CN110961137A - Nitrogen-doped graphitized porous carbon-loaded cobalt-based catalyst and preparation method thereof - Google Patents
Nitrogen-doped graphitized porous carbon-loaded cobalt-based catalyst and preparation method thereof Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 29
- 239000010941 cobalt Substances 0.000 title claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 29
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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Abstract
The invention discloses a nitrogen-doped graphitized porous carbon-supported cobalt-based catalyst and a preparation method thereof, belonging to the technical field of metal catalysts. The preparation method of the nitrogen-doped graphitized porous carbon material NGMC-800 comprises the following steps: (1) mesoporous carbon material GMC-800 and dicyanodiamine C2H4N4Mixing and grinding to obtain a mixture; (2) and (2) calcining the mixture obtained in the step (1) to obtain the nitrogen-doped carbon material NGMC-800. The inventionThe graphitized mesoporous carbon NGMC-800 obtained by the preparation method has regular and ordered mesoporous structure, relatively large pore volume and specific surface area, and relatively concentrated pore size distribution.
Description
Technical Field
The invention relates to a nitrogen-doped graphitized porous carbon-supported cobalt-based catalyst and a preparation method thereof, belonging to the technical field of metal catalysts.
Background
Fischer-Tropsch synthesis can convert synthesis gas into clean chemical fuels such as olefin, gasoline and diesel oil or valuable chemicals. In the Fischer-Tropsch synthesis reaction using cobalt as a catalyst, SiO is usually selected2、Al2O3And TiO2However, these carriers are liable to form a species which is difficult to reduce with cobalt at low temperature, and are disadvantageous in that the active metal is utilized sufficiently. And for the carbon material, the surface of the carbon material has the characteristics of inertia, acid and alkali resistance, excellent heat resistance and the like, so that a compound which is difficult to reduce is not easily generated in the preparation and calcination process of the catalyst, and the reduction of cobalt is facilitated. However, the surface of mesoporous carbon is inert due to its strong hydrophobicity. Therefore, it is necessary to modify the structure of the mesoporous carbon to introduce groups for activation, thereby improving the dispersibility of cobalt on the mesoporous carbon.
In general, a carbon material is subjected to oxidation treatment with a strongly oxidizing acid such as nitric acid or sulfuric acid to introduce an oxygen-containing group. Although the introduction of the oxygen-containing groups effectively enhances the interaction force between the metal and the carbon carrier and also reduces the surface tension of the carbon carrier, the acid has certain damage to the performance of the carbon material, thereby influencing the use of the catalyst.
In another method, mesoporous carbon is treated at high temperature in a nitrogen atmosphere. As Carbon Nanotubes, Hsu et al (HsuS.C., Lu C., Su F., et al, Thermodynmics and Regeneration Studies of CO2Adsorption on Multi-walled Carbon Nanotubes [ J]Chem.eng.sci.,2010,65(4):1354-2Adsorption, they found by study that at a water vapor content of 2.2%, CO2The maximum adsorbent amount reaches 107.8mg/g, and the CO is obtained after 100 cycles2The decrease of the adsorption amount is not significant.
Disclosure of Invention
In order to solve at least one problem, the invention provides a nitrogen-doped graphitized porous carbon-supported cobalt-based catalyst and a preparation method thereof. The invention takes soybean oil as a carbon source, adopts simple one-step solid-liquid ball milling to synthesize the graphitized ordered mesoporous carbon material with high specific surface area and pore volume, and then adopts a simple one-step solid-solid grinding method to mix the mesoporous carbon material with C2H4N4Grinding and calcining to obtain the nitrogen-doped graphitized porous carbon-supported cobalt-based catalyst.
The invention provides a preparation method of a nitrogen-doped graphitized porous carbon material, which comprises the following steps:
(1) mixing mesoporous carbon material with dicyanodiamine C2H4N4Mixing and grinding to obtain a mixture;
(2) and (2) calcining the mixture obtained in the step (1) to obtain the nitrogen-doped graphitized porous carbon material which is marked as NGMC-800.
In one embodiment, the method for preparing the mesoporous carbon material comprises the following steps:
s1: uniformly mixing SBA-15 and soybean oil by adopting a solid-liquid ball milling template method;
s2: transferring the mixture of S1 into a quartz tube furnace, and heating to 800 ℃ for carbonization;
s3: and etching the mixture of S2 with NaOH solution to obtain the mesoporous carbon material, which is marked as GMC-800.
In one embodiment, step (1) includes mesoporous carbon material (GMC-800) and dicyanodiamine (C)2H4N4) The mass ratio is 1: 1.
In one embodiment, the grinding in step (1) is grinding in an agate mortar for 15 min.
In one embodiment, the preparation method of the mesoporous carbon material GMC-800 comprises the following steps: mixing SBA-15 and soybean oil (mass ratio of 1:2) by solid-liquid ball milling template method at 400rpm min-1Ball milling for 5h at a rotating speed, mixing uniformly, transferring into a quartz tube furnace, and performing ball milling in N2At 4 ℃ per minute under protection-1Respectively heating to 800 deg.CCarbonizing at the temperature of 5h to obtain the calcined material. And etching the obtained product for 3 times by using NaOH solution (with the concentration of 2mol/L), wherein the etching time is 24h each time, and finally obtaining a calcined porous material, namely the mesoporous carbon material GMC-800.
In one embodiment, the preparation method of SBA-15 comprises: first, 3.0g of surfactant P123 and 3.0g of glycerol were mixed, and then added to 115.0mL of a dilute hydrochloric acid solution (1.5 mol.L)-1) Stirring the mixture in a water bath kettle at 37 ℃ for transparency, stirring the mixture vigorously after 3 hours, dropwise adding 6.45g of diethyl orthosilicate (TEOS) dropwise, and stirring vigorously for 5min after the addition is finished; then standing the mixed solution in a water bath at 37 ℃ for 24h, taking out the mixture and putting the mixture into an oven at 110 ℃ for 12 h; cooling to room temperature, repeatedly performing suction filtration and washing on the obtained white solid until the pH value is 7, then washing the white solid for 2-3 times by using absolute ethyl alcohol, then putting the product into an oven at 80 ℃ for drying, and then putting the product into a muffle furnace for roasting at 550 ℃ for 5 hours (the heating rate is 3 ℃ C. min.)-1) Finally, the ordered mesoporous material SBA-15 is prepared.
In one embodiment, the calcination in step (2) is specifically: in N2Calcining at 600 deg.C in atmosphere, and heating at 4 deg.C/min-1The calcination time is 5-10 h.
The second purpose of the invention is to obtain the nitrogen-doped graphitized porous carbon material NGMC-800 by adopting the preparation method of the nitrogen-doped graphitized porous carbon material NGMC-800.
The third object of the invention is a cobalt-based catalyst loaded with nitrogen-doped graphitized porous carbon material, which is marked as Co/NGMC-800.
The fourth purpose of the invention is that the preparation method of the cobalt-based catalyst Co/NGMC-800 loaded by the nitrogen-doped graphitized porous carbon material specifically comprises the following steps:
(1) mixing Co (NO)3)2·6H2Dissolving O in absolute ethyl alcohol solution; wherein said Co (NO)3)2·6H2The mass ratio of the O to the absolute ethyl alcohol is 1: 5-50;
(2) immersing nitrogen-doped graphitized porous carbon material NGMC-800 into the solution in the step (1), and then evaporating in a rotary evaporator to obtain a mixture; wherein the temperature of the rotary evaporator is 35 ℃, and the evaporation time is 30-40 min;
(3) putting the mixture obtained in the step (2) into an oven for drying; then calcining to obtain the catalyst Co/NGMC, wherein the drying temperature is 50 ℃ and the drying time is 2-7 h; the calcination is specifically as follows: in N2Calcining at 350 deg.C in atmosphere, and heating at 3 deg.C/min-1The calcination time is 2-10 h.
In one embodiment, the Co (NO) of step (1)3)2·6H2O and the NGMC-800 in the step (2) in a mass ratio of 1.08: 1;
the fifth purpose of the invention is to apply the nitrogen-doped graphitized porous carbon material NGMC-800 in the fields of gas separation, water purification, chromatographic analysis, photocatalysis and energy storage.
The sixth purpose of the invention is to apply the catalyst Co/NGMC in Fischer-Tropsch synthesis catalysis.
The invention has the beneficial effects that:
(1) the invention adopts a one-step solid-liquid ball milling method, graphitized mesoporous carbon material GMC-800 calcined at 800 ℃, and then nitrogen doping modification is carried out on the GMC-800 to obtain the graphitized mesoporous carbon material NGMC-800 with regular and ordered mesoporous structure, relatively large pore volume and specific surface area and relatively concentrated pore size distribution. After nitrogen doping, the specific surface area of the catalyst is relatively increased, and the pore diameter and the average pore volume do not change greatly compared with those before nitrogen doping.
(2) Compared with Co/GMC, the catalyst Co/NGMC obtained by the invention has larger specific surface area, and Fischer-Tropsch synthesis catalytic performance evaluation shows that: Co/NGMC with higher CO conversion and lower CO2Rate of formation of C5+The mesoporous carbon material NGMC is superior to CMK-3 and activated carbon AC carbon carriers in the performance of the Fischer-Tropsch synthesis catalyst taking the mesoporous carbon material NGMC as the carbon carrier, so that the performance of the GMC carrier is improved to a certain extent by doping nitrogen, and the mesoporous carbon material NGMC has certain significance in Fischer-Tropsch synthesis catalysis.
Drawings
FIG. 1 is an X-ray diffraction pattern of Co/NGMC of example 1 and Co/GMC of comparative example 1.
FIG. 2 is a TEM micrograph of Co/NGMC of example 1 and Co/GMC of comparative example 1 (a) is Co/NGMC; (b) is Co/GMC.
FIG. 3 is a graph of the nitrogen sorption and desorption curves for Co/NGMC of example 1 and Co/GMC of comparative example 1.
FIG. 4 is a plot of the pore size distribution of the Co/NGMC of example 1 and the Co/GMC of comparative example 1.
FIG. 5 is the H of Co/NGMC of example 1 and Co/GMC of comparative example 12-a TPR map.
FIG. 6 is the change in CO conversion during the Fischer-Tropsch synthesis reaction for the Co/NGMC of example 1 and the Co/GMC of comparative example 1.
FIG. 7 is a TEM micrograph of Co/NGMC of example 1 and Co/GMC of comparative example 1 after Fischer-Tropsch synthesis reaction (a) is Co/NGMC; (b) is Co/GMC.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The X-ray powder diffraction utilizes XRD to effectively determine the structure of an actually measured substance, and different substances have different structural properties, so that the lattice interplanar spacing and the diffraction characteristic peak intensity of the actually measured substance can be combined with standard PDF card for comparison, and the phase composition of the actually measured substance can be further determined, in addition, the diffraction peak intensity and the diffraction peak position of different substances are different, the structural parameter information can be determined by combining with XRD spectrum analysis, CuK α is adopted as a radiation source, the tube pressure is 40KV, the tube current is 200mA, the scanning range (2 theta) is 10-80 degrees, and the scanning step length is 0.02 degree, and the X-ray powder diffraction is obtained by calculation through a Sheble formula:
wherein D is the grain size, K is the Sieve constant, β is the half-peak width of the diffraction peak, lambda is the incident X-ray wavelength, and theta is the diffraction angle.
Transmission electron microscope: the method is characterized in that an electron beam with a short wavelength is used as a light source, then the electron beam is accelerated, gathered and projected on a measured sample, electrons collide with atoms in the sample to change the direction, so that the three-dimensional scattering is generated, and finally the generated influence is amplified and displayed on an imaging device. Preparing a sample: and (3) mixing the ultrasonic sample and absolute ethyl alcohol, then dripping the mixture on a carbon film copper net, and testing after drying.
Nitrogen physical adsorption desorption: the determination of pore size distribution by nitrogen adsorption and desorption is a relatively mature and common method. The method can effectively measure the physical structure characteristics of the catalyst such as specific surface area, pore diameter, pore volume and the like.
H2Temperature programmed reduction (H)2-TPR): placing 0.05g sample in a U-shaped quartz reaction tube, then treating for 2H in He inert atmosphere at 500 ℃, cooling to 60 ℃, and switching to 10% H2Heating the mixed gas of Ar and Ar to 800 ℃ (10 ℃ min)-1Temperature rise) and finally detecting the hydrogen consumption.
Evaluation of catalyst Performance: the Fischer-Tropsch operation flow is as follows: putting a certain amount of catalyst in the middle of a stainless steel reaction tube, opening reducing gas, adjusting a certain pressure for reduction, and adjusting the temperature to 450 ℃ for rise. After the reduction reaction is carried out for 16h, the reducing gas is closed and the reaction furnace is rapidly cooled to room temperature. Gas chromatographs GC-9160 and GC-2060 were opened and the protocol was followed. And opening the synthesis gas and regulating the synthesis gas to a constant flow rate, then heating the reaction furnace to a certain temperature, sampling every 5 hours, reacting for 60 hours, stopping sampling, and closing the synthesis gas and the gas chromatography. The reaction products can be detected analytically by gas chromatography: GC-9160 type gas chromatograph detection: detection of C Using FID1-C30A reaction product; unreacted synthesis gas and short-chain hydrocarbons can be detected by a gas chromatograph model GC-2060: CH detection using FID4、C2H6、C3H8And C4H10(ii) a Detection of H Using TCD2、N2、CO、CH4And CO2。
The specific performance was evaluated as follows:
1) CO conversion (in N) was calculated from the carbon balance2As internal standard):
(2) in the formula, SPrimary N2、SFinal N2And SInitial CO、SFinal CORespectively expressed as initial N corresponding to TCD chromatogram2Finally N2And peak areas of initial CO, final CO.
2)CH4Amount of product:
n after separation according to TDX-01 column2And CH4The peak area of (A) can be determined to obtain CH formed in the reaction4The amount of substance(s) of (c).
In the formula (3), SCH4、SN2And fCH4、fN2Respectively expressed as corresponding CH in TCD chromatogram4And N2Area peaks and their internal standard factors.
3)CnSelectivity of the product:
the amount of each hydrocarbon product substance (in terms of the amount of carbon atom-containing substance) in the reaction product was determined from the proportional relationship of all the products detected by gas chromatography. Then with CH4And as a second internal standard, the peak area of each hydrocarbon after FID separation is used for respectively obtaining the amount of each component substance in the product:
the hydrocarbon product selectivity is calculated from equation (5)
Example 1
A preparation method of a nitrogen-doped graphitized porous carbon material-loaded cobalt-based catalyst Co/NGMC specifically comprises the following steps:
(1) preparation of nitrogen-doped graphitized porous carbon material NGMC-800
The preparation method of SBA-15 comprises the following steps: firstly, 3.0g of surfactant P123 and 3.0g of glycerol are uniformly mixed, added into 115.0mL of dilute hydrochloric acid solution (1.5mol.L-1), stirred and transparent in a water bath kettle at 37 ℃, stirred vigorously after 3 hours, and dropwise added with 6.45g of diethyl orthosilicate (TEOS) dropwise, and stirred vigorously for 5min after the addition is finished; then standing the mixed solution in a water bath at 37 ℃ for 24h, taking out the mixture and putting the mixture into an oven at 110 ℃ for 12 h; and cooling to room temperature, repeatedly carrying out suction filtration and washing on the obtained white solid until the pH value is 7, then washing for 2-3 times by using absolute ethyl alcohol, then putting the product into an oven at 80 ℃ for drying, putting the product into a muffle furnace, and roasting for 5 hours at 550 ℃ (the heating rate is 3 ℃ and min < -1 >), and finally preparing the ordered mesoporous material SBA-15.
The preparation method of the mesoporous carbon material GMC-800 comprises the following steps: mixing SBA-15 and soybean oil (mass ratio of 1:2) by solid-liquid ball milling template method at 400rpm min-1Ball milling for 5h at a rotating speed, mixing uniformly, transferring into a quartz tube furnace, and performing ball milling in N2At 4 ℃ per minute under protection-1Respectively heating to 800 ℃ and carbonizing for 5h to prepare the calcined material. And etching the obtained product for 3 times by using NaOH solution (with the concentration of 2mol/L), wherein the etching time is 24h each time, and finally obtaining a calcined porous material, namely the mesoporous carbon material GMC-800.
Mixing a mesoporous carbon material (GMC-800) and dicyanodiamine (C) in a mass ratio of 1:12H4N4) Grinding in agate mortar for 15min, mixing the materials in N2Calcining under atmosphere at 600 deg.C (4 deg.C. min)-1And heating) to obtain the nitrogen-doped carbon material NGMC-800.
(2) Preparation of cobalt-based catalyst Co/NGMC loaded by nitrogen-doped graphitized porous carbon material
0.8719g of Co (NO) was taken3)2·6H2O was dissolved in an excess of anhydrous ethanol solution, and then 0.8g of nitrogen-doped carbon material NGMC-800 was immersed in an excess of cobalt nitrate ethanol solution, followed by slow evaporation at 35 ℃ in a rotary evaporator, and then the sample was put into an oven to be dried at 50 ℃. Then it is placed in N2Calcining at 350 deg.C (at 3 deg.C. min) under atmosphere-1Temperature rise) to finally obtain theThe cobalt-based catalyst Co/NGMC loaded by the nitrogen-doped graphitized porous carbon material.
Comparative example 1 (not doped with nitrogen)
A preparation method of a cobalt-based catalyst Co/GMC-800 loaded by a porous carbon material specifically comprises the following steps:
(1) preparation of ordered mesoporous carbon material (GMC-800):
mixing SBA-15 and soybean oil (mass ratio of 1:2) by solid-liquid ball milling template method at 400rpm min-1Ball milling for 5h at a rotating speed, mixing uniformly, transferring into a quartz tube furnace, and performing ball milling in N2At 4 ℃ per minute under protection-1Heating to 800 ℃ and carbonizing for 5h to prepare the calcined material. And etching the porous material by using NaOH solution (with the concentration of 2mol/L) for 3 times, wherein the etching time is 24h each time, and finally obtaining the calcined porous material GMC-800.
(2) Preparing Co/GMC-800 by an impregnation method:
0.8719g of Co (NO) was taken3)2·6H2O is dissolved in an excessive absolute ethanol solution, then 0.8g of a porous carbon material GMC-800 is immersed in an excessive cobalt nitrate ethanol solution, followed by slow evaporation at 35 ℃ in a rotary evaporator, and then the sample is put into an oven to be dried at 50 ℃. Finally, the sample is placed in N2Calcining at 350 deg.C (at 3 deg.C. min) under atmosphere-1Raising the temperature), and finally obtaining the catalyst Co/GMC-800.
And (3) testing and results:
the Co/NGMC catalyst of example 1 and the Co/GMC-800 catalyst of comparative example 1 were tested for their performance, and the results were as follows:
FIG. 1 is an X-ray diffraction pattern of Co/NGMC of example 1 and Co/GMC of comparative example 1. As can be seen from the figure: the diffraction peak at 26.6 ° corresponds to the characteristic diffraction peak of graphitized carbon, while the diffraction peaks at 36.4 °, 42.3 °, 61.6 °, 73.9 ° and 77.8 ° indicate that the cobalt nanoparticles in the catalyst are mainly present in the form of CoO (JCPDS 43-1004). From the XRD pattern, only CoO was present on the surface of the support, and other compounds of cobalt were not present. By comparing the difference of XRD diffraction peaks of the carrier-supported cobalt catalyst before and after nitrogen doping, the graphitization degree of the mesoporous carbon material is reduced after the nitrogen doping treatment. In addition, the diffraction peak intensities of the CoO on the surface of the nitrogen-doped and nitrogen-undoped catalysts are different, namely the particle size of the CoO becomes smaller after the nitrogen doping, which shows that the particle size of the CoO is influenced by the nitrogen-doped GMC. The particle sizes of the CoO before and after nitrogen doping are respectively calculated to be 11.6nm and 6.1nm through the Sherle formula.
FIG. 2 is a TEM micrograph of Co/NGMC of example 1 and Co/GMC of comparative example 1 (a) is Co/NGMC; (b) is Co/GMC. As can be seen from the figure: the morphology of the catalyst before and after nitrogen doping is changed, and the dispersion degree of cobalt particles loaded on nitrogen-doped mesoporous carbon GMC is lower than that of cobalt particles loaded on nitrogen-doped mesoporous carbon NGMC, which indicates that the carbon carrier after nitrogen doping can better disperse cobalt. Comparing mesoporous carbon before and after nitrogen doping, the mesoporous structure of Co/NGMC collapses, the cobalt oxide particles of the catalyst become smaller, and the dispersibility of the catalyst is higher. In addition, the particle size distribution graph obtained by TEM shows that the particle sizes of CoO in Co/GMC and Co/NGMC are respectively 9-12 nm and 5-6 nm.
FIG. 3 is a graph of the nitrogen sorption and desorption curves for Co/NGMC of example 1 and Co/GMC of comparative example 1. As can be seen from the figure: an obvious hysteresis loop exists between the relative pressure of 0.4-0.9, which shows that the adsorption curve is a typical IV-type curve and has a mesoporous structure.
FIG. 4 is a plot of the pore size distribution of the Co/NGMC of example 1 and the Co/GMC of comparative example 1. As can be seen from the figure: the pore size distributions of Co/GMC and Co/GMC were all centered at 3.9 nm.
Table 1 shows the surface texture parameters of the Co/NGMC of example 1 and the Co/GMC of comparative example 1, as shown in the table: for the nitrogen-doped mesoporous carbon material, the average pore diameter of the mesoporous carbon is reduced from 3.62nm to 3.55nm, and the specific surface area and the pore volume do not change greatly.
TABLE 1 surface texture parameters of Co/NGMC of example 1 and Co/GMC of comparative example 1
| Sample (I) | Specific surface area (m)2.g-1) | Pore size (nm) | Average pore diameter (cm)3.g-1) |
| Co/GMC | 246 | 3.62 | 0.22 |
| Co/NGMC | 274 | 3.55 | 0.24 |
FIG. 5 is the H of Co/NGMC of example 1 and Co/GMC of comparative example 12-a TPR map. As can be seen from the figure: the two supported cobalt catalysts before and after nitrogen doping both present three hydrogen reduction peaks. Wherein the first reduction peak from left to right represents Co3O4The hydrogen reduction peak → CoO, while the second represents the hydrogen reduction peak CoO → Co, and the third represents the vaporization peak of the carbon carrier. In addition, no reduction peak appeared above 700 ℃, indicating that no difficultly reducible compounds were formed on the catalyst surface. Comparing the hydrogen reduction peak of the Co-based catalyst before and after the nitrogen doping treatment, the Co-based catalyst loaded on the carrier after the nitrogen doping treatment3O4→ CoO → Co reduction temperature is higher, which indicates that the nitrogen doping process increases the interaction force between the mesoporous carbon carrier and cobalt.
FIG. 6 is the change in CO conversion during the Fischer-Tropsch synthesis reaction for the Co/NGMC of example 1 and the Co/GMC of comparative example 1. As can be seen from the figure: the conversion rate of CO is obviously increased after the nitrogen doping treatment. In addition, the stability of the catalyst before and after nitrogen doping is also changed, and after 60 hours of catalytic reaction, the CO conversion rate of the carbon-supported cobalt-based catalyst doped with nitrogen is reduced from 78% to 56%, and the CO conversion rate of the carbon-supported cobalt-based catalyst not doped with nitrogen is reduced from 37% to 26%.
Table 2 shows the Fischer-Tropsch reaction performance of the Co/NGMC of example 1 and the Co/GMC of comparative example 1. As can be seen from the table: after nitrogen doping C5+The selectivity is increased.
TABLE 2 shows the Fischer-Tropsch synthesis reaction performance of the Co/NGMC of example 1 and the Co/GMC of comparative example 1
aThe reaction conditions are that T is 270 ℃, P is 2MPa, and H2/CO＝2,GHSV＝3.6L·h-1g-1
bThe selectivity of hydrocarbons is standardized, except for carbon dioxide.
cC＝/CnIs C2-4The molar ratio of olefin to paraffin wax.
FIG. 7 is a TEM micrograph of Co/NGMC of example 1 and Co/GMC of comparative example 1 after Fischer-Tropsch synthesis reaction (a) is Co/NGMC; (b) is Co/GMC. As can be seen from the figure: along with the change of the reaction time, the particle size of CoO particles is continuously increased to generate an agglomeration phenomenon, and the particle size is increased to 12.5-17.5 nm and 10-20 nm from 9-12 nm and 5-6 nm before the reaction respectively.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a nitrogen-doped graphitized porous carbon material is characterized by comprising the following steps:
(1) mixing mesoporous carbon material with dicyanodiamine C2H4N4Mixing and grinding to obtain a mixture;
(2) calcining the mixture obtained in the step (1) to obtain a nitrogen-doped graphitized porous carbon material;
the preparation method of the mesoporous carbon material comprises the following steps:
s1: uniformly mixing SBA-15 and soybean oil by adopting a solid-liquid ball milling template method;
s2: transferring the mixture of S1 into a quartz tube furnace, and heating to 800 ℃ for carbonization;
s3: and etching the mixture of S2 with NaOH solution to obtain the mesoporous carbon material.
2. The method according to claim 1, wherein the mesoporous carbon material and dicyanodiamine C in step (1)2H4N4The mass ratio is 1: 1.
3. The preparation method according to claim 1, wherein the grinding in step (1) is carried out in an agate mortar for 15 min.
4. The preparation method according to claim 1, wherein the calcination in the step (2) is specifically: in N2Calcining at 600 deg.C in atmosphere, and heating at 4 deg.C/min-1The calcination time is 5-10 h.
5. The nitrogen-doped graphitized porous carbon material obtained by the preparation method of claim 1.
6. A cobalt-based catalyst supported by the nitrogen-doped graphitized porous carbon material as claimed in claim 5.
7. The preparation method of the nitrogen-doped graphitized porous carbon material-supported cobalt-based catalyst as claimed in claim 6, characterized by comprising the following steps:
(1) mixing Co (NO)3)2·6H2Dissolving O in absolute ethyl alcohol solution; wherein said Co (NO)3)2·6H2The mass ratio of the O to the absolute ethyl alcohol is 1: 5-50;
(2) immersing a nitrogen-doped graphitized porous carbon material into the solution obtained in the step (1), and then evaporating in a rotary evaporator to obtain a mixture; wherein the temperature of the rotary evaporator is 35 ℃, and the evaporation time is 30-40 min;
(3) putting the mixture obtained in the step (2) into an oven for drying; then calcining to obtain the catalyst, wherein the drying temperature is 50 ℃ and the drying time is 2-7 h; the calcination is specifically as follows: in N2Calcining at 350 deg.C under atmosphere, and heating at 3 deg.C/min-1The calcination time is 2-10 h.
8. The method according to claim 7, wherein the Co (NO) of step (1)3)2·6H2And (3) the mass ratio of O to the nitrogen-doped graphitized porous carbon material in the step (2) is 1.08: 1.
9. the nitrogen-doped graphitized porous carbon material of claim 5, for use in the fields of gas separation, water purification, chromatography, photocatalysis or energy storage.
10. The use of the nitrogen-doped graphitized porous carbon material-supported cobalt-based catalyst according to claim 6 in Fischer-Tropsch synthesis catalysis.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112777582A (en) * | 2021-01-25 | 2021-05-11 | 西北工业大学 | Preparation method of nitrogen-doped ordered mesoporous carbon/cobalt metal composite material |
| WO2021121088A1 (en) * | 2019-12-20 | 2021-06-24 | 常州工学院 | Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor |
| CN114335462A (en) * | 2021-12-24 | 2022-04-12 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material for low temperature, preparation method thereof and lithium battery |
| CN115779950A (en) * | 2022-11-29 | 2023-03-14 | 中山大学 | Carbonized mesoporous silica nanosphere-coated ultrafine cobalt cluster catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021121088A1 (en) * | 2019-12-20 | 2021-06-24 | 常州工学院 | Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor |
| CN112777582A (en) * | 2021-01-25 | 2021-05-11 | 西北工业大学 | Preparation method of nitrogen-doped ordered mesoporous carbon/cobalt metal composite material |
| CN112777582B (en) * | 2021-01-25 | 2022-09-09 | 西北工业大学 | Preparation method of nitrogen-doped ordered mesoporous carbon/cobalt metal composite material |
| CN114335462A (en) * | 2021-12-24 | 2022-04-12 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material for low temperature, preparation method thereof and lithium battery |
| CN114335462B (en) * | 2021-12-24 | 2023-06-02 | 陕西煤业化工技术研究院有限责任公司 | Graphite negative electrode material for low temperature, preparation method thereof and lithium battery |
| CN115779950A (en) * | 2022-11-29 | 2023-03-14 | 中山大学 | Carbonized mesoporous silica nanosphere-coated ultrafine cobalt cluster catalyst and preparation method and application thereof |
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