CN115500256A - Photocatalysis nitrogen fixation plant water planting growth device - Google Patents
Photocatalysis nitrogen fixation plant water planting growth device Download PDFInfo
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- CN115500256A CN115500256A CN202211394786.0A CN202211394786A CN115500256A CN 115500256 A CN115500256 A CN 115500256A CN 202211394786 A CN202211394786 A CN 202211394786A CN 115500256 A CN115500256 A CN 115500256A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 45
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000012010 growth Effects 0.000 title claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 238000005192 partition Methods 0.000 claims abstract description 12
- 230000008635 plant growth Effects 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 8
- 235000015097 nutrients Nutrition 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003501 hydroponics Substances 0.000 claims description 13
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical group O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 13
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 150000003657 tungsten Chemical class 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 150000003681 vanadium Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000000618 nitrogen fertilizer Substances 0.000 abstract description 9
- 239000003337 fertilizer Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 2
- 235000016709 nutrition Nutrition 0.000 abstract description 2
- 230000035764 nutrition Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 240000000385 Brassica napus var. napus Species 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002362 energy-dispersive X-ray chemical map Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G31/00—Soilless cultivation, e.g. hydroponics
- A01G31/02—Special apparatus therefor
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
-
- 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
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photocatalytic nitrogen fixation plant water culture growth device. The device is an annular transparent pot body, and a middle cavity is used for plant growth; the bottom end of the inner wall of the annular transparent pot body is not connected with the bottom of the pot body; the top ends of the inner wall and the outer wall of the annular transparent pot body are sealed by a cover plate; a cavity between the inner wall and the outer wall of the annular pot body is provided with a perforated clapboard, and a gas one-way valve is arranged above the perforated clapboard; when the device is used, the photocatalyst is uniformly dispersed on the filter membrane and is placed on the porous partition plate, nutrient solution or water for plant growth is poured into the pot body, and the liquid level is higher than the bottom end of the inner wall and lower than the porous partition plate. The device cultivates integration with photocatalysis solid nitrogen and plant, can evenly continuously stably provide nitrogen fertilizer nutrition for vegetation, need not additionally to add the nitrogen source, can enough satisfy the normal growth of plant, can accomplish the low carbon saving again simultaneously, reduces the use of fertilizer.
Description
Technical Field
The invention belongs to the technical field of plant hydroponics devices, and particularly relates to a photocatalytic nitrogen fixation plant hydroponics growing device.
Background
Ammonia/nitrate is one of the important raw materials in modern industry, and the global ammonia production reaches about 2 hundred million tons per year, and is widely used in chemical production, fertilizer production and the like. The Haber-Bosch process is mainly used for industrial production to produce ammonia at high temperature and high pressure by hydrogenating nitrogen, and then to make ammonia (NH) pass through Ostwald 4 + ) Conversion to Nitrate (NO) 3 - ). The above processes consume large amounts of energy and are accompanied by large greenhouse gas emissions. How to reduce energy waste and avoid environmental pollution is urgent to be researched and has practical value. Solar energy, because of its wide source, selectively activates partial bonds, in the field of photocatalysis, e.g. photolysis of water, CO 2 Reduction, N 2 Reduction, etc. have numerous applications. Therefore, scientists have been dedicated to the decentralized production of nitrogen fertilizer in planting sites using nitrogen and water (or air) as raw materials and solar energy as energy.
The catalyst reported at present mainly adopts noble metals such as Pd, pt, rh and the like, and has the problems of high price, complex reaction system, difficulty in enriching products after reaction and the like. Furthermore, there is NO patent or literature on in-situ photocatalytic Nitrate (NO) delivery 3 - ) The system is introduced into a nutrient solution cultivation system, whether a device for in-situ nitrogen fixation cultivation of plants can be successfully designed, and a high-efficiency nitrogen fixation catalyst is designed, so that an effectively absorbable and utilizable nitrate nitrogen fertilizer is provided for plant growth, and the key problem of whether a photocatalytic nitrate production system can be popularized and applied in the field of agriculture is solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention designs a photocatalytic nitrogen fixation plant water culture growth device which is used for directly supplying nitrogen to plant growth through photocatalysis. The device cultivates integration with photocatalysis fixed nitrogen and plant, the tungsten oxide photocatalyst of vanadium doping that uses is under normal atmospheric temperature and sunlight, turns into nitrogen monoxide with the nitrogen gas in the air, and the nitrogen monoxide that generates and the oxygen in the air get into aquatic reaction and generate the nitrate, and the air check valve in the device can supply the air that the reaction consumed, realizes evenly continuously steadily providing nitrogen fertilizer nutrition for vegetation, need not additionally to add the nitrogen source, can enough satisfy the normal growth of plant, can accomplish low carbon saving again simultaneously, reduces the use of fertilizer.
The photocatalytic nitrogen fixation plant water culture growth device is an annular transparent pot body, and a middle cavity is used for plant growth; the bottom end of the inner wall of the annular transparent pot body is not connected with the bottom of the pot body; the top ends of the inner wall and the outer wall of the annular transparent pot body are sealed by a cover plate; a cavity between the inner wall and the outer wall of the annular pot body is provided with a perforated clapboard, and a gas one-way valve is arranged above the perforated clapboard; when the device is used, the photocatalyst is uniformly dispersed on the filter membrane and is placed on the porous partition plate, nutrient solution or water for plant growth is poured into the pot body, and the liquid level is higher than the bottom end of the inner wall and lower than the porous partition plate.
The photocatalyst is tungsten oxide doped with vanadium atoms.
The preparation method of the vanadium atom doped tungsten oxide comprises the following steps: dissolving soluble tungsten salt in an alcohol solvent, and then adding soluble vanadium salt to obtain a mixed solution; adding the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out solvothermal reaction for 10-12 hours at 160-200 ℃, carrying out centrifugal washing and vacuum drying to obtain the vanadium atom doped tungsten oxide.
The soluble tungsten salt and the soluble vanadium salt are respectively one or more of nitrate, sulfate or chloride.
The alcohol solvent is ethanol and/or propanol.
The concentration of the soluble tungsten salt in the mixed solution is 5-25mM; the addition amount of the soluble vanadium salt is 0.5-9% of the mol amount of the soluble tungsten salt.
The specific operation of uniformly dispersing the photocatalyst on the filter membrane is as follows: and ultrasonically dispersing the photocatalyst by using water, then carrying out suction filtration by using a filter membrane to obtain the photocatalyst which is uniformly dispersed on the filter membrane, and drying the photocatalyst for use.
Compared with the prior art, the invention has the following beneficial effects:
(1) The photocatalysis nitrogen fixation device is portable and simple, integrates photocatalysis nitrogen fixation and plant cultivation, and reduces nitrogen transportation cost. The nitrogen fixation reaction condition is mild, and air is used as the reaction under the sunlightThe preparation can be carried out at normal temperature and normal pressure without using H 2 Reducing energy consumption and being environment-friendly.
(2) The components of the solution after the reaction are nontoxic to plants, the product can be continuously enriched, and the concentration can be adjusted according to the nitrogen requirements in different growth stages for comprehensive management, so that the normal growth of the crops can be met, low carbon can be saved, and the waste of the fertilizer can be reduced.
(3) The catalyst is easy to synthesize and low in cost. Vanadium in the catalyst is highly dispersed in a monoatomic state, active sites on the surface of the catalyst are highly exposed, adsorption and activation of nitrogen are facilitated, and meanwhile, separation of photon-generated carriers is promoted by adjusting an energy band structure of the catalyst, so that the nitrogen oxidation reaction is promoted; meanwhile, the loaded monodisperse metal is used as a new nitrogen adsorption site and an active site, so that the NOR reaction is facilitated, and the photocatalytic nitrogen fixation performance is obviously improved.
Drawings
FIG. 1 is a schematic overall sectional structural view of a photocatalytic nitrogen fixation plant hydroponics growing device of the present invention; wherein, 1, a middle cavity; 2. an outer wall; 3. an inner wall; 4. a cover plate; 5. a perforated partition; 6. a gas check valve; 7. a photocatalyst.
FIG. 2 is a sample V-W obtained in example 1 18 O 49 XRD spectrum of (1);
FIG. 3 is a sample V-W obtained in example 1 18 O 49 HRTEM image of (A);
FIG. 4 is a sample V-W obtained in example 1 18 O 49 EDX maps of (E);
FIG. 5 is a graph comparing the growth of the hydroponic brassica napus in example 1 with no photocatalyst;
FIG. 6 is a graph comparing fresh and dry weight of hydroponic canola with no photocatalyst in example 1;
FIG. 7 is a comparative graph of nitrogen content testing for the hydroponic canola plants with no photocatalyst in example 1.
Detailed Description
[ example 1 ]
Referring to the attached drawing 1, the main body of the photocatalytic nitrogen fixation plant water culture growth device designed in the embodiment is an annular quartz pot body, the total height of the pot body is 155mm, the inner diameter of the pot body is 150mm, the outer diameter of the pot body is 170mm, the thickness of the inner wall is 3mm, and the bottom end of the inner wall is 15mm away from the bottom of the pot body; the top ends of the inner wall and the outer wall of the annular quartz pot body are sealed by a full-transmission quartz glass cover plate; a partition plate with holes is arranged in the upper quarter of the cavity between the inner wall and the outer wall, and the partition plate with holes is made of a quartz sand core; a gas one-way valve is arranged above the perforated clapboard, and the gas enters the device from the outside; uniformly dispersing the photocatalyst on the filter membrane, placing the filter membrane on the porous partition plate, adding 400mL of nitrogen-free Hoagland nutrient solution into the pot body, wherein the liquid level is higher than the bottom end of the inner wall and lower than the porous partition plate.
Preparing a photocatalyst: 100mg of tungsten chloride are dispersed in 75ml of absolute ethanol, and 1.982mg of VCl are then weighed 3 Adding the mixed solution (the molar ratio of vanadium to tungsten is 0.05), stirring for 40min, putting into a polytetrafluoroethylene reaction kettle, and carrying out solvothermal reaction for 12h at 200 ℃. After cooling to room temperature, washing with absolute ethyl alcohol, and vacuum drying at 27 ℃ to obtain the tungsten oxide doped with the vanadium atoms in atomic-scale dispersion, wherein the prepared sample is marked as V-W 18 O 49 。
Taking 50mg of V-W 18 O 49 The photocatalyst is dispersed in 20mL of ultrapure water by ultrasonic wave, the obtained suspension is filtered by a filter membrane (glass fiber membrane, outer diameter 169mm, inner diameter 155mm, aperture 0.2 μm) to uniformly disperse the photocatalyst on the membrane, and the membrane is dried at 60 ℃ for 12 hours and then placed on a porous partition plate.
As shown in FIG. 2, W 18 O 49 And V-W 18 O 49 The XRD pattern of the standard card corresponds to the diffraction peaks of the standard card one by one.
As shown in FIG. 3, W 18 O 49 After the V load of atomic level dispersion, the shape of the nano-wire is not obviously changed, the nano-wire is still superfine and has uniform grain diameter.
As shown in FIG. 4, W, O and V elements exist in the tungsten oxide doped with the atomically dispersed vanadium atoms, and the V element is in W 18 O 49 The surface is uniformly dispersed.
The photo-catalytic nitrogen fixation plant water culture growth device is placed under simulated sunlight for irradiation for 12 hours, and then is taken out and put inThe resulting nitrate ion was detected by ion chromatography with the inner solution, and the yield was calculated to be 33.34. Mu. Mol g -1 h -1 。
Above-mentioned photocatalysis nitrogen fixation plant hydroponics growing device is used for vegetable cultivation: transferring the rape (Suzhou green) germinated for 5 days into the middle cavity of the device, and performing other management on the rape in the same day, and supplementing water every day; after 10 days, the small rape is picked off, and the indexes are measured: measuring the fresh mass of each plant by using an electronic balance, deactivating enzymes at 105 ℃ for 15min, drying at 75 ℃ to constant weight, and measuring the dry mass and the total nitrogen content of the plant. The same test was performed on the obtained canola plants using the same cultivation conditions and plant hydroponics growing apparatus without photocatalyst as a comparison.
As shown in fig. 5, the addition of the photocatalyst can promote plant growth. As shown in FIG. 6 and 7, the fresh weight, dry weight and total nitrogen content of the rape obtained by adding the photocatalyst are all higher than those of the rape obtained by adding no photocatalyst. Illustrating the nitrogen fertilizer (NO) produced by the nitrogen fixation method 3 - ) Can be absorbed and utilized by crops, and can improve the yield of vegetables.
Comparative example 1
100mg of tungsten chloride and 75mL of absolute ethyl alcohol are mixed, stirred for 30 minutes and then placed into a polytetrafluoroethylene reaction kettle to be treated for 12 hours at 200 ℃. After cooling to room temperature, washing with absolute ethyl alcohol, and vacuum drying at 27 ℃ to obtain the photocatalyst W 18 O 49 . W is to be 18 O 49 Alternative example 1 photocatalytic nitrogen fixation plant hydroponics growing apparatus photocatalyst, nitrate ion test results are shown in table 1.
Comparative example 2
100mg of tungsten chloride were dispersed in 75ml of absolute ethanol, and 12.6. Mu.L of TiCl was weighed 4 (1mol L -1 ) Adding the mixed solution (the molar ratio of titanium to tungsten oxide in titanium chloride is 0.05), stirring for 40min, placing into a polytetrafluoroethylene reaction kettle, and treating at 200 deg.C for 12h. After cooling to room temperature, washing with absolute ethyl alcohol, and vacuum drying at 27 ℃ to obtain the titanium/tungsten oxide material Ti-W 18 O 49 . Mixing Ti-W 18 O 49 Alternative example 1 photocatalyst in a photocatalytic nitrogen fixation plant hydroponics growing apparatus,the nitrate ion test results are shown in table 1.
Comparative example 3
100mg of tungsten chloride were dispersed in 75ml of absolute ethanol, and 1mg of CrCl was then weighed 3 Adding the mixed solution (the molar ratio of chromium to tungsten oxide in the chromium chloride is 0.05), stirring for 40min, putting into a polytetrafluoroethylene reaction kettle, and treating at 200 ℃ for 12h. After cooling to room temperature, washing with absolute ethyl alcohol, and vacuum drying at 27 ℃ to obtain a chromium/tungsten oxide material, wherein the prepared sample is marked as Cr-W 18 O 49 . Mixing Cr-W 18 O 49 Alternative example 1 photocatalytic nitrogen fixation plant hydroponics growing apparatus photocatalyst, nitrate ion test results are shown in table 1.
Comparative example 4
Adding TiO into the mixture 2 Alternative example 1 photocatalytic nitrogen fixation plant hydroponics growing apparatus photocatalyst, nitrate ion test results are shown in table 1.
Comparative example 5
1.0g of TiO was weighed 2 In a tube furnace, in H 2 Calcining in an Ar atmosphere, wherein the temperature of the reduction roasting is 500 ℃, the flow rate of the reduction gas is 80mL/min, the heating rate is 5 ℃/min, and the time is 2h. After the baking, introducing H 2 Cooling to room temperature with/Ar and marking the prepared sample as H-TiO 2 . Reacting H-TiO 2 Alternative example 1 photocatalytic nitrogen fixation plant hydroponics growing device in the photocatalyst, nitrate ion test results are shown in table 1.
Comparative example 6
1.0g of TiO was weighed 2 And 1wt.% of RuCl of corresponding mass 3 30ml of ultrapure water was added and stirring was continued at 60 ℃ for 2 hours. After drying, in H 2 Calcining in a tubular furnace atmosphere of/Ar, wherein the temperature of reduction roasting is 500 ℃, the flow rate of reduction gas is 80mL/min, the heating rate is 5 ℃/min, and the time is 2h. After baking, H is introduced 2 cooling/Ar to room temperature to obtain a sample, which is recorded as Ru/H-TiO 2 . Ru/H-TiO 2 Alternative example 1 photocatalytic nitrogen fixation plant hydroponics growing device in the photocatalyst, nitrate ion test results are shown in table 1.
TABLE 1 photocatalytic Nitrogen fixation reaction results
Claims (7)
1. A photocatalysis nitrogen fixation plant water culture growth device is characterized in that the device is an annular transparent pot body, and a middle cavity is used for plant growth; the bottom end of the inner wall of the annular transparent pot body is not connected with the bottom of the pot body; the top ends of the inner wall and the outer wall of the annular transparent pot body are sealed by a cover plate; a cavity between the inner wall and the outer wall of the annular pot body is provided with a perforated clapboard, and a gas one-way valve is arranged above the perforated clapboard; when the device is used, the photocatalyst is uniformly dispersed on the filter membrane and is placed on the porous partition plate, nutrient solution or water for plant growth is poured into the pot body, and the liquid level is higher than the bottom end of the inner wall and lower than the porous partition plate.
2. The device for growing a photocatalytic nitrogen fixation plant in water as claimed in claim 1, wherein the photocatalyst is tungsten oxide doped with vanadium atoms.
3. The photocatalytic nitrogen fixation plant hydroponics growing device of claim 2, wherein the preparation method of the tungsten oxide doped with vanadium atoms is as follows: dissolving soluble tungsten salt in an alcohol solvent, and then adding soluble vanadium salt to obtain a mixed solution; adding the mixed solution into a reaction kettle of polytetrafluoroethylene, carrying out solvothermal reaction for 10-12 hours at 160-200 ℃, carrying out centrifugal washing and vacuum drying to obtain the vanadium atom doped tungsten oxide.
4. The device for the water culture growth of the photocatalytic nitrogen fixation plant as claimed in claim 3, wherein the soluble tungsten salt and the soluble vanadium salt are respectively one or more of nitrate, sulfate or chloride.
5. The device as claimed in claim 3, wherein the alcohol solvent is ethanol and/or propanol.
6. The device for growing a photocatalytic nitrogen fixation plant in water as claimed in claim 3, wherein the concentration of the soluble tungsten salt in the mixed solution is 5-25mM; the addition amount of the soluble vanadium salt is 0.5-9% of the mol amount of the soluble tungsten salt.
7. The photocatalytic nitrogen fixation plant hydroponics growing apparatus of claim 1, wherein the specific operation of dispersing the photocatalyst evenly on the filter membrane is: and ultrasonically dispersing the photocatalyst by using water, then carrying out suction filtration by using a filter membrane to obtain the photocatalyst which is uniformly dispersed on the filter membrane, and drying the photocatalyst for use.
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