CN110075926B - Catalyst for photocatalytic reduction of nitrogen and preparation method thereof - Google Patents
Catalyst for photocatalytic reduction of nitrogen and preparation method 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 93
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 34
- 230000009467 reduction Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006902 nitrogenation reaction Methods 0.000 title description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 17
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 17
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 17
- HMPXSWYLSSRSQF-UHFFFAOYSA-J ac1l4snl Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].C12=CC(S(=O)(=O)[O-])=CC=C2C(N=C2[N-]C(C3=CC=C(C=C32)S([O-])(=O)=O)=N2)=NC1=NC([C]1C=CC(=CC1=1)S([O-])(=O)=O)=NC=1N=C1[C]3C=CC(S([O-])(=O)=O)=CC3=C2[N-]1 HMPXSWYLSSRSQF-UHFFFAOYSA-J 0.000 claims abstract description 11
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 claims abstract description 11
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical group [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 24
- 239000002131 composite material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- VTVVPPOHYJJIJR-UHFFFAOYSA-N carbon dioxide;hydrate Chemical compound O.O=C=O VTVVPPOHYJJIJR-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- -1 3,4,9, 10-perylene tetracarboxylic acid anion Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for photocatalytic reduction of nitrogen and a preparation method thereof. The catalyst is nickel iron hydrotalcite intercalated with copper phthalocyanine tetrasulfonic acid tetrasodium salt and/or 3,4,9, 10-perylene tetracarboxylic acid, and is prepared by coprecipitation and hydrothermal crystallization. The catalyst prepared by the invention is a novel organic-inorganic nano composite material, and the material has the advantages of good light absorption, low price, high catalytic performance, good stability and the like. The catalyst prepared by the invention effectively improves the performance of photocatalytic reduction of nitrogen, and can change the performance of photocatalytic reduction of nitrogen by regulating and controlling the proportion of intercalated organic molecules.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for photocatalytic reduction of nitrogen and a preparation method thereof.
Background
Nitrogen is the most abundant gas in the atmosphere and is also an important source of nitrogen. Ammonia (NH)3) Is one of the most important chemical basic substances in human production and life. However, the Haber Bosch process found in the twentieth century is still used by the industrial subjects, and the synthesis conditions of the process need to be carried out at high temperature and high pressure, and the process causes great pollution and waste to the environment and resources. Therefore, the search for a clean and efficient nitrogen reduction catalyst is an important research topic in the energy field at present. The organic molecule has the advantages of rich source of raw materials, low price, large optical modulation range and the like, and can be well combined with the adjustable performance between hydrotalcite layers. Experiments show that the efficiency of catalytic reduction of nitrogen is greatly improved by introducing organic micromolecules between layers of hydrotalcite.
Layered Double Hydroxides (LDHs) are typical anionic Layered materials, and have many advantages as follows: interlayer controllability, memory effect and the like, and more LDHs-based composite materials appear in the life of people. A Ni-Fe LDHs system is selected to carry out an organic micromolecule intercalation experiment, the influence on the performance of photocatalytic reduction nitrogen is explored through the adjustment of the proportion of organic molecules, the optimal proportion for improving the performance is found, and various functional composite materials can be designed and synthesized.
Disclosure of Invention
The invention aims to provide a catalyst for photocatalytic reduction of nitrogen and a preparation method thereof, and the catalyst improves the performance of photocatalytic reduction of nitrogen.
The catalyst for photocatalytic reduction of nitrogen is nickel iron hydrotalcite intercalated with copper phthalocyanine tetrasulfonic acid tetrasodium salt and/or 3,4,9, 10-perylene tetracarboxylic acid.
The preparation method of the catalyst for photocatalytic reduction of nitrogen comprises the following steps:
1) using CO removal2Preparing a mixed solution A of nickel nitrate and ferric nitrate by using deionized water; using CO removal2Preparing a mixed solution B of copper phthalocyanine tetrasulfonic acid tetrasodium salt and/or 3,4,9, 10-perylene tetracarboxylic acid and NaOH by using deionized water;
2) respectively adding the mixed solution A and the mixed solution B into a constant-pressure funnel, slowly dripping the mixed solution A and the mixed solution B into a four-neck flask at the temperature of 50-90 ℃ under the conditions of nitrogen protection and stirring, and controlling the pH of the solutions to be 9-10 in the dripping process; after the dropwise addition is finished, the slurry is sealed and placed for 20-40 min;
3) transferring the slurry obtained in the step 2) into a reaction kettle, reacting at 100 ℃ and 140 ℃ for 24-36h, and removing CO2And centrifugally washing the deionized water and ethanol, and drying in vacuum to obtain the catalyst for photocatalytic reduction of nitrogen.
The catalytic reaction conditions of the prepared catalyst for photocatalytic reduction of nitrogen are as follows: the catalyst for photocatalytic reduction of nitrogen is placed in water into which high-purity nitrogen is continuously introduced, then the catalyst is placed in a photocatalytic reaction box, and a light source is turned on to perform photocatalytic reduction of nitrogen.
The method comprises the steps of introducing pc (copper phthalocyanine tetrasulfonic acid tetrasodium salt) and PTCB (3,4,9, 10-perylenetetracarboxylic acid) serving as objects into the interlayer of layered material ferronickel hydrotalcite to form an inorganic/organic compound, and regulating and controlling the performance of the catalyst by utilizing the interaction of a host-object and an object-object; the performance of improving the nitrogen for photocatalytic reduction is found by regulating and controlling the adding proportion of the nitrogen and the nitrogen; at the same time, the physical and chemical stability of the guest molecule can also be improved. At present, researches on photocatalytic nitrogen reduction by introducing pc (copper phthalocyanine tetrasulfonic acid tetrasodium salt) and PTCB (3,4,9, 10-perylenetetracarboxylic acid) into layered material nickel-iron hydrotalcite interlamination have not been reported yet.
The catalyst prepared by the invention is a novel organic-inorganic nano composite material. The material has the advantages of good light absorption, low price, high performance, good stability and the like. The catalyst effectively improves the performance of the nitrogen gas in photocatalytic reduction, and can change the performance of the nitrogen gas in photocatalytic reduction by regulating and controlling the proportion of intercalated organic molecules. The film prepared by the material when the feeding ratio of organic molecules is 1:1 has high absorption range, high nitrogen reducing performance and good circulation stability.
Drawings
FIG. 1 shows XRD patterns of hydrotalcites of different anion ratios obtained in examples 1 to 3 of the present invention, (a) pc/LDHs, (b) pc-PTCB/LDHs, (c) PTCB/LDHs.
FIG. 2 is an SEM and HRTEM image of a catalyst prepared according to the present invention; a is SEM picture of pc/LDHs, B is SEM picture of PTCB/LDHs, C is SEM picture of pc-PTCB/LDHs, and D is lattice diffraction fringe picture of pc-PTCB/LDHs.
FIG. 3 is a FTIR plot of catalysts prepared in examples 1-3.
FIG. 4 is a graph of the performance of the catalysts obtained in examples 1-3. (a) Ni/Fe-LDHs (b) pc/LDHs (c) PTCB/LDHs (d) pc-PTCB/LDHs.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
1) 2.9529g of Ni (NO) were weighed out3)2·6H2O and 2.02g Fe (NO)3)3·9H2O dissolved in 75ml to remove CO2And deionized water to obtain solution A, Ni2+/Fe3+The molar ratio is 2: 1;
2) 0.5354g of PTCB (3,4,9, 10-perylene tetracarboxylic acid) is dissolved in 75ml of water, and then 1.2g of NaOH is added for adjusting the pH value to obtain a solution B;
3) respectively adding the prepared solution A and the prepared solution B into different constant-pressure funnels, slowly dropwise adding the solution A and the solution B into a four-neck flask in a 75 ℃ water bath kettle, continuously stirring in the dropwise adding process to keep the pH value of the solution at 9-10, and introducing nitrogen all the time;
4) obtaining slurry D, keeping the slurry D in a water bath kettle for half an hour, and then transferring the slurry D to a high-pressure reaction kettle to be placed in a 110 ℃ drying oven to react for 36 hours;
5) removing CO from the reaction products obtained in the step 4) respectively2And centrifugally washing the deionized water and ethanol for 5 times until the washing liquid is colorless, and carrying out vacuum drying on a filter cake obtained by centrifugation at 60 ℃ overnight to obtain the catalyst for photocatalytic reduction of nitrogen of the 3,4,9, 10-perylene tetracarboxylic acid anion intercalated hydrotalcite.
6) The method for testing the performance of the nitrogen through photocatalytic reduction comprises the following steps: 50mg of the prepared catalyst is placed into 20mL of Waohaha water into which high-purity nitrogen is continuously introduced for 30min, the catalyst is placed in a photocatalytic reaction box, the mixture is stirred in the dark for 15 min to ensure that the nitrogen is fully mixed with the water, and a light source is turned on to perform reaction to test the performance of photocatalytic reduction of the nitrogen.
The XRD pattern of PTCB intercalated hydrotalcite can be known from characteristic peaks of 003, 006, 015 and the like in figure 1 c; FIG. 2b shows an SEM image of PTCB/LDHs; from FIG. 3c, the infrared absorption of PTCB/LDH is known; the change in the performance of this catalyst for photocatalytic reduction of nitrogen can be seen in fig. 4 c.
Example 2
1) Weighing 2.9529gNi (NO)3)2·6H2O and 2.02g Fe (NO)3)3·9H2O dissolved in 75ml to remove CO2And deionized water to obtain solution A, Ni2+/Fe3+The molar ratio is 2: 1;
2) dissolving 1.23g of pc (copper phthalocyanine tetrasulfonic acid tetrasodium salt) in 75ml of water, and then adding 1.2g of NaOH to adjust the pH value to obtain a solution B;
3) the same as example 1;
4) the same as example 1;
5) the same as example 1;
6) the same as in example 1.
The XRD pattern of pc intercalated hydrotalcite can be seen from characteristic peaks of 003, 006, 015 and the like in FIG. 1 a; FIG. 2a shows an SEM image of pc/LDHs; from FIG. 3a, the infrared absorption of PTCB/LDH is known; the change in the performance of this catalyst for photocatalytic reduction of nitrogen can be seen in fig. 4 b.
Example 3
1) Weighing 2.9529gNi (NO)3)2·6H2O and 2.02g Fe (NO)3)3·9H2O dissolved in 75ml to remove CO2In deionized waterObtaining solution A, Ni2+/Fe3+The molar ratio is 2: 1;
2) 0.984g of pc (copper phthalocyanine tetrasulfonic acid tetrasodium salt) and 0.107g of PTCB (3,4,9, 10-perylenetetracarboxylic acid) were dissolved in 75ml of water, and 1.2g of NaOH was added to adjust the pH, to obtain a solution B;
3) the same as example 1;
4) the same as example 1;
5) the same as example 1;
6) the same as in example 1.
The XRD pattern of pc/PTCB co-intercalated hydrotalcite can be known from characteristic peaks of 003, 006, 015 and the like in the figure 1 b; from FIG. 2c, SEM image and 2d of pc-PTCB/LDHsHRTEM are shown and lattice fringes are obtained; from FIG. 3b, the infrared absorption of pc-PTCB/LDHs is known; the change of the performance of the catalyst on photocatalytic reduction of nitrogen can be seen from fig. 4d, which is compared with the performance of the photocatalytic nitrogen of 4a carbonate hydrotalcite.
In the above characterization:
1. XRD and FTIR characterization are carried out, which shows that pc (copper phthalocyanine tetrasulfonic acid tetrasodium salt) and PTCB (3,4,9, 10-perylene tetracarboxylic acid) anions are successfully inserted into hydrotalcite interlayers;
2. performing SEM and HRTEM representation, and displaying the morphology and the lattice fringes of the composite material;
3. and performance tests show that the hydrotalcite intercalation composite material has obviously improved nitrogen photocatalytic reduction performance.
The characterization and test results show that the composite material fully utilizes the space confinement effect between hydrotalcite layers and the interaction between the subject and the object, and improves the nitrogen photocatalytic reduction performance.
Claims (2)
1. A method for photocatalytic reduction of nitrogen is characterized in that the reaction conditions of the method are as follows: placing a catalyst for photocatalytic reduction of nitrogen into water continuously filled with high-purity nitrogen, then placing the catalyst into a photocatalytic reaction box, and turning on a light source to perform photocatalytic reduction of nitrogen; the catalyst for photocatalytic reduction of nitrogen is any one of nickel iron hydrotalcite intercalated with copper phthalocyanine tetrasulfonic acid tetrasodium salt, nickel iron hydrotalcite intercalated with 3,4,9, 10-perylene tetracarboxylic acid, copper phthalocyanine tetrasulfonic acid tetrasodium salt and nickel iron hydrotalcite intercalated with 3,4,9, 10-perylene tetracarboxylic acid.
2. The method of claim 1, wherein the method for preparing the catalyst for photocatalytic reduction of nitrogen gas comprises:
1) using CO removal2Preparing a mixed solution A of nickel nitrate and ferric nitrate by using the deionized water; using CO removal2Preparing a mixed solution B of copper phthalocyanine tetrasulfonic acid tetrasodium salt and/or 3,4,9, 10-perylene tetracarboxylic acid and NaOH by using the deionized water;
2) respectively adding the mixed solution A and the mixed solution B into a constant-pressure funnel, slowly dripping the mixed solution A and the mixed solution B into a four-neck flask at the temperature of 50-90 ℃ under the conditions of nitrogen protection and stirring, and controlling the pH of the solutions to be 9-10 in the dripping process; after the dropwise addition is finished, the slurry is sealed and placed for 20-40 min;
3) transferring the slurry obtained in the step 2) into a reaction kettle, reacting at 100 ℃ and 140 ℃ for 24-36h, and removing CO2And centrifugally washing the deionized water and ethanol, and drying in vacuum to obtain the catalyst for photocatalytic reduction of nitrogen.
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