CN114308124A - Efficient catalyst for nitrogen fixation and preparation method and application thereof - Google Patents
Efficient catalyst for nitrogen fixation and preparation method and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000013110 organic ligand Substances 0.000 claims abstract description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 28
- 239000010941 cobalt Substances 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000004729 solvothermal method Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 24
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 235000010265 sodium sulphite Nutrition 0.000 claims description 12
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- MPXAYYWSDIKNTP-UHFFFAOYSA-N n-(2-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC=C1N MPXAYYWSDIKNTP-UHFFFAOYSA-N 0.000 claims description 5
- 229960001413 acetanilide Drugs 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- ALMHSXDYCFOZQD-UHFFFAOYSA-N n-(3-methylphenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(C)=C1 ALMHSXDYCFOZQD-UHFFFAOYSA-N 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N meta-toluidine Natural products CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of nitrogen fixation catalysts, and discloses a high-efficiency catalyst for nitrogen fixation, and a preparation method and application thereof. The high-efficiency catalyst for nitrogen fixation comprises an aromatic amine organic ligand and a cobalt-based carrier which are combined through a coordination bond, and the preparation method comprises the following steps: (1) mixing N, N-dimethylformamide and absolute ethyl alcohol, adding an aromatic amine organic ligand, dissolving, adding divalent cobalt salt, and stirring for reacting for 30-40min to obtain a precursor; (2) and carrying out solvothermal reaction on the precursor, and separating out a product after the reaction is finished to obtain the high-efficiency catalyst for fixing nitrogen. The catalyst has good nitrogen fixation effect, can convert nitrogen into ammonia under both light and dark conditions, and can be used for nitrogen fixation under the light condition at normal temperature and normal pressure.
Description
Technical Field
The invention relates to the field of nitrogen fixation catalysts, in particular to a high-efficiency catalyst for nitrogen fixation and a preparation method and application thereof.
Background
Nitrogen is one of the inert gases, because nitrogen is the highest content of gas in the earth environment, but the molecular bond energy of nitrogen is high, and large energy is required for immobilization. The Haber-Bosch process (300 ℃ C., 500 ℃ C., 15-25MPa) has been used for fixing nitrogen industrially, but the process requires a large amount of fossil fuel to provide heat and generates a large amount of greenhouse gases, so that the development of a new sustainable method for replacing the conventional nitrogen fixing method is urgently needed.
The photocatalytic nitrogen fixation technology utilizes solar energy to convert nitrogen into ammonia, has the advantages of mild conditions, energy conservation, environmental protection and the like, and is considered to be one of the best alternative methods of the traditional Haber-Bosch method. How to improve the nitrogen fixation efficiency of the photocatalyst is a main problem faced by the existing photocatalytic nitrogen fixation technology, and in the reported photocatalytic nitrogen fixation catalysts, the nitrogen fixation efficiency is low, and most of the nitrogen fixation efficiency is 10-50 mu mol.L-1·h-1. Among the usual photocatalytic media, the graphite phase carbon nitride (g-C)3N4) And modifications thereof are one of the most widely and extensively studied catalysts at present. But due to g-C3N4The solar energy collector has a wide energy gap (Eg is 2.77eV), only ultraviolet rays and near ultraviolet rays with high energy can be excited, and the content of ultraviolet radiation in sunlight is low (only accounts for about 3 percent), so that the solar energy utilization rate is low.
Transition metals contain d orbitals that are not completely filled with electrons to varying degrees and therefore have many potential properties. The organic ligand is coordinated on the transition metal, so that the performance of the organic ligand and the transition metal can be combined, and the forbidden bandwidth of the catalyst can be adjusted, so that the catalyst is adjusted towards the direction beneficial to nitrogen fixation, and a new idea is provided for the design of the nitrogen fixation catalyst. However, the nitrogen fixing effect of the organic ligand coordinated transition metal photocatalyst reported before is still limited, and the nitrogen fixing condition is harsh, for example, high temperature or low temperature needs to be applied in the nitrogen fixing process, or the wavelength of light is limited. For example, a nitrogen-fixing catalyst [ (TPB) Fe (N) Fe is disclosed in the literature, Catalytic conversion of Nitrogen to Ammonia by an iron model complex (Anderson, J.S.; Rittle, J.; Peters, J.C., Catalytic conversion of Nitrogen to Ammonia by an iron model complex, Nature 2013,501(7465),84-7.)2)][Na(12-crown-4)2]It has high catalytic activity at-78 deg.c, so that the nitrogen fixing reaction must be performed at low temperature for high nitrogen fixing efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-efficiency catalyst for nitrogen fixation, and a preparation method and application thereof. The catalyst has good nitrogen fixation effect, can convert nitrogen into ammonia under both light and dark conditions, and can be used for nitrogen fixation under the light condition at normal temperature and normal pressure.
The specific technical scheme of the invention is as follows:
a high-efficiency catalyst for nitrogen fixation comprises an aromatic amine organic ligand and a cobalt-based carrier which are combined through coordination bonds.
The mechanism of the catalyst for catalyzing the nitrogen fixation reaction is as follows: first, nitrogen is adsorbed at catalyst oxygen vacancies; under the condition of light, the light excites the catalyst semiconductor to generate electron-hole pairs, electrons are rapidly transferred from an amino position of the organic ligand to a metal position, then transferred to an oxygen hole and finally transferred to nitrogen, so that N [ identical to ] N of the nitrogen is broken, and reduction reaction is carried out. Meanwhile, a sacrificial reagent (such as sodium sulfite) used cooperatively consumes the hole to generate oxidation reaction; final N is NH3Is released from the catalyst again because of NH3Very soluble in water and therefore in NH4 +Is present in water. Under the condition of no light, the catalyst absorbs heat from the environment to generate electrons and holes, so that nitrogen fixation is realized.
The invention adopts aromatic amine and cobalt-based carrier for coordination, the reduction potential of the obtained catalyst is-0.1 eV-0.2 eV which is higher than the potential (-0.092eV) required by nitrogen fixation, thus the invention has better nitrogen fixation catalysis effect, the nitrogen fixation reaction can easily occur without inputting large energy, the requirement on nitrogen fixation condition is low, nitrogen can be converted into ammonia under both light and dark conditions, and the nitrogen fixation process under the light condition can be carried out under normal temperature and normal pressure, the nitrogen fixation rate can reach 174 mu mol.L-1·h-1。
Preferably, the aromatic amine organic ligand is one or more of p-anisidine, phthalimide, acetyl-m-toluidine, acetanilide and o-aminoacetanilide.
Further, the aromatic amine organic ligand is p-anisidine.
Compared with other aromatic amine organic ligands, the p-anisidine coordination cobalt-based carrier has higher catalytic activity because: in p-anisidine, methoxyl is connected on a benzene ring to serve as an electron-donating group, and one end of methoxyl is connected with amino to serve as an electron-withdrawing group, so that electrons have a directional transfer tendency on an organic ligand, the ligand has a good effect of separating electron hole pairs, and the catalytic efficiency of the nitrogen fixation reaction can be improved.
Preferably, the molar ratio of the aromatic amine organic ligand to the cobalt element in the cobalt-based carrier is 0.4-10: 1.
In the catalyst of the invention, the relative content of the aromatic amine organic ligand and the cobalt-based carrier influences the nitrogen fixation performance of the catalyst: if the relative content of the aromatic amine organic ligand is too small, electrons and holes are directly quenched due to too high photocatalytic activity of the cobalt-based carrier, so that the nitrogen fixation efficiency is too low, and even the nitrogen fixation reaction cannot be catalyzed; if the relative content of the aromatic amine organic ligand is too large, the cobalt-based carrier surface is covered by the organic ligand, and not enough active sites exist, so that the nitrogen fixation effect is also influenced, and even the nitrogen fixation reaction cannot be carried out.
A preparation method of the catalyst comprises the following steps:
(1) mixing N, N-dimethylformamide and absolute ethyl alcohol, adding an aromatic amine organic ligand, dissolving, adding divalent cobalt salt, and stirring for reacting for 30-40min to obtain a precursor;
(2) and carrying out solvothermal reaction on the precursor, and separating out a product after the reaction is finished to obtain the high-efficiency catalyst for fixing nitrogen.
Preferably, in the step (1), the molar ratio of the aromatic amine organic ligand to the cobalt ion in the divalent cobalt salt is 0.1-10: 1.
Preferably, the divalent cobalt salt is Co (NO)3)2·6H2O。
Preferably, in the step (1), the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 1: 0.5-1.5.
Preferably, in the step (2), the temperature of the solvothermal reaction is 150-210 ℃ and the time is 15-20 h.
In the invention, the temperature of the solvothermal reaction needs to be controlled within a certain range, and if the temperature is too low, the catalyst is not completely crystallized, so that the nitrogen fixation performance of the catalyst is influenced; if the temperature is too high, the inner container of the reaction kettle is broken, the solvent is volatilized, and the catalyst cannot be synthesized.
The nitrogen fixing condition is dark or under visible light or natural light.
Preferably, the specific process of the method is as follows: dispersing the catalyst in sodium sulfite solution, and fixing nitrogen in dark or under visible light or natural light.
Preferably, the mass volume ratio of the catalyst to the sodium sulfite solution is 1mg:0.5-1.5 mL; in the sodium sulfite solution, the concentration of sodium sulfite is 0.01-1 mol/L.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the aromatic amine organic ligand and the cobalt-based carrier are coordinated to be used as the nitrogen fixation catalyst, the catalytic activity is high, the requirement on nitrogen fixation conditions is low, nitrogen can be converted into ammonia under both light and dark conditions, and the nitrogen fixation process under the light condition can be carried out at normal temperature and normal pressure;
(2) by controlling the relative content of the aromatic amine organic ligand and the cobalt-based carrier, the aromatic amine organic ligand and the cobalt-based carrier can better play a synergistic effect, so that the nitrogen fixation effect of the catalyst is improved.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A high-efficiency catalyst for nitrogen fixation comprises an aromatic amine organic ligand and a cobalt-based carrier which are combined through coordination bonds. The aromatic amine organic ligand is one or more of p-anisidine, phthalimide, acetyl-m-toluidine, acetanilide and o-aminoacetanilide. The molar ratio of the aromatic amine organic ligand to the cobalt element in the cobalt-based carrier is 0.4-10: 1.
A preparation method of the catalyst comprises the following steps:
(1) mixing N, N-dimethylformamide and absolute ethyl alcohol according to the volume ratio of 1:0.5-1.5, adding an aromatic amine organic ligand, dissolving, adding divalent cobalt salt, wherein the molar ratio of the aromatic amine organic ligand to cobalt ions in the divalent cobalt salt is 0.4-10:1, and stirring for reaction for 30-40min to obtain a precursor;
(2) carrying out solvothermal reaction on the precursor at the temperature of 150-210 ℃, wherein the reaction time is 15-20 h; and after the reaction is finished, separating out a product to obtain the high-efficiency catalyst for fixing nitrogen.
A method for fixing nitrogen by using the catalyst, comprising the following steps: dispersing the catalyst in 0.01-1mol/L sodium sulfite solution, wherein the mass volume ratio of the catalyst to the sodium sulfite solution is 1mg:0.5-1.5mL, and carrying out nitrogen fixation under the conditions of light shielding, visible light or natural light.
Example 1
A high-efficiency catalyst for nitrogen fixation comprises a p-anisidine organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) mixing N, N-dimethylformamide and anhydrous ethanol 10mL respectively, adding p-anisidine organic ligand 0.5mmol, dissolving, adding Co (NO) 0.5mmol3)2·6H2O, stirring and reacting for 30min to obtain a precursor;
(2) and transferring the precursor into a reaction kettle with a 50mL polytetrafluoroethylene inner container, carrying out solvothermal reaction at the temperature of 200 ℃ for 15h, and centrifuging, washing and drying to obtain the high-efficiency nitrogen-fixing catalyst.
Example 2
A high-efficiency catalyst for fixing nitrogen comprises an acetyl m-toluidine organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) mixing N, N-dimethylformamide and anhydrous ethanol 10mL each, adding 0.5mmol of acetyl m-toluidine organic ligand, dissolving, and adding 0.5mmol of Co (NO)3)2·6H2O, stirring and reacting for 30minObtaining a precursor;
(2) and transferring the precursor into a reaction kettle with a 50mL polytetrafluoroethylene inner container, carrying out solvothermal reaction at the temperature of 200 ℃ for 15h, and centrifuging, washing and drying to obtain the high-efficiency nitrogen-fixing catalyst.
Example 3
A high-efficiency catalyst for nitrogen fixation comprises an o-aminoacetanilide organic ligand and a cobalt-based carrier which are combined through a coordination bond, and the preparation method comprises the following steps:
(1) mixing N, N-dimethylformamide and anhydrous ethanol each 10mL, adding 0.5mmol of o-aminoacetanilide organic ligand, dissolving, and adding 0.5mmol of Co (NO)3)2·6H2O, stirring and reacting for 30min to obtain a precursor;
(2) and transferring the precursor into a reaction kettle with a 50mL polytetrafluoroethylene inner container, carrying out solvothermal reaction at the temperature of 200 ℃ for 15h, and centrifuging, washing and drying to obtain the high-efficiency nitrogen-fixing catalyst.
Example 4
A high-efficiency catalyst for nitrogen fixation comprises a p-anisidine organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) mixing N, N-dimethylformamide and anhydrous ethanol 10mL respectively, adding p-anisidine organic ligand 0.5mmol, dissolving, adding Co (NO) 1.25mmol3)2·6H2O, stirring and reacting for 30min to obtain a precursor;
(2) and transferring the precursor into a reaction kettle with a 50mL polytetrafluoroethylene inner container, carrying out solvothermal reaction at the temperature of 200 ℃ for 15h, and centrifuging, washing and drying to obtain the high-efficiency nitrogen-fixing catalyst.
Example 5
A high-efficiency catalyst for nitrogen fixation comprises a p-anisidine organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) mixing N, N-dimethylformamide and anhydrous ethanol each 10mL, adding p-anisidine organic ligand 0.5mmol, dissolving, and adding 0.05 mmoll Co(NO3)2·6H2O, stirring and reacting for 30min to obtain a precursor;
(2) and transferring the precursor into a reaction kettle with a 50mL polytetrafluoroethylene inner container, carrying out solvothermal reaction at the temperature of 200 ℃ for 15h, and centrifuging, washing and drying to obtain the high-efficiency nitrogen-fixing catalyst.
Comparative example 1
A high-efficiency catalyst for nitrogen fixation comprises a p-anisidine organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) mixing N, N-dimethylformamide and anhydrous ethanol 10mL respectively, adding p-anisidine organic ligand 0.5mmol, dissolving, adding Co (NO) 5mmol3)2·6H2O, stirring and reacting for 30min to obtain a precursor;
(2) and transferring the precursor into a reaction kettle with a 50mL polytetrafluoroethylene inner container, carrying out solvothermal reaction at the temperature of 200 ℃ for 15h, and centrifuging, washing and drying to obtain the high-efficiency nitrogen-fixing catalyst.
Comparative example 2
A high-efficiency catalyst for nitrogen fixation comprises a p-anisidine organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) mixing N, N-dimethylformamide and anhydrous ethanol 10mL respectively, adding p-anisidine organic ligand 0.5mmol, dissolving, adding Co (NO) 0.033mmol3)2·6H2O, stirring and reacting for 30min to obtain a precursor;
(2) and transferring the precursor into a reaction kettle with a 50mL polytetrafluoroethylene inner container, carrying out solvothermal reaction at the temperature of 200 ℃ for 15h, and centrifuging, washing and drying to obtain the high-efficiency nitrogen-fixing catalyst.
Comparative example 3
A high-efficiency catalyst for nitrogen fixation comprises a p-anisidine organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) mixing N, N-dimethylformamide and anhydrous ethanol each 10mL, adding0.5mmol of p-anisidine organic ligand is dissolved and 0.5mmol of Co (NO) is added3)2·6H2O, stirring and reacting for 30min to obtain a precursor;
(2) and transferring the precursor into a reaction kettle with a 50mL polytetrafluoroethylene inner container, carrying out solvothermal reaction at 120 ℃ for 15h, and centrifuging, washing and drying to obtain the high-efficiency nitrogen-fixing catalyst.
Application example
A method for fixing nitrogen by using the catalyst, comprising the following steps: 10mg of the catalysts prepared in examples 1 to 5 and comparative examples 1 to 3 were dispersed in 15mL of a 0.3mol/L sodium sulfite solution, nitrogen gas was introduced, nitrogen fixation was performed in the dark or in the visible, the ammonium concentration was measured by a Naeser reagent, and the nitrogen fixation rate was calculated, and the results are shown in Table 1.
TABLE 1
From table 1 the following conclusions can be drawn:
(1) examples 1-3 each used a different aromatic amine to complex with a cobalt-based support to form a catalyst. The nitrogen fixation rate of the catalysts of the examples is significantly higher than that of the examples 2-3, which shows that the catalysts using p-anisidine as the ligand have better nitrogen fixation effect than other aromatic amines, presumably because: in p-anisidine, methoxyl is connected on a benzene ring to serve as an electron supply group, and one end of the methoxyl is connected with amino to serve as an electron-withdrawing group, so that electrons have a directional transfer tendency on an organic ligand, the ligand has a good effect of separating electron hole pairs, and the catalytic efficiency of the nitrogen fixation reaction can be improved; in addition, in the organic ligand of the acyl group connected to the benzene ring, although the electron cloud can also shift to the acyl group, the electron transfer tendency of the organic ligand is not as obvious as that of p-anisidine, so that the electron transfer capability of the organic ligand is weaker, and the nitrogen fixing effect of the catalyst is not as good as that of the p-anisidine.
(2) In examples 1, 4 and 5 and comparative examples 1 and 2, an aromatic amine-based organic ligand was reacted with Co (NO)3)2·6H2The molar ratios between O are 1:1, 0.4:1, 1:10, 0.1:1 and 15:1, respectively. Nitrogen fixation rate example 1 > example 4 > comparative example 1, and example 1 > example 5 > comparative example 2, which show that too large or too small a relative amount of the aromatic amine-based organic ligand in the catalyst affects the nitrogen fixation effect of the catalyst, presumably because: if the relative content of the aromatic amine organic ligand is too small, electrons and holes are directly quenched due to too high photocatalytic activity of the cobalt-based carrier, so that the nitrogen fixation efficiency is too low; if the relative content of the aromatic amine organic ligand is too large, the surface of the cobalt-based carrier is covered by the organic ligand, so that enough active sites are not available, and the nitrogen fixation effect is also influenced.
(3) In example 1 and comparative example 3, the solvothermal reaction temperatures were 200 ℃ and 120 ℃, respectively. The nitrogen fixation rate of the catalyst prepared in comparative example 3 is significantly lower compared to example 1, which indicates that the nitrogen fixation effect of the catalyst is affected by too low a solvothermal reaction temperature, presumably because: the catalyst crystallization is incomplete due to the fact that the solvothermal reaction temperature is too low, and the nitrogen fixation performance of the catalyst is affected.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The high-efficiency catalyst for nitrogen fixation is characterized by comprising an aromatic amine organic ligand and a cobalt-based carrier which are combined through coordination bonds.
2. The catalyst according to claim 1, wherein the organic ligand of aromatic amine is one or more of p-anisidine, phthalimide, acetyl-m-toluidine, acetanilide, o-aminoacetanilide, and the like.
3. The catalyst of claim 1, wherein the aromatic amine-based organic ligand is p-anisidine.
4. The catalyst of claim 1 or 2, wherein the molar ratio between the aromatic amine-based organic ligand and the cobalt-based support is 0.4-10: 1.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, comprising the steps of:
(1) mixing N, N-dimethylformamide and absolute ethyl alcohol, adding an aromatic amine organic ligand, dissolving, adding divalent cobalt salt, and stirring for reacting for 30-40min to obtain a precursor;
(2) and carrying out solvothermal reaction on the precursor, and separating out a product after the reaction is finished to obtain the high-efficiency catalyst for fixing nitrogen.
6. The method according to claim 5, wherein in the step (1), the molar ratio of the aromatic amine-based organic ligand to the cobalt ion in the divalent cobalt salt is 0.4 to 10: 1.
7. The method according to claim 5, wherein the temperature of the solvothermal reaction in step (2) is 150 ℃ to 210 ℃ for 15-20 h.
8. A method for fixing nitrogen by using the catalyst according to any one of claims 1 to 4, wherein the nitrogen fixing condition is dark or under visible light or natural light.
9. The method of claim 8, wherein the specific process is as follows: dispersing the catalyst in sodium sulfite solution, and fixing nitrogen in dark or under visible light or natural light.
10. The method of claim 8, wherein the mass to volume ratio of the catalyst to the sodium sulfite solution is 1mg:0.5-1.5 mL; in the sodium sulfite solution, the concentration of sodium sulfite is 0.01-1 mol/L.
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