CN114534766A - Method for preparing carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting gel method and application - Google Patents

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

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CN114534766A
CN114534766A CN202210276521.4A CN202210276521A CN114534766A CN 114534766 A CN114534766 A CN 114534766A CN 202210276521 A CN202210276521 A CN 202210276521A CN 114534766 A CN114534766 A CN 114534766A
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carbon
catalytic material
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CN114534766B (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 obtained gel precursor at a certain temperature to finally obtain the target mesoporous M-N-C catalyst. The raw materials used by the invention are economical, the process is simple, the obtained catalytic material has good stability, 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, has good Faraday efficiency, higher current density and good product selectivity, and has longer-time 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.

Description

Method for preparing carbon-based non-noble metal mesoporous M-N-C catalytic material by adopting gel method and application
Technical Field
The invention belongs to the technical field of preparation of electrocatalytic materials, 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, the emission of CO in large quantities is inevitable2Causes a series of serious environmental problems such as greenhouse effect, ocean acidification and the like, and seriously influences the living conditions of human beings and other animals and plants on the earth. The energy crisis is becoming more serious, and people have urgent need to find an alternative energy source. Thus, carbon dioxide electroreduction process (CO) driven by renewable power2RR) converts CO abundant in atmosphere2The conversion into usable energy not only helps to solve the energy crisis but also, more importantly, can reduce the amount of greenhouse gases. In CO2In the RR process, the catalytic material is responsible for CO2The key factors of reduction efficiency and composition are proved at present that some catalysts prepared from noble metal elements have excellent performance for reducing carbon dioxide, but the cost is high, the prospect for large-scale utilization is not good, so that the catalysts prepared from non-noble metal elements are urgently needed to be found and used for reducing carbon dioxide, an M-N-C catalytic system prepared from non-noble metal elements has low cost, has good performance for reducing carbon dioxide, and is expected to realize large-scale utilization, so that CO is reduced2Becomes a new energy utilization technology.
In recent years, carbon materials have attracted attention because of their characteristics of abundant raw materials, acid and alkali resistance, high temperature resistance, environmental friendliness, and the like, and have a certain catalytic activity for carbon dioxide electroreduction. When hetero atoms having different electronegativities are introduced into the carbon material, the catalytic activity of the raw carbon material can be significantly improved. Moreover, if considering the influence of limited active sites and poor conduction paths on the activity of the catalyst, designing the catalyst to have a porous structure characteristic has great significance for improving the performance of the catalyst.
According to international standards, there are three types of pore sizes. Those with a size of less than 2nm are called micropores; those greater than 50nm are called macropores; those having a size between 2nm and 50nm are called mesopores. The research and development of the mesoporous material have important significance for theoretical research and actual production. It has excellent properties not found in other porous materials: has a more ordered pore channel structure; the pore size is distributed in a single way, and can be changed in a wide range; the mesoporous shape is various and can be regulated and controlled through the composition and the property of the pore wall; high thermal stability can be obtained by optimizing the synthesis conditions. It is noteworthy that the large number of mesoporous structures in the carbon material are more favorable for mass transfer during catalytic reactions than are microporous structures because their diffusion paths are relatively short and they have a larger electrochemically active surface area than the macroporous structures, exposing more catalytically active sites. Therefore, the carbon material with the mesoporous structure is prepared, non-noble metal heteroatoms with different electronegativities are introduced into the carbon material, and the M-N-C catalyst with the mesoporous structure is designed and prepared for efficiently and electrically reducing CO2The realization of transformation techniques is of great significance.
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;
the invention also aims to provide application of the catalytic material in carbon dioxide electroreduction, oxygen reduction, oxygen evolution and electrochemical ammonia synthesis processes.
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 process:
(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, adding a metal source compound, and stirring to dissolve; sealing the solution and standing and storing at 90-100 ℃ for 6-8 h to obtain gel; aging the obtained gel at 5-80 ℃ for 2-60 h, and after aging, freezing at-50-1 ℃ for 2-50 h 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 a metal salt, and comprises one or more of iron 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, ethylene glycol, carbon tetrachloride, dioxane, cyclohexane and benzene.
(2) Preparation of mesoporous M-N-C catalytic material
And (3) carrying out heat treatment on the obtained catalyst gel precursor under the nitrogen or argon atmosphere, carrying out ball milling for 2-12 h 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 mesoporous M-N-C catalytic material has a pore structure size of 2-40 nm; the specific surface area is 100-2200 m2g-1In the meantime.
The heat treatment process comprises the following steps: in a tubular furnace, the temperature is firstly 0.5 to 20 ℃ for min-1Heating to 50-500 deg.C, keeping the temperature for 0.5-15 h, and heating to 1-20 deg.C for min-1Heating to 500-1500 deg.C, maintaining at constant temperature for 0.5-15 hr, and cooling at 0.5-20 deg.C for min-1The rate of (2) is decreased to room temperature.
Characterization of porous non-noble metal M-N-C carbon-based catalytic material
The mesoporous Ni-N-C carbon electro-catalytic material (Mp-NiNC) is taken as an example, and the catalytic material is characterized by TEM, XRD and XPS.
TEM representation: TEM images (FIGS. 1a and b) reveal the morphology of the best MP-NiNC prepared at different resolutions. FIG. 1a, FIG. 1b and FIG. 1c are TEM images of Mp-NiNC in different scales. As can be seen from FIG. 1b, Mp-NiNC has a clear pore structure. The existence of the porous structure enables the catalyst to have more Ni-Nx active sites which are easy to be accessed by reaction substances, and has the advantages of high mass transfer speed, small interface resistance and the like, thereby being applied to CO2RR applications show higher CO faradaic efficiency and lower current density. The lattice fringes between the (002) planes of the carbon in Mp-NiNC, with a spacing of 0.347nm, are clearly visible in FIG. 1d, demonstrating that this material is a typical carbon-based material.
XRD characterization: to obtain more carbon structure information, XRD testing was performed on Mp-NiNC catalysts. FIG. 2a shows the result of XRD test of 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 ° corresponding to Ni3The (113) plane of C. Under the mesoporous size, the porous carbon material is more beneficial to the contact of the catalyst and the reaction solution, and simultaneously enhances the dispersion of active sites, thereby promoting the reaction.
XPS characterization: FIG. 2b shows four peaks of 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 N oxide (405.7 eV). Fig. 2d shows the split peak of Ni2 p. It can be seen that Ni2p3/2Has a peak at about 854.0eV, a satellite peak at about 860.2eV, and Ni2p1/2At around 871.4eV, and at around 878.1 eV. Among them, the peaks at 852.9eV and 870.3eV can be classified as Ni3+The peaks at 854.0eV and 871.3eV can be assigned to Ni, and the peaks at 855.4eV and 872.7eV can be assigned to Ni2+. Wherein pyridine N accounts for 34.34%, Ni-Nx accounts for 17.87%23.82 percent of pyrrole N, 17.07 percent of graphite N and 6.88 percent of oxidized N. It can be seen that the pyridine N content is the greatest. Pyridine N is reported to enhance the para-CO2And stabilization of CO by H bond2RR intermediate COOH, so abundant pyridine N will improve the performance of the catalyst. Meanwhile, Ni-Nx also occupies a larger proportion, which indicates that Ni forms good coordination with N, and the activity of the catalyst is further improved.
BET test: to further understand the information on the pore structure, the BET test was performed on Mp-NiNC. FIG. 2e is a graph showing nitrogen adsorption-desorption of Mp-NiNC. It can be seen that the adsorption hysteresis loop appears in the middle of the adsorption isotherm and is the characteristic isotherm of the mesoporous material. In addition, the pore size distribution of Mp-NiNC was characterized as shown in FIG. 2 f. It can be seen that it has obvious mesopore distribution, average pore diameter is about 4.1 nm, specific surface area is about 500 m2 g-1. The mesoporous carbon can be used as a way for transferring charge to an active site, which greatly improves CO of the catalyst2RR performance.
Activity test of porous non-noble metal M-N-C carbon-based catalytic material
To illustrate the performance of the prepared porous non-noble metal M-N-C carbon-based catalytic material, an activity test is performed below by taking an Mp-NiNC carbon electrocatalytic material as an example.
FIG. 3a shows the CO Faraday Efficiencies (FE) of Ni-N-C samples at 900 deg.C, 950 deg.C, 1000 deg.C and 1050 deg.C under applied potentials of-0.9V to-1.5VCO). Optimal FE of Ni-N-C samples in the applied potential range at 900 deg.C, 950 deg.C, 1000 deg.C and 1050 deg.CCO90.90%, 94.73%, 95.85% and 95.00%. It is clear that the FE of the Ni-N-C sample at 900 ℃ can be seenCOSignificantly lower than the other samples. While Ni-N-C samples at 950 deg.C, 1000 deg.C and 1050 deg.C all showed the best FE at a potential of-1.3VCO. In which FE of a sample at 1000 ℃ isCOMost preferably. Optimum FE of 950 ℃ and 1050 ℃COSlightly below 1000 ℃ but all over 94.5%. Samples FE of 950 ℃, 1000 ℃ and 1050 ℃ were observed in a voltage range of-1.0 to-1.5VCOAlways kept above 90%. This indicates that the prepared Ni-N-C precursor is opposite to the calcinationThe burning temperature and the application potential have larger adaptability. FIG. 3b shows the H of the samples at 900 deg.C, 950 deg.C, 1000 deg.C and 1050 deg.C from-0.9 to-1.5V2Faraday Efficiency (FE)H2). Accordingly, FE of a 900 ℃ sampleH2FE of larger (minimum 9.10%), 950 ℃, 1000 ℃ and 1050 ℃ samplesH2All reach the lowest value at-1.3V. 5.27%, 4.15% and 5.00%, respectively. It can be seen that the FE of the 1000 ℃ treated Ni-N-C sampleH2And the lowest.
FIG. 3c shows the CO current density (j) of the samples from-0.9 to-1.5V at 900 deg.C, 950 deg.C, 1000 deg.C and 1050 deg.CCO). It can be seen that the maximum j of the samples at 900 ℃ and 1050 ℃ isCOValues (15.71 mA cm each)-2And-12.49 mA cm-2) Significantly lower than samples at 950 ℃ and 1000 ℃ (20.88 mA cm, respectively)-2And-21.29 mA cm-2). It is clear that,
the 1000 ℃ sample showed the best j at-1.3VCO. J of samples at 950 ℃ and 1000 ℃ in a voltage range of-1.0 to-1.3VCOIn close proximity. This again demonstrates the excellent compatibility of the prepared Ni-N-C precursor with the calcination temperature and the applied potential. Meanwhile, it can be observed that j of the sample at 950 ℃, 1000 ℃ and 1050 ℃ when the applied potential exceeds-1.3VCOAnd begins to fall. It can be explained that CO reaches the gas diffusion layer2Reducing at high potential immediately, but CO as the reduction product can not escape too late, and blocking active sites and electrolyte and reactant CO2Of lead to jCOAnd decreases. FIG. 3d shows the H of Ni-N-C samples at different temperatures of-0.9 to-1.5V2Current density (j)H2). It is evident that, from an overall perspective, j for the 900 deg.C, 950 deg.C, 1000 deg.C and 1050 deg.C samplesH2The value gradually decreased. Their maximum jH2The value was-1.60 mA cm-2，-1.21mA cm-2，-0.90mA cm-2And-0.69 mA cm-2. Notably, j for the Ni-N-C samples at different temperaturesH2Remains relatively stable at all potentials. This result indicates that the product yield of hydrogen evolution is relatively constant and has no linear relationship with voltage. General (1)Based on the above results, FE of the sample at 1000 ℃ was determinedCOMaximum, FEH2Lowest, jCOMaximum, jH2Is relatively small. A sample at 1000 ℃ was selected as the target sample and designated Mp-NiNC.
FIG. 4a shows FE of optimal sample Mp-NiNC at different applied potentialsCOAnd FEH2. As can be seen, FECOThe tendency of increasing and then decreasing is shown at-0.9 to-1.5V, but the fluctuation of such increase and decrease is relatively small, indicating the tolerance of Mp-NiNC to a wide voltage range. Stability is also one of the important parameters in measuring catalyst performance. Therefore, the stability test was carried out for 10 hours at-1.3V for Mp-NiNC, and the test results are shown in FIG. 4b, where FE is shownCOIn a gradually decreasing trend while FE isH2The opposite is true. The current density (j) shows the same as FECOSimilar trend. In the stability test, although FECOGradually decreased, but still kept above 95%, and the current density (j) also kept at-20 mA cm-2And the left and right show that the prepared Mp-NiNC has good stability.
In order to evaluate the effect of nickel on the catalytic performance, a nitrogen-doped carbon (N-C) catalyst containing no nickel was prepared as a comparative sample and subjected to an electrochemical test under the same electrolytic conditions as Mp-NiNC, and the test results are shown in FIG. 4C. FE of the N-C sample was measured at-0.9 to-1.5VCO50.46%, 31.07%, 22.52%, 15.71%, 10.85%, 8.20% and 6.44%, respectively. It can be seen that the FE of N-C is in the range of-0.9 to-1.5VCOMuch lower than 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 splitting, which is more advantageous for it. It is reported that the Ni-Nx sites in Ni-N-C catalysts have a low CO binding energy and therefore require a large overpotential to initiate the reaction. At the same time, it binds weakly to nh, which inhibits HER activity at a larger applied potential, thus achieving high CO selectivity.
In conclusion, different compounds are selected as a metal source (M), a nitrogen source (N) and a carbon source (C), a template is added, and a catalyst gel precursor is prepared and formed under a certain condition under the action of a proper solvent; and then carrying out heat treatment, ball milling treatment and impurity removal treatment on the obtained 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 obtained catalytic material has good stability, and especially the mesoporous structure between 2nm and 40nm is very beneficial to the mass transfer process of the electrocatalysis process, so the material is an ideal electrocatalysis material. Results, particularly in carbon dioxide electroreduction applications, 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, has good Faraday efficiency, higher current density and good product selectivity, and has longer-time 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, and also has good catalytic performance.
Drawings
FIG. 1 is a TEM image of the best performing Mp-NiNC made according to the present invention (a, b, c), (d) is a line profile of the lattice fringe spacing;
FIG. 2 is a high resolution XPS spectrum of the XRD spectra of Mp-NiNC prepared by the present invention (a), C1s (b), N1 s (C) and Ni2p (d); nitrogen adsorption-desorption isotherms of Mp-NiNC (e); analysis of pore width for Mp-NiNC (f).
FIG. 3 shows FE of Ni-N-C samples prepared by the present invention at different temperatures of 900 deg.C, 950 deg.C, 1000 deg.C and 1050 deg.CCO(a) And FEH2(b) (ii) a J of Ni-N-C samples at different temperatures (900 deg.C, 950 deg.C, 1000 deg.C, 1050 deg.C)CO(c) And jH2（d）；
FIG. 4 shows FE of Mp-NiNC prepared by the present invention under different applied potentialsCOAnd FEH2(a) (ii) a Stability test at-1.3V for Mp-NiNC (b); Mp-NiNC and FE of reference N-CCO（c）。
Detailed Description
The preparation and performance of the carbon-based non-noble metal mesoporous M-N-C catalytic material of the invention are further explained by the specific examples below.
Example 1
Preparation of Ni-N-C porous carbon catalyst and CO thereof2RR reduction Performance
(1) Preparation of Ni-N-C porous carbon catalyst precursor: first 4.0 g of melamine, 8.8 mL of formaldehyde solution, 62.0 mL of H2O and 0.028 g Na2CO3Mixing, and heating at 75 deg.C for 30 min to obtain clear solution. HCl was then added dropwise to adjust the pH to 2 and 2.0 g NiCl was added2Stirring for 30 min to obtain NiCl2And completely dissolving. The solution was then sealed and stored at 95 ℃ for 6.5 h to give a gelatinous gel. The prepared gel was aged at 25 ℃ for 48 h to allow the reaction to proceed more fully. After aging, the solvent is replaced by ethanol and acetone solution, and redundant water and other small molecules in the system are removed. And then freeze-drying the treated gel at-10 ℃ for 48 h to obtain the Ni-N-C precursor.
(2) Preparation of Ni-N-C porous carbon catalyst: the Ni-N-C precursor was heat treated in an ultra pure argon stream (operation: in a tube furnace, first at 300 deg.C (5 deg.C for min)-1) Maintaining for 1h, and further heating to 1000 deg.C (5 deg.C for min)-1) Charring for 2h, and finally at 5 deg.C for min-1Reducing the speed to room temperature, ball-milling in a ball mill for 6 hours after the treatment is finished, adding hydrochloric acid (1M) to adjust the pH value to 2, removing impurities, and converting the precursor into the mesoporous carbon material.
(3) CO of Ni-N-C porous carbon catalyst2RR reduction Performance: when the prepared Ni-N-C porous carbon catalyst is used in the reaction of carbon dioxide electroreduction to carbon monoxide, the faradaic efficiency of CO is-1.3VvsRHE can reach 95.85%, and can be kept stable for 20 hours, and has better product selectivity.
Example 2
Preparation of Mn, Cr-N-C porous carbon catalyst and CO thereof2RR reducing Properties
(1) Preparation of Mn, Cr-N-C porous carbon catalyst precursor: first 4.0 g of melamine, 15.6 mL of formaldehyde solution, 82.0 mL of H2O and 0.046 g Na2CO3Mixing, and heating at 80 deg.C for 40 min to obtain clear solution. Then HCl is added dropwise to adjust the pH value to about 2, and 4.0 g of MnCl is added2And CrCl3Stirring the mixture for 40 min to obtain MnCl2And CrCl3And completely dissolving. The solution was then sealed and stored at 90 ℃ for 6h to give a gelatinous gel. The prepared gel was aged at 20 ℃ for 40 h to allow the reaction to proceed more fully. After aging, the solvent is replaced by ethanol and acetone solution, and redundant water and other small molecules in the system are removed. And then freeze-drying the treated gel at-20 ℃ for 50h to obtain the Mn, Cr-N-C precursor.
(2) Preparation of Mn, Cr-N-C porous carbon catalyst: the precursor was subjected to a heat treatment at different temperatures in an ultra-pure argon gas stream (operation: first 200 ℃ C. (10 ℃ C. min.) in a tube furnace-1) Maintaining for 2 hr, and further heating to 1000 deg.C (10 deg.C for min)-1) Charring for 2h, and finally heating at 10 deg.C for min-1The speed is reduced to room temperature), ball milling is carried out in a ball mill for 6 hours after the treatment is finished, hydrochloric acid (1.5M) is added to adjust the pH value to 2.4 for impurity removal treatment, and the precursor is converted into the mesoporous carbon material.
(3) CO of Mn, Cr-N-C porous carbon catalyst2RR reduction Performance: when the prepared Mn, Cr-N-C porous carbon catalyst is used in the reaction of carbon dioxide electro-reduction to carbon monoxide, the faradaic efficiency of CO can reach 95.55 percent at-1.3 Vvs. RHE and the catalyst is kept stable for 30 hours.
Example 3
Preparation of Ni, Mn-N-C porous carbon catalyst and CO thereof2RR reducing Properties
(1) Preparation of Ni, Mn-N-C porous carbon catalyst precursor: first 4.0 g of melamine, 12.0 mL of formaldehyde solution, 85.0 mL of H2O and 0.36 g Na2CO3Mixing, and heating at 70 deg.C for 30 min to obtain clear solution. Then HCl is added dropwise to adjust the pH value to about 2, and 3.8 g NiCl is added2And MnCl2Stirring the mixture for 35 min to obtain NiCl2And MnCl2And completely dissolving. The solution was then sealed and stored at 93 ℃ for 7.5 h to give a gelatinous gel. The prepared gel was aged at 30 ℃ for 40 h to allow the reaction to proceed more fully. After aging, the solvent is replaced by ethanol and acetone solution, and redundant water and other small molecules in the system are removed. However, the device is not suitable for use in a kitchenAnd then freeze-drying the treated gel at-25 ℃ for 40 h to obtain the Ni, Mn-N-C precursor.
(2) Preparation of Ni, Mn-N-C porous carbon catalyst: the precursor was subjected to heat treatment at different temperatures in an ultra-pure argon gas stream (specific operation: first at 100 deg.C (1 deg.C for min)-1) Maintaining for 1h, and heating to 550 deg.C (3 deg.C for min)-1) Charring for 2h, and finally at 5 deg.C for min-1Reducing the speed to room temperature), ball-milling in a ball mill for 6 hours after the treatment is finished, adding hydrochloric acid (0.6M) to adjust the pH value to 4.2, removing impurities, and converting the precursor into the mesoporous carbon material.
(3) CO of Ni, Mn-N-C porous carbon catalyst2RR reduction Performance: when the prepared Ni, Mn and N CO-doped porous carbon catalyst is used in the reaction of carbon dioxide electro-reduction to carbon monoxide, the faradaic efficiency of CO is-1.3VvsRHE reached 94.55% and remained stable for 40 hours.
Example 4
Preparation of Fe-N-C porous carbon catalyst and oxygen reduction performance thereof
(1) Preparation of Fe-N-C porous carbon catalyst precursor: first 4.0 g of melamine, 21.6 mL of formaldehyde solution, 84.6 mL of H2O and 2.36 g Na2CO3Mixing, and heating at 75 deg.C for 35 min to obtain clear solution. Then HCl is added dropwise to adjust the pH value to about 2, and 5.5 g FeCl is added2Stirring for 30 min to make FeCl2And completely dissolving. The solution was then sealed and stored at 98 ℃ for 7.5 h to give a gelatinous gel. The prepared gel was aged at 28 ℃ for 55 h to allow the reaction to proceed more fully. After aging, the solvent is replaced by ethanol and acetone solution, and redundant water and other small molecules in the system are removed. And then freeze-drying the treated gel at-35 ℃ for 25 h to obtain the Fe-N-C precursor.
(2) Preparation of Fe-N-C porous carbon catalyst: the precursor was subjected to heat treatment at different temperatures in an ultra-pure argon gas stream (specific operation: first 400 deg.C (12 deg.C for min)-1) Maintaining for 1h, and heating to 1050 deg.C (12 deg.C for min)-1) Charring for 4h, and finally cooling at 8 deg.C for min-1The rate of (c) is reduced to room temperature), the treatment is endedAnd then ball-milling the mixture in a ball mill for 6 hours, adding hydrochloric acid (1.8M) to adjust the pH value to 3.5, removing impurities, and converting the precursor into the mesoporous carbon material.
(3) Oxygen reduction performance of Fe-N-C porous carbon catalyst: oxygen reduction electrochemical test results, the initial potential (0.02V vs. Ag/AgCl) of the Fe-N-C catalyst was slightly more positive than commercial Pt/C (-0.02V vs. Ag/AgCl), and the half-potential of the Fe-N-C catalyst was shifted positive by 20 mV compared to Pt/C. After 30000 s, the current of the Fe-N-C catalyst decreased by 26.0% relative to the initial current, while the Pt/C current attenuated by 50.0%. The Fe-N-C catalyst is shown to have better oxygen reduction catalytic activity and good stability compared with the commercial Pt/C catalyst.
Example 5
Preparation of Cr-N-C porous carbon catalyst and oxygen precipitation performance thereof
(1) Preparation of Cr-N-C porous carbon catalyst precursor: first 4.0 g of melamine, 28.5 mL of formaldehyde solution, 86.0 mL of H2O and 3.5 g Na2CO3Mixing, and heating at 72 deg.C for 25 min to obtain clear solution. Then HCl is added dropwise to adjust the pH to about 2, and 5.5 g CrCl is added3Stirring for 30 min to allow CrCl to react3And completely dissolving. The solution was then sealed and stored at 95 ℃ for 6.5 h to give a gelatinous gel. The prepared gel was aged at 65 ℃ for 55 h to allow the reaction to proceed more fully. After aging, the solvent is replaced by ethanol and acetone solution, and redundant water and other small molecules in the system are removed. And then freeze-drying the treated gel at-5 ℃ for 40 h to obtain a Cr-N-C precursor.
(2) Preparation of Cr-N-C porous carbon catalyst: the precursor was subjected to heat treatment at different temperatures in an ultra-pure argon gas stream (specific operation: first 360 deg.C (5 deg.C for min)-1) Maintaining for 1h, and heating to 950 deg.C (4 deg.C for min)-1) Charring for 2.5h, and finally at 5 deg.C for min-1Reducing the speed to room temperature), ball-milling in a ball mill for 6 hours after the treatment is finished, adding hydrochloric acid (1.5M) to adjust the pH value to 2.4, removing impurities, and converting the precursor into the mesoporous carbon material.
(3) Oxygen evolution performance of Cr-N-C porous carbon catalyst: as a result of an oxygen evolution electrochemical performance test, the oxygen evolution current density of the Cr-N-C catalyst at-0.7V (vs. SCE) is 2.5 times that of commercial Ir/C, and the peak potential of the Cr-N-C catalyst is shifted by 100 mV in comparison with the Ir/C. The Cr-N-C catalyst has good oxygen evolution catalytic activity.

Claims (10)

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, adding a metal source compound, and stirring to dissolve; sealing the solution and standing and storing at 90-100 ℃ for 6-8 h to obtain gel; aging the obtained gel at 5-80 ℃ for 2-60 h, and after aging, freezing 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 a metal salt, and comprises one or more of iron 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;
(2) preparing a mesoporous M-N-C catalytic material: carrying out heat treatment on the obtained catalyst gel precursor under a certain gas atmosphere, carrying out ball milling after the treatment is finished, adding hydrochloric acid to adjust the pH value to 1-6, carrying out impurity removal treatment, and drying to obtain a mesoporous M-N-C catalytic material;
the heat treatment process comprises the following steps: in a tubular furnace, the temperature is firstly 0.5 to 20 ℃ for min-1Heating to 50-500 deg.C, keeping the temperature for 0.5-15 h, and heating to 1-20 deg.C for min-1Heating to 500-1500 deg.C, maintaining at constant temperature for 0.5-15 hr, and cooling at 0.5-20 deg.C for min-1The rate of (2) is decreased to room temperature.
2. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by the gel method according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the nitrogen source compound, the carbon source compound and the metal source compound is 1: 0.05: 0.01-1: 500: 100.
3. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by the gel method according to claim 1, wherein the method comprises the following steps: in the step (1), 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.
4. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by the gel method according to claim 1, wherein the method comprises the following steps: in the step (1), the solvent is one or more of water, ethanol, ethylene glycol, carbon tetrachloride, dioxane, cyclohexane and benzene.
5. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by the gel method according to claim 1, wherein the method comprises the following steps: in the step (1), the freezing temperature of the freezing treatment is-50 ℃ to 1 ℃, and the time is 2 to 50 hours.
6. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by the gel method according to claim 1, wherein the method comprises the following steps: in the step (2), the gas atmosphere condition is nitrogen or argon.
7. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by the gel method according to claim 1, wherein the method comprises the following steps: in the step (2), the ball milling time is 2-12 h.
8. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by the gel method according to claim 1, wherein the method comprises the following steps: in the step (2), the pore structure size of the mesoporous M-N-C catalytic material is 2-40 nm.
9. The method for preparing the carbon-based non-noble metal mesoporous M-N-C catalytic material by the gel method according to claim 1, wherein the method comprises the following steps: in the step (2), the specific surface area of the mesoporous M-N-C catalytic material is 100-2200M2g-1。
10. The use of the carbon-based non-noble metal mesoporous M-N-C catalytic material prepared by the method of claim 1 in carbon dioxide electroreduction reactions.
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