention has the advantages of economical raw materials, simple process and good stability of the obtained catalytic material, and the results in the application of carbon dioxide electroreduction show that: the carbon-based non-noble metal mesoporous M-N-C catalytic material constructed by the invention has good catalytic performance on carbon dioxide electroreduction reaction, good Faraday efficiency, higher current density, good product selectivity and longer stability. The catalytic material can also be used for electrochemical catalytic processes such as oxygen reduction, oxygen precipitation, hydrogen precipitation, electrochemical synthesis of ammonia and the like.

Description

Method for preparing carbon-based non-noble metal mesoporous M-N-C catalytic material by gel method and application
Technical Field
The invention belongs to the technical field of electrocatalytic material preparation, and relates to a method for preparing a carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting a gel method.
Background
With the rapid development of industry, a large amount of discharged CO is unavoidable 2 Causing greenhouse effect and ocean acidChemical and other serious environmental problems seriously affect the living conditions of human beings and other animals and plants on the earth. The energy crisis is becoming more serious, and there is an urgent need for humans to find an alternative energy source. Whereby carbon dioxide electroreduction process (CO) driven by renewable electricity 2 RR) will be rich in CO in the atmosphere 2 The conversion into usable energy not only helps to solve the energy crisis, but more importantly, the amount of greenhouse gases can be reduced. And at CO 2 In RR process, the catalytic material is used for determining CO 2 The key factors of reduction efficiency and composition have now proven that some catalysts prepared from noble metal elements have very excellent performance for carbon dioxide reduction, but are not very good for large-scale utilization due to high cost, so that urgent needs are to find catalysts prepared from non-noble metal elements and use the catalysts for carbon dioxide reduction, and M-N-C catalytic systems prepared from non-noble metal elements have low cost, good performance for carbon dioxide reduction, and hopeful realization of large-scale utilization of CO 2 Becomes a new energy utilization technology.
In recent years, carbon materials have been attracting attention because of their rich raw materials, acid and alkali resistance, high temperature resistance, environmental friendliness and other characteristics, and have a certain catalytic activity for the electroreduction of carbon dioxide. When heteroatoms having different electronegativity are introduced into the carbon material, the catalytic activity of the original carbon material can be significantly improved. And if the influence of the limited active sites and the poor conductive paths on the activity of the catalyst is considered, the design of the catalyst with porous structure features is of great importance for improving the performance of the catalyst.
According to international standards, there are three types of pore sizes. Those dimensions less than 2nm are referred to as micropores; greater than 50nm is referred to as macropores; the size is between 2nm and 50nm, called mesopores. The research and development of mesoporous materials have important significance for theoretical research and actual production. It has excellent properties not possessed by other pore materials: has a more ordered pore canal structure; the pore size is single distributed, and the pore size can be changed in a wider range; the mesoporous shape is various, and can be regulated and controlled by the composition and the property of the pore wall; by virtue of the bestThe synthesis conditions can give high thermal stability. Notably, the large number of mesoporous structures in carbon materials is more conducive to mass transfer during catalytic reactions than microporous structures because of their relatively short diffusion paths and their greater electrochemically active surface area than macroporous structures, exposing more catalytically active sites. Therefore, the mesoporous carbon material is prepared, non-noble metal heteroatoms with different electronegativity are introduced into the mesoporous carbon material, and the M-N-C catalyst with the mesoporous structure is designed and prepared for high-efficiency electroreduction of CO 2 It is of great importance to implement the conversion technique.
Disclosure of Invention
The invention aims to provide a method for preparing a carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting a gel method;
it is another object of the present invention to provide the use of the catalytic material in electrochemical processes for carbon dioxide electroreduction, oxygen reduction, oxygen evolution, electrochemical synthesis of ammonia.
1. Preparation of carbon-based non-noble metal mesoporous M-N-C catalytic material
The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting the gel method comprises the following specific preparation processes:
(1) Preparation of gel precursors
Adding a nitrogen source compound, a carbon source compound and a template agent into a solvent, mixing, heating and stirring to completely dissolve to obtain a clear solution, adding HCl to adjust the pH value to 1.8-2.2, and then adding a metal source compound to stir and dissolve; sealing the solution, standing at 90-100 ℃ and preserving for 6-8 hours to obtain gel; aging the obtained gel at 5-80 ℃ for 2-60 hours, and after aging, freezing at-50-1 ℃ for 2-50 hours to obtain a catalyst gel precursor;
the nitrogen source compound is one or more of urea, amide, amine, melamine and ammonium chloride;
the carbon source compound is one or more of starch, glucose, sucrose, succinic acid, citric acid and lactic acid;
the metal source compound is metal salt, including one or more of ferric salt, cobalt salt, nickel salt, manganese salt, copper salt, tin salt and molybdenum salt, and the metal salt is one or more of hydroxide, sulfate, nitrate, chloride and composite salt;
the mass ratio of the nitrogen source compound to the carbon source compound to the metal source compound is 1:0.05:0.01-1:500:100;
the template agent is one or more of pyrrolidine, ethylenediamine, n-butylamine, sodium carbonate and sodium chloride; the mass ratio of the template agent to the carbon source compound is 1:0.1-1:300;
the solvent is one or more of water, ethanol, glycol, carbon tetrachloride, dioxane, cyclohexane and benzene.
(2) Preparation of mesoporous M-N-C catalytic material
And carrying out heat treatment on the obtained catalyst gel precursor under the nitrogen or argon atmosphere condition, carrying out ball milling for 2-12 hours after the treatment is finished, adding hydrochloric acid (with the concentration of 0.1-2M) to adjust the pH value to 1-6, carrying out impurity removal treatment, and drying to obtain the mesoporous M-N-C catalytic material. The pore structure size of the mesoporous M-N-C catalytic material is 2-40 nm; the specific surface area is 100-2200 m 2 g -1 Between them.
The heat treatment process comprises the following steps: in a tube furnace, the temperature is firstly between 0.5 and 20 ℃ for min -1 The temperature is raised to 50-500 ℃ at a constant temperature of 0.5-15 h, and then the temperature is raised to 1-20 ℃ for min -1 Heating to 500-1500 ℃ at a constant temperature for 0.5-15 h, and finally cooling to 0.5-20 ℃ for min -1 The rate of (2) is reduced to room temperature.
2. Characterization of Kong Zhuangfei noble metal M-N-C carbon-based catalytic materials
The mesoporous Ni-N-C carbon electrocatalytic material (Mp-NiNC) is used as an example and is characterized by TEM, XRD, XPS.
TEM characterization: TEM images (FIGS. 1a and b) reveal the morphology of the prepared optimal Mp-NiNC at different resolutions. Fig. 1a, 1b and 1c show TEM images of different dimensions of Mp-NiNC. As can be seen from fig. 1b, mp-NiNC has a clear pore structure. The catalyst has more Ni-Nx active sites which are easily accessible to reaction substances, and has the advantages of high mass transfer speed, small interface resistance and the like due to the existence of a porous structure, so that the catalyst can be used for preparing CO 2 RR applications exhibit higher CO faraday efficiencies and lower current densities. From FIG. 1d, it is clear that the lattice fringes between the (002) planes of carbon in Mp-NiNC are 0.347nm apart, demonstrating that this material is a typical carbon-based material.
XRD characterization: XRD testing was performed on Mp-NiNC catalysts in order to obtain more carbon structure information. FIG. 2a is XRD test results for Mp-NiNC. It can be seen that the characteristic peak at 26.1 ° corresponds to the (002) crystal plane of C; characteristic peak at 44.5 ° corresponds to Ni 3 The (113) crystal plane of C. The porous carbon material is more beneficial to the contact of the catalyst and the reaction solution under the mesoporous size, and simultaneously enhances the dispersion of active sites, thereby promoting the reaction.
XPS characterization: FIG. 2b shows four peaks for C1s, corresponding to C-C (283.3 eV), C-N (283.7 eV), C-O (284.9 eV) and O-C=O (289.0 eV), respectively. FIG. 2c shows 5 peaks of N1 s, pyridine N (397.7 eV), ni-Nx (399.4 eV), pyrrole N (399.8 eV), graphite N (401.7 eV) and oxidized N (405.7 eV), respectively. FIG. 2d shows the cleavage peak of Ni2 p. As can be seen, ni2p 3/2 The peak of (2) is about 854.0eV, the satellite peak is about 860.2eV, and Ni is 2p 1/2 Is around 871.4eV and the satellite peak is around 878.1 eV. Wherein the peaks at 852.9eV and 870.3eV can be categorized as Ni 3+ Peaks at 854.0eV and 871.3eV can be classified as Ni, and peaks at 855.4eV and 872.7eV can be classified as Ni 2+ . Wherein, pyridine N accounts for 34.34 percent, ni-Nx accounts for 17.87 percent, pyrrole N accounts for 23.82 percent, graphite N accounts for 17.07 percent, and oxidized N accounts for 6.88 percent. It can be seen that the content of pyridine N is the greatest. Pyridine N is reported to enhance P-CO 2 And stabilize CO through H bond 2 RR intermediate COOH, so the abundance of pyridine N will improve the catalyst performance. Meanwhile, ni-Nx also occupies a larger proportion, which indicates that Ni and N form good coordination, and the activity of the catalyst is further improved.
BET test: to further understand the information on pore structure, a BET test was performed on Mp-NiNC. FIG. 2e is a nitrogen adsorption-desorption diagram of Mp-NiNC. It can be seen that the adsorption hysteresis loop appears in the middle of the adsorption isotherm, which is a characteristic isotherm of the mesoporous material. In addition, also to Mp-NiNThe pore size distribution of C was characterized as shown in fig. 2 f. It can be seen that it has a distinct mesoporous distribution with an average pore size of about 4.1 and nm and a specific surface area of about 500 m 2 g -1 . Mesoporous carbon can be used as a path for charge transfer to active sites, which greatly improves CO of the catalyst 2 RR performance.
3. Activity test of Kong Zhuangfei noble metal M-N-C carbon-based catalytic material
To illustrate the performance of the prepared Kong Zhuangfei noble metal M-N-C carbon-based catalytic material, activity tests were performed below using Mp-NiNC carbon electrocatalytic material as an example.
FIG. 3a shows the CO Faraday Efficiency (FE) of Ni-N-C samples at 900, 950, 1000 and 1050 ℃ with applied potentials of-0.9V to-1.5V CO ). The optimal FE of the Ni-N-C sample is in the applied potential range at 900 ℃,950 ℃,1000 ℃ and 1050 DEG C CO 90.90%,94.73%,95.85% and 95.00%. It is apparent that at 900℃the FE of the Ni-N-C sample was found CO Significantly lower than other samples. While Ni-N-C samples at 950 ℃,1000 ℃ and 1050 ℃ all showed the best FE at a potential of-1.3V CO . Wherein FE of 1000 ℃ sample CO Preferably, the method comprises the steps of. Optimum FE at 950 ℃ and 1050 DEG C CO Slightly below 1000 c but all exceeding 94.5%. Samples FE at 950 ℃,1000 ℃ and 1050 ℃ can be observed in the voltage range of-1.0 to-1.5V CO Always keep above 90%. This shows that the prepared Ni-N-C precursor has great adaptability to the calcining temperature and application potential. FIG. 3b shows the samples from-0.9 to-1.5V H at 900 ℃,950 ℃,1000 ℃ and 1050 DEG C 2 Faraday Efficiency (FE) H2 ). Accordingly, FE of 900℃sample H2 Samples with larger (9.10% minimum) FE at 950 ℃,1000 ℃ and 1050 ℃ H2 All reached a minimum at-1.3V. 5.27%,4.15% and 5.00%, respectively. As can be seen, FE of 1000℃treated Ni-N-C samples H2 Lowest.
FIG. 3c shows the CO current density (j) of the sample from-0.9 to-1.5V at 900 ℃,950 ℃,1000 ℃ and 1050 DEG C CO ). It can be seen that the maximum j of the samples at 900℃and 1050 ℃ CO Value (15.7 respectively1 mA cm -2 And-12.49 mA cm -2 ) Samples significantly below 950 ℃ and 1000 ℃ (20.88 mA cm respectively -2 And-21.29 mA cm -2 ). It is obvious that the process is not limited to,
the 1000℃sample showed the best j at-1.3V CO . J of sample at 950 ℃ and 1000 ℃ in the voltage range of-1.0 to-1.3V CO Very close together. This again demonstrates the excellent compatibility of the prepared Ni-N-C precursor with the calcination temperature and applied potential. At the same time, it can be observed that when the applied potential exceeds-1.3V, the sample is at j at 950 ℃,1000 ℃ and 1050 DEG C CO And starts to descend. It can be explained that CO reaches the gas diffusion layer 2 Immediately reducing under high potential, but the reduction product CO can not escape too late, thus obstructing the active site and the electrolyte and reactant CO 2 Is brought into contact with, resulting in j CO And (3) lowering. FIG. 3d shows H of the Ni-N-C samples at different temperatures of-0.9 to-1.5V 2 Current density (j) H2 ). It is evident that from an overall point of view, samples j at 900 ℃,950 ℃,1000 ℃ and 1050 DEG C H2 The values were in a gradual decreasing trend. Their maximum j H2 The value was-1.60 mA cm -2 ，-1.21mA cm -2 ，-0.90mA cm -2 And-0.69 mA cm -2 . Notably, j for Ni-N-C samples at different temperatures H2 Remain relatively stable at all potentials. This result shows that the product yield of hydrogen evolution is relatively fixed and has no linear relationship with voltage. In summary, according to the above results, FE of 1000℃sample CO Highest, FE H2 Minimum j CO Maximum, j H2 Smaller. A sample at 1000℃was selected as the target sample and designated Mp-NiNC.
FIG. 4a shows FE's of the optimal sample Mp-NiNC at different applied potentials CO And FE H2 . It can be seen that FE CO The trend of increasing and decreasing at-0.9 to-1.5V is shown, but the fluctuation of the increase and decrease is relatively small, which indicates the tolerance of MP-NiNC to a wide voltage range. Stability is also one of the important parameters for measuring the performance of the catalyst. Thus, a 10 hour stability test was performed at-1.3V for Mp-NiNC, with the test results shown in FIG. 4bTo see, FE CO In a gradually decreasing trend, and FE H2 The opposite is true. The current density (j) shows the same as FE CO A similar trend. In the stability test, although FE CO Gradually decreasing but still remaining above 95%, the current density (j) is also kept at-20 mA cm -2 About, the prepared Mp-NiNC is shown to have good stability.
To evaluate the effect of nickel on catalytic performance, a nitrogen-doped carbon (N-C) catalyst without nickel was prepared as a comparative sample, and an electrochemical test was performed under the same electrolytic conditions as Mp-NiNC, and the test results are shown in fig. 4C. Measuring the FE of the N-C sample under the pressure of-0.9 to-1.5V CO 50.46%,31.07%,22.52%,15.71%,10.85%,8.20% and 6.44%, respectively. As can be seen, the range of-0.9 to-1.5V is the FE of N-C CO Well below Mp-NiNC and shows a gradual downward trend. This is because, as the potential increases, the applied potential is closer to the partial pressure of water decomposition, which is more advantageous. The Ni-Nx sites in Ni-N-C catalysts are reported to have lower CO binding energy and therefore require greater overpotential to initiate the reaction. At the same time, its binding to H is also weak, which will inhibit HER activity at larger application potentials, thus achieving high CO selectivity.
In summary, the invention selects different compounds as metal source (M), nitrogen source (N) and carbon source (C), and adds template agent, under the action of proper solvent, prepares and forms catalyst gel precursor under certain condition; and then carrying out heat treatment, ball milling treatment and impurity removal treatment on the gel precursor at a certain temperature to finally obtain the target mesoporous M-N-C catalyst. The raw materials used in the invention are economical, the process is simple, the stability of the obtained catalytic material is good, and especially, the mesoporous structure between 2nm and 40nm is very favorable for the mass transfer process of the electrocatalytic process, so that the catalyst is an ideal electrocatalytic material. Results, particularly in carbon dioxide electroreduction applications, indicate that: the carbon-based non-noble metal mesoporous M-N-C catalytic material constructed by the invention has good catalytic performance on carbon dioxide electroreduction reaction, good Faraday efficiency, higher current density, good product selectivity and longer stability. The catalytic material can also be used in electrochemical catalytic processes such as oxygen reduction, oxygen precipitation, hydrogen precipitation, electrochemical synthesis of ammonia and the like, and also has good catalytic performance.
Drawings
FIG. 1 is a TEM image of an optimal performance Mp-NiNC (a, b, c) prepared according to the invention, (d) is the line profile of lattice fringe spacing;
FIG. 2 is a XRD spectrum of Mp-NiNC prepared by the invention, and high resolution XPS spectra of C1s (b), N1 s (C) and Ni2p (d); nitrogen adsorption-desorption isotherms for Mp-NiNC (e); analysis of pore width of Mp-NiNC (f).
FIG. 3 shows FE's of Ni-N-C samples prepared by the present invention at different temperatures of 900 ℃,950 ℃,1000 ℃, 1050 DEG C CO (a) And FE H2 (b) The method comprises the steps of carrying out a first treatment on the surface of the Ni-N-C samples j at different temperatures (900 ℃,950 ℃,1000 ℃, 1050 ℃ C.) CO (c) And j H2 （d）；
FIG. 4 shows FE's of the MP-NiNC prepared according to the present invention at different applied potentials CO And FE H2 (a) The method comprises the steps of carrying out a first treatment on the surface of the Stability test of Mp-NiNC at-1.3V (b); mp-NiNC and N-C referenced FE CO （c）。
Detailed Description
The preparation and the performance of the carbon-based non-noble metal mesoporous M-N-C catalytic material of the invention are further described below by specific examples.
Example 1
Preparation of Ni-N-C Kong Zhuangtan catalyst and CO thereof 2 RR reduction Property
(1) Preparation of Ni-N-C Kong Zhuangtan catalyst precursor: first, 4.0. 4.0 g melamine, 8.8. 8.8 mL formaldehyde solution, 62.0 mL H 2 O and 0.028 g Na 2 CO 3 Mixing, heating at 75deg.C for 30 min to obtain clear solution. Then HCl is added dropwise to adjust the pH to 2, and then 2.0 g of NiCl is added 2 Stirring for 30 min to obtain NiCl 2 Completely dissolved. The solution was then sealed and stored at 95℃for 6.5. 6.5 h to give a gummy gel. The prepared gel was aged 48 h at 25 ℃ to allow the reaction to proceed more fully. After aging, ethanol and acetone solution are used to replace solventAnd removing redundant water and other small molecules in the system. The treated gel was then freeze-dried 48 at-10 ℃ h to give the Ni-N-C precursor.
(2) Preparation of Ni-N-C Kong Zhuangtan catalyst: the Ni-N-C precursor was heat treated in an ultra-pure argon stream (specifically, in a tube furnace, first at 300 ℃ (5 ℃ C. For min) -1 ) Holding for 1 hr, and heating to 1000deg.C (5deg.C for min) -1 ) Carbonizing for 2 hr, and finally cooling at 5deg.C for min -1 And (3) reducing the reaction rate to room temperature, ball-milling for 6 hours in a ball mill after the treatment is finished, adding hydrochloric acid (1M) to adjust the pH value to 2, performing impurity removal treatment, and converting the precursor into the mesoporous carbon material.
(3) CO of Ni-N-C Kong Zhuangtan catalyst 2 RR reduction performance: for the prepared Ni-N-C Kong Zhuangtan catalyst, when the catalyst is used in the reaction of carbon dioxide electroreduction into carbon monoxide, the Faraday efficiency of CO is-1.3VvsRHE can reach 95.85%, and is stable for 20 hours, and has good product selectivity.
Example 2
Preparation of Mn, cr-N-C Kong Zhuangtan catalyst and CO thereof 2 RR reduction Property
(1) Preparation of Mn, cr-N-C Kong Zhuangtan catalyst precursor: first, 4.0. 4.0 g melamine, 15.6. 15.6 mL formaldehyde solution and 82.0 mL H are added 2 O and 0.046 g Na 2 CO 3 Mixing, heating at 80deg.C for 40 min to obtain clear solution. Then dripping HCl to adjust the pH to about 2, and adding 4.0 g MnCl 2 And CrCl 3 Is stirred for 40 min to make MnCl 2 And CrCl 3 Completely dissolved. The solution was then sealed and stored at 90℃for 6h to give a gel-like gel. The prepared gel was aged at 20 ℃ for 40 h to allow the reaction to proceed more fully. After aging, ethanol and acetone solution are used for replacing solvent, and redundant water and other small molecules in the system are removed. The treated gel was then freeze-dried at-20℃for 50h to give a Mn, cr-N-C precursor.
(2) Preparation of Mn, cr-N-C Kong Zhuangtan catalyst: the precursor is subjected to heat treatment at different temperatures in an ultra-pure argon gas stream (the specific operation is as follows: in a tube furnace, first at 200 ℃ C. ("C.)10℃ min -1 ) Holding for 2 hr, and heating to 1000deg.C (10deg.C for min) -1 ) Carbonizing for 2 hr, and finally cooling at 10deg.C for min -1 And (3) cooling to room temperature), ball milling for 6 hours in a ball mill after the treatment is finished, adding hydrochloric acid (1.5M) to adjust the pH value to 2.4, performing impurity removal treatment, and converting the precursor into the mesoporous carbon material.
(3) CO of Mn, cr-N-C Kong Zhuangtan catalyst 2 RR reduction performance: for the prepared Mn, cr-N-C Kong Zhuangtan catalyst, when the catalyst is used in a reaction for electrically reducing carbon dioxide into carbon monoxide, the Faraday efficiency of CO is-1.3 Vvs. RHE can reach 95.55 percent, and the catalyst is stable for 30 hours.
Example 3
Preparation of Ni, mn-N-C Kong Zhuangtan catalyst and CO thereof 2 RR reduction Property
(1) Preparation of Ni, mn-N-C Kong Zhuangtan catalyst precursor: first, 4.0. 4.0 g melamine, 12.0 mL formaldehyde solution, 85.0 mL H 2 O and 0.36 g Na 2 CO 3 Mixing, heating at 70deg.C for 30 min to obtain clear solution. Then dripping HCl to adjust the pH to about 2, and then adding 3.8 g NiCl 2 And MnCl 2 Is stirred for 35 min to make NiCl 2 And MnCl 2 Completely dissolved. The solution was then sealed and stored at 93℃for 7.5. 7.5 h to give a gummy gel. The prepared gel was aged at 30℃for 40. 40 h to allow the reaction to proceed more fully. After aging, ethanol and acetone solution are used for replacing solvent, and redundant water and other small molecules in the system are removed. The treated gel was then freeze-dried at-25 ℃ for 40 h to yield the Ni, mn-N-C precursor.
(2) Preparation of Ni, mn-N-C Kong Zhuangtan catalyst: the precursor is subjected to different temperature heat treatments in ultra-pure argon gas stream (specifically, the operation is as follows: first at 100deg.C (1 deg.C for min) -1 ) Holding for 1 hr, and heating to 550deg.C (3deg.C for min) -1 ) Carbonizing for 2 hr, and finally cooling at 5deg.C for min -1 And (3) cooling to room temperature), ball milling for 6 hours in a ball mill after the treatment is finished, adding hydrochloric acid (0.6M) to adjust the pH value to 4.2, performing impurity removal treatment, and converting the precursor into the mesoporous carbon material.
(3) Ni, mn-N-C Kong ZhuangtanCO of catalyst 2 RR reduction performance: for the prepared Ni, mn and N codoped Kong Zhuangtan catalyst, when the catalyst is used in the reaction of carbon dioxide electroreduction into carbon monoxide, the Faraday efficiency of CO is-1.3VvsRHE can reach 94.55% and remain stable for 40 hours.
Example 4
Preparation of Fe-N-C Kong Zhuangtan catalyst and oxygen reduction performance thereof
(1) Preparation of Fe-N-C Kong Zhuangtan catalyst precursor: first, 4.0. 4.0 g melamine, 21.6. 21.6 mL formaldehyde solution, and 84.6 mL H 2 O and 2.36 g Na 2 CO 3 Mixing, heating at 75deg.C for 35 min to obtain clear solution. Then dripping HCl to adjust the pH to about 2, and then adding 5.5 g FeCl 2 Stirring for 30 min to obtain FeCl 2 Completely dissolved. The solution was then sealed and stored at 98℃for 7.5. 7.5 h to give a gummy gel. The prepared gel was aged 55 h at 28 ℃ to allow the reaction to proceed more fully. After aging, ethanol and acetone solution are used for replacing solvent, and redundant water and other small molecules in the system are removed. The treated gel was then freeze-dried at-35℃for 25 h to give Fe-N-C precursor.
(2) Preparation of Fe-N-C Kong Zhuangtan catalyst: the precursor was subjected to different temperature heat treatments in an ultra-pure argon stream (specific operations are as follows: first at 400 ℃ (12 ℃ C. Min) -1 ) Holding for 1 hr, and heating to 1050 deg.C (12 deg.C for min) -1 ) Carbonizing for 4 hr, and finally cooling at 8deg.C for min -1 And (3) cooling to room temperature), ball milling for 6 hours in a ball mill after the treatment is finished, adding hydrochloric acid (1.8M) to adjust the pH value to 3.5, performing impurity removal treatment, and converting the precursor into the mesoporous carbon material.
(3) Oxygen reduction performance of Fe-N-C Kong Zhuangtan catalyst: as a result of the oxygen reduction electrochemical test, the initial potential (0.02V vs. Ag/AgCl) of the Fe-N-C catalyst was slightly higher than that of the commercial Pt/C (-0.02V vs. Ag/AgCl), and the half potential of the Fe-N-C catalyst was shifted by 20 mV as compared to that of the Pt/C. After 30000 and s, the current of the Fe-N-C catalyst was reduced by 26.0% relative to the initial current, while the Pt/C current was attenuated by 50.0%. The Fe-N-C catalyst has better oxygen reduction catalytic activity compared with a commercial Pt/C catalyst and has good stability.
Example 5
Preparation of Cr-N-C Kong Zhuangtan catalyst and oxygen precipitation performance thereof
(1) Preparation of Cr-N-C Kong Zhuangtan catalyst precursor: first, 4.0. 4.0 g melamine, 28.5. 28.5 mL formaldehyde solution, 86.0 mL H 2 O and 3.5 g Na 2 CO 3 Mixing, heating at 72deg.C for 25 min to obtain clear solution. Then drop HCl to adjust pH to about 2, then add 5.5 g CrCl 3 Stirring for 30 min to obtain CrCl 3 Completely dissolved. The solution was then sealed and stored at 95℃for 6.5. 6.5 h to give a gummy gel. The prepared gel was aged 55 h at 65 ℃ to allow the reaction to proceed more fully. After aging, ethanol and acetone solution are used for replacing solvent, and redundant water and other small molecules in the system are removed. The treated gel was then freeze-dried at-5℃for 40 h to give a Cr-N-C precursor.
(2) Preparation of Cr-N-C Kong Zhuangtan catalyst: the precursor was subjected to different temperature heat treatments in an ultra-pure argon stream (specific operations are as follows: first at 360 ℃ (5 ℃ C. Min) -1 ) Holding for 1 hr, and heating to 950 deg.C (4 deg.C for min) -1 ) Carbonizing for 2.5 hr, and finally cooling at 5 deg.c for min -1 And (3) cooling to room temperature), ball milling for 6 hours in a ball mill after the treatment is finished, adding hydrochloric acid (1.5M) to adjust the pH value to 2.4, performing impurity removal treatment, and converting the precursor into the mesoporous carbon material.
(3) Oxygen evolution performance of Cr-N-C Kong Zhuangtan catalyst: as a result of the oxygen evolution electrochemical performance test, the oxygen evolution current density of the Cr-N-C catalyst at-0.7. 0.7V (vs. SCE) was 2.5 times that of the commercial Ir/C, and the peak potential of the Cr-N-C catalyst was shifted negatively by 100 mV compared to Ir/C. The Cr-N-C catalyst has good oxygen evolution catalytic activity.

Claims (8)

1. A method for preparing a carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting a gel method comprises the following steps:
(1) Preparation of gel precursor: adding a nitrogen source compound, a carbon source compound and a template agent into a solvent, mixing, heating and stirring to completely dissolve to obtain a clear solution, adding HCl to adjust the pH value to 1.8-2.2, and then adding a metal source compound to stir and dissolve; sealing the solution, standing at 90-100 ℃ and preserving for 6-8 hours to obtain gel; aging the obtained gel at 5-80 ℃ for 2-60 hours, and freezing after the aging is finished to obtain a catalyst gel precursor;
the nitrogen source compound is one or more of urea, melamine and ammonium chloride; the carbon source compound is one or more of starch, glucose, sucrose, succinic acid, citric acid and lactic acid; the metal source compound is metal salt, which is one or more of ferric salt, cobalt salt, nickel salt, manganese salt, copper salt, tin salt and molybdenum salt, and the metal salt is one or more of hydroxide, sulfate, nitrate, chloride and composite salt; the mass ratio of the nitrogen source compound to the carbon source compound to the metal source compound is 1:0.05:0.01-1:500:100; the template agent is one or more of pyrrolidine, ethylenediamine, n-butylamine, sodium carbonate and sodium chloride; the mass ratio of the template agent to the carbon source compound is 1:0.1-1:300;
(2) Preparation of mesoporous M-N-C catalytic material: performing heat treatment on the obtained catalyst gel precursor under a certain gas atmosphere condition, performing ball milling after the treatment, adding hydrochloric acid to adjust the pH value to 1-6, performing impurity removal treatment, and drying to obtain the mesoporous M-N-C catalytic material;
the heat treatment process comprises the following steps: in a tube furnace, the temperature is firstly between 0.5 and 20 ℃ for min -1 The temperature is raised to 50-500 ℃ at a constant temperature of 0.5-15 h, and then the temperature is raised to 1-20 ℃ for min -1 Heating to 500-1500 ℃ at a constant temperature for 0.5-15 h, and finally cooling to 0.5-20 ℃ for min -1 The rate of (2) is reduced to room temperature.
2. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting the gel method according to claim 1, which is characterized in that: in the step (1), the solvent is one or more of water, ethanol, glycol, carbon tetrachloride, dioxane, cyclohexane and benzene.
3. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting the gel method according to claim 1, which is characterized in that: in the step (1), the freezing temperature of the freezing treatment is-50-1 ℃ and the time is 2-50 h.
4. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting the gel method according to claim 1, which is characterized in that: in the step (2), the gas atmosphere condition is nitrogen or argon.
5. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting the gel method according to claim 1, which is characterized in that: in the step (2), the ball milling time is 2-12 hours.
6. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting the gel method according to claim 1, which is characterized in that: in the step (2), the pore structure size of the mesoporous M-N-C catalytic material is 2-40 nm.
7. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting the gel method according to claim 1, which is characterized in that: in the step (2), the specific surface area of the mesoporous M-N-C catalytic material is 100-2200M 2 g -1 。
8. The use of a carbon-based non-noble metal mesoporous M-N-C catalytic material prepared according to the method of claim 1 in carbon dioxide electroreduction reactions.
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