CN114308124B - High-efficiency catalyst for nitrogen fixation and preparation method and application thereof - Google Patents
High-efficiency 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 203
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 54
- 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 32
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000004729 solvothermal method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 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
- 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
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 3
- 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
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000000969 carrier Substances 0.000 abstract 1
- -1 acetom-toluidine Chemical compound 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 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
- 230000001699 photocatalysis Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- ACTLYQCWIWMUSY-UHFFFAOYSA-N 2-amino-1-(2-aminophenyl)ethanone Chemical compound NCC(=O)C1=CC=CC=C1N ACTLYQCWIWMUSY-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 238000009620 Haber process Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 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
- 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
- MPXAYYWSDIKNTP-UHFFFAOYSA-N n-(2-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC=C1N MPXAYYWSDIKNTP-UHFFFAOYSA-N 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 230000005855 radiation 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
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of nitrogen fixation catalysts, and discloses a high-efficiency catalyst for nitrogen fixation, a preparation method and application thereof. The high-efficiency catalyst for nitrogen fixation comprises aromatic amine organic ligands and cobalt-based carriers which are combined through coordination bonds, and the preparation method comprises the following steps: (1) Mixing N, N-dimethylformamide and absolute ethyl alcohol, adding aromatic amine organic ligand, dissolving, adding bivalent cobalt salt, and stirring for reaction 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 nitrogen fixation. The catalyst has better catalytic nitrogen fixation effect, can convert nitrogen into ammonia under both bright and dark conditions, and can carry out the nitrogen fixation process under the bright 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 the highest content gas in the earth's environment, but the molecular bond energy of this nitrogen is very high and requires much energy to fix, so nitrogen is one of the inert gases. The Haber-Bosch process (300-500 c, 15-25 MPa) has been used for industrial nitrogen fixation, but it requires a large amount of fossil fuel to provide heat and generates a large amount of greenhouse gases, so that development of a new sustainable process is needed to replace the conventional nitrogen fixation process.
The photocatalysis nitrogen fixation technology converts nitrogen into ammonia by utilizing solar energy, has the advantages of mild conditions, energy conservation, environmental protection and the like, and is considered as 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 facing the prior photocatalysis nitrogen fixation technology, and in the reported photocatalysis nitrogen fixation catalysts, the nitrogen fixation efficiency is relatively low, and is mostly 10-50 mu mol.L -1 ·h -1 . In a common photocatalytic medium, graphite-phase carbon nitride (g-C 3 N 4 ) And its modification is one of the most widely and deeply studied catalysts at present. But due to g-C 3 N 4 Has a wider forbidden bandwidth (eg=2.77 eV), and only ultraviolet rays with higher energyAnd near ultraviolet rays can be excited, and ultraviolet radiation content in sunlight is low (only accounting for about 3 percent), so that the utilization rate of solar energy is low.
Transition metals contain d orbitals that are not fully charged to varying degrees and thus 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 nitrogen fixation direction, and a new thought is provided for the design of the nitrogen fixation catalyst. However, the reported organic ligand coordination transition metal photocatalyst has still limited nitrogen fixation effect, and the nitrogen fixation condition is harsh, such as the need of applying high temperature or low temperature in the nitrogen fixation process, or limiting the light wavelength. For example, document 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) discloses a nitrogen fixation catalyst [ (TPB) Fe (N.) 2 )][Na(12-crown-4) 2 ]It has high catalytic activity at-78 deg.c, so that nitrogen fixing reaction must be performed at low temperature in order to obtain 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 better catalytic nitrogen fixation effect, can convert nitrogen into ammonia under both bright and dark conditions, and can carry out the nitrogen fixation process under the bright condition at normal temperature and normal pressure.
The specific technical scheme of the invention is as follows:
a high-efficiency catalyst for fixing nitrogen is composed of aromatic amine organic ligand and Co-base carrier.
The mechanism of the catalyst for catalyzing the nitrogen fixation reaction is as follows: first, nitrogen is adsorbed at the catalyst oxygen vacancies; under the condition of light, the photo-excited catalyst semiconductor generates electron-hole pairs, electrons are quickly transferred from the amino position of the organic ligand to the metal position, then transferred to oxygen holes, finally transferred to nitrogen, and N is identical to N of the nitrogen is brokenCracking and reduction reaction. Meanwhile, a sacrificial reagent (such as sodium sulfite) is used in combination to oxidize the hole consumption; final N is NH 3 Form(s) of (a) are detached from the catalyst, again because of NH 3 Is very soluble in water and therefore takes the form of NH 4 + In the form of (2) is present in water. In the absence of light, the catalyst absorbs heat from the environment to generate electrons and holes, thereby achieving nitrogen fixation.
The invention adopts the coordination of aromatic amine and cobalt-based carrier, the reduction potential of the obtained catalyst is-0.1 eV to-0.2 eV which is higher than the potential required by nitrogen fixation (-0.092 eV), thus having better catalytic nitrogen fixation effect, being capable of easily generating nitrogen fixation reaction without inputting large energy, having low requirement on nitrogen fixation condition, being capable of converting nitrogen into ammonia under both light and no light condition, and being capable of being carried out under normal temperature and normal pressure, and the nitrogen fixation rate being up to 174 mu mol.L -1 ·h -1 。
Preferably, the aromatic amine organic ligand is one or more of p-methoxyaniline, phthalimide, acetom-toluidine, acetanilide and o-amino acetanilide.
Further, the aromatic amine organic ligand is p-methoxy aniline.
Compared with other aromatic amine organic ligands, the p-methoxyaniline coordinated cobalt-based carrier is adopted, and the catalytic activity is higher, because: in p-methoxyaniline, methoxy is connected to benzene ring as electron-donating group, and one end is connected with amino as electron-withdrawing group, so that electrons have a tendency of directional transfer on organic ligand, and the ligand has a good effect of separating electron-hole pairs, so that the catalysis efficiency of nitrogen fixation reaction can be improved.
Preferably, the molar ratio between the aromatic amine organic ligand and 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 can influence 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 the 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 surface of the cobalt-based carrier is covered by the organic ligand, and the cobalt-based carrier has no enough active sites, so that the nitrogen fixation effect is also affected, and even the nitrogen fixation reaction cannot be performed.
A method for preparing the catalyst, comprising the steps of:
(1) Mixing N, N-dimethylformamide and absolute ethyl alcohol, adding aromatic amine organic ligand, dissolving, adding bivalent cobalt salt, and stirring for reaction 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 nitrogen fixation.
Preferably, in the step (1), the molar ratio between the aromatic amine organic ligand and cobalt ions in the divalent cobalt salt is 0.1-10:1.
Preferably, the divalent cobalt salt is Co (NO 3 ) 2 ·6H 2 O。
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 solvothermal reaction is carried out at a temperature of 150-210 ℃ for 15-20h.
In the invention, the temperature of the solvothermal reaction is controlled within a certain range, and if the temperature is too low, incomplete crystallization of the catalyst can be caused, and the nitrogen fixation performance of the catalyst is affected; if the temperature is too high, the liner of the reaction kettle is broken, the solvent volatilizes, and the catalyst cannot be synthesized.
A method for fixing nitrogen by using the catalyst has the nitrogen fixing condition of light shielding or 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 under the light-proof or visible light or natural light.
Preferably, the mass volume ratio of the catalyst to the sodium sulfite solution is 1mg:0.5-1.5mL; in the sodium sulfite solution, the concentration of sodium sulfite is 0.01-1mol/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, so that the catalytic activity is high, the requirement on nitrogen fixation conditions is low, nitrogen can be converted into ammonia under both bright and dark conditions, and the nitrogen fixation process under the bright condition can be performed at normal temperature and normal pressure;
(2) The relative content of the aromatic amine organic ligand and the cobalt-based carrier is controlled, so that the aromatic amine organic ligand and the cobalt-based carrier can better play a synergistic effect, and the nitrogen fixation effect of the catalyst is improved.
Detailed Description
The invention is further described below with reference to examples.
General examples
A high-efficiency catalyst for fixing nitrogen is composed of aromatic amine organic ligand and Co-base carrier. The aromatic amine organic ligand is one or more of p-methoxyaniline, phthalimide, m-methylaniline, acetanilide and o-aminoacetonilide. The molar ratio of the aromatic amine organic ligand to cobalt element in the cobalt-based carrier is 0.4-10:1.
A method for preparing the catalyst, comprising the steps of:
(1) Mixing N, N-dimethylformamide and absolute ethyl alcohol in a volume ratio of 1:0.5-1.5, adding an aromatic amine organic ligand, dissolving, adding bivalent cobalt salt, wherein the molar ratio of the aromatic amine organic ligand to cobalt ions in the bivalent cobalt salt is 0.4-10:1, and stirring for reacting for 30-40min to obtain a precursor;
(2) Carrying out solvothermal reaction on the precursor at 150-210 ℃ for 15-20h; after the reaction is finished, separating out a product to obtain the high-efficiency catalyst for nitrogen fixation.
A method for nitrogen fixation using the catalyst, comprising the steps of: 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 to 0.5-1.5mL, and fixing nitrogen under the conditions of light shielding or visible light or natural light.
Example 1
A high-efficiency catalyst for nitrogen fixation comprises a p-methoxyaniline organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) After 10mL of each of N, N-dimethylformamide and absolute ethanol were mixed, 0.5mmol of p-methoxyaniline organic ligand was added thereto, and after dissolution, 0.5mmol of Co (NO) 3 ) 2 ·6H 2 O, stirring and reacting for 30min to obtain a precursor;
(2) Transferring the precursor into a reaction kettle with 50mL polytetrafluoroethylene liner, performing solvothermal reaction at 200 ℃ for 15h, centrifuging, washing and drying to obtain the high-efficiency catalyst for nitrogen fixation.
Example 2
A high-efficiency catalyst for nitrogen fixation comprises an acetyl meta-toluidine organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) After 10mL of N, N-dimethylformamide and 10mL of absolute ethyl alcohol were mixed, 0.5mmol of an organic ligand of acetom-toluidine was added thereto, and after dissolution, 0.5mmol of Co (NO) 3 ) 2 ·6H 2 O, stirring and reacting for 30min to obtain a precursor;
(2) Transferring the precursor into a reaction kettle with 50mL polytetrafluoroethylene liner, performing solvothermal reaction at 200 ℃ for 15h, centrifuging, washing and drying to obtain the high-efficiency catalyst for nitrogen fixation.
Example 3
A high-efficiency catalyst for nitrogen fixation comprises an o-aminoacetylaniline organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) After 10mL of each of N, N-dimethylformamide and absolute ethanol were mixed, 0.5mmol of an organic ligand of o-aminoacetylaniline was added thereto, and after dissolution, 0.5mmol of Co (NO) 3 ) 2 ·6H 2 O, stirring and reacting for 30min to obtain a precursor;
(2) Transferring the precursor into a reaction kettle with 50mL polytetrafluoroethylene liner, performing solvothermal reaction at 200 ℃ for 15h, centrifuging, washing and drying to obtain the high-efficiency catalyst for nitrogen fixation.
Example 4
A high-efficiency catalyst for nitrogen fixation comprises a p-methoxyaniline organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) After 10mL of each of N, N-dimethylformamide and absolute ethanol were mixed, 0.5mmol of p-methoxyaniline organic ligand was added thereto, and after dissolution, 1.25mmol of Co (NO) 3 ) 2 ·6H 2 O, stirring and reacting for 30min to obtain a precursor;
(2) Transferring the precursor into a reaction kettle with 50mL polytetrafluoroethylene liner, performing solvothermal reaction at 200 ℃ for 15h, centrifuging, washing and drying to obtain the high-efficiency catalyst for nitrogen fixation.
Example 5
A high-efficiency catalyst for nitrogen fixation comprises a p-methoxyaniline organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) After 10mL of each of N, N-dimethylformamide and absolute ethanol were mixed, 0.5mmol of p-methoxyaniline organic ligand was added thereto, and after dissolution, 0.05mmol of Co (NO) 3 ) 2 ·6H 2 O, stirring and reacting for 30min to obtain a precursor;
(2) Transferring the precursor into a reaction kettle with 50mL polytetrafluoroethylene liner, performing solvothermal reaction at 200 ℃ for 15h, centrifuging, washing and drying to obtain the high-efficiency catalyst for nitrogen fixation.
Comparative example 1
A high-efficiency catalyst for nitrogen fixation comprises a p-methoxyaniline organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) After 10mL of each of N, N-dimethylformamide and absolute ethanol were mixed, 0.5mmol of p-methoxyaniline organic ligand was added thereto, and after dissolution, 5mmol of Co (NO 3 ) 2 ·6H 2 O, stirring and reacting for 30min to obtain a precursor;
(2) Transferring the precursor into a reaction kettle with 50mL polytetrafluoroethylene liner, performing solvothermal reaction at 200 ℃ for 15h, centrifuging, washing and drying to obtain the high-efficiency catalyst for nitrogen fixation.
Comparative example 2
A high-efficiency catalyst for nitrogen fixation comprises a p-methoxyaniline organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) After 10mL of each of N, N-dimethylformamide and absolute ethanol were mixed, 0.5mmol of p-methoxyaniline organic ligand was added thereto, and after dissolution, 0.033mmol of Co (NO) 3 ) 2 ·6H 2 O, stirring and reacting for 30min to obtain a precursor;
(2) Transferring the precursor into a reaction kettle with 50mL polytetrafluoroethylene liner, performing solvothermal reaction at 200 ℃ for 15h, centrifuging, washing and drying to obtain the high-efficiency catalyst for nitrogen fixation.
Comparative example 3
A high-efficiency catalyst for nitrogen fixation comprises a p-methoxyaniline organic ligand and a cobalt-based carrier which are combined through coordination bonds, and the preparation method comprises the following steps:
(1) After 10mL of each of N, N-dimethylformamide and absolute ethanol were mixed, 0.5mmol of p-methoxyaniline organic ligand was added thereto, and after dissolution, 0.5mmol of Co (NO) 3 ) 2 ·6H 2 O, stirring and reacting for 30min to obtain a precursor;
(2) Transferring the precursor into a reaction kettle with 50mL polytetrafluoroethylene liner, performing solvothermal reaction at 120 ℃ for 15h, centrifuging, washing and drying to obtain the high-efficiency catalyst for nitrogen fixation.
Application example
A method for nitrogen fixation using the catalyst, comprising the steps of: 10mg of the catalyst prepared in examples 1-5 and comparative examples 1-3 was dispersed in 15mL of a 0.3mol/L sodium sulfite solution, nitrogen was introduced, nitrogen fixation was performed under light-shielding or visible light, the concentration of ammonium groups was measured by Navier's 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 coordinated to a cobalt-based support to form a catalyst. The nitrogen fixation rate of the catalyst of the example is significantly higher than that of examples 2-3, demonstrating that the catalyst using p-methoxyaniline as a ligand has better catalytic nitrogen fixation effect than other aromatic amines, presumably due to: in the p-methoxyaniline, methoxy is connected to a benzene ring as an electron donating group, and one end of the p-methoxyaniline is connected with an amino group as an electron withdrawing group, so that electrons have a tendency of directional transfer on an organic ligand, the ligand has a good effect of separating electron hole pairs, and the catalysis efficiency of nitrogen fixation reaction can be improved; in the organic ligand with acyl group connected to benzene ring, the electron cloud will shift to acyl group, but the electron transfer trend is less obvious than that of p-methoxy aniline, so that the ligand has weak electron transfer capacity and the catalyst has no nitrogen fixing effect.
(2) In examples 1, 4, 5 and comparative examples 1, 2, the aromatic amine organic ligand was reacted with Co (NO 3 ) 2 ·6H 2 The molar ratios between O were 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), it is assumed that too large or too small a relative content of aromatic amine organic ligands in the catalyst affects the nitrogen fixation effect of the catalyst, presumably due to: if the relative content of the aromatic amine organic ligand is too small, electrons and holes are directly quenched due to the too high photocatalytic activity of the cobalt-based carrier, so that the nitrogen fixation efficiency is too low; if the relative content of aromatic amine organic ligands is too large, the cobalt-based carrier surface is covered by organic ligands, and there are not enough active sites, so that the nitrogen fixation effect is also affected.
(3) In example 1 and comparative example 3, the solvothermal reaction temperatures were 200℃and 120℃respectively. The catalyst prepared in comparative example 3 had significantly lower nitrogen fixation rate than example 1, indicating that too low a solvothermal reaction temperature would affect the nitrogen fixation effect of the catalyst, presumably due to: too low a solvothermal reaction temperature can cause incomplete crystallization of the catalyst and affect the nitrogen fixation performance of the catalyst.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (5)
1. Use of a catalyst for nitrogen fixation, wherein the catalyst comprises an aromatic amine organic ligand and a cobalt-based carrier combined by coordination bonds; the aromatic amine organic ligand is one or more of p-methoxyaniline, phthalimide, m-methylaniline, acetanilide and o-aminoacetonilide; the preparation method of the catalyst comprises the following steps:
(1) Mixing N, N-dimethylformamide and absolute ethyl alcohol, adding aromatic amine organic ligand, dissolving, adding bivalent cobalt salt, and stirring for reaction for 30-40min to obtain a precursor; the molar ratio between the aromatic amine organic ligand and cobalt ions in the bivalent cobalt salt is 0.4-10:1;
(2) And carrying out solvothermal reaction on the precursor at 150-210 ℃ for 15-20h, and separating out a product after the reaction is finished to obtain the catalyst.
2. The use according to claim 1, wherein the aromatic amine organic ligand is p-methoxyaniline.
3. The use according to claim 1, wherein the nitrogen fixation conditions are in the absence of light or visible or natural light.
4. The use according to claim 1, characterized by the following specific procedures: dispersing the catalyst in sodium sulfite solution, and fixing nitrogen under the light-proof or visible light or natural light.
5. The use according to claim 4, wherein the mass to volume ratio of catalyst to sodium sulfite solution is 1mg:0.5-1.5mL; in the sodium sulfite solution, the concentration of sodium sulfite is 0.01-1mol/L.
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