CN115500256B - Photocatalysis nitrogen fixation plant hydroponic growing device - Google Patents
Photocatalysis nitrogen fixation plant hydroponic growing device Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 44
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 31
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- 238000005192 partition Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 230000012010 growth Effects 0.000 claims abstract description 13
- 230000008635 plant growth Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 10
- 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 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 12
- 239000003501 hydroponics Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- 150000003657 tungsten Chemical class 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 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
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001035 drying 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
- 238000002360 preparation method Methods 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 8
- 239000003337 fertilizer Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 235000016709 nutrition Nutrition 0.000 abstract description 2
- 230000035764 nutrition Effects 0.000 abstract description 2
- 241000196324 Embryophyta Species 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 240000000385 Brassica napus var. napus Species 0.000 description 4
- 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
- 238000001816 cooling Methods 0.000 description 4
- 230000009467 reduction Effects 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
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 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
- 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
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 230000009418 agronomic effect 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
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 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
- 230000002349 favourable 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
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 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
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium 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
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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 photocatalysis nitrogen fixation plant hydroponic growth device. The device is an annular transparent basin body, and the middle cavity is used for plant growth; the bottom end of the inner wall of the annular transparent basin body is not connected with the bottom of the basin body; the top ends of the inner wall and the outer wall of the annular transparent basin body are sealed by a cover plate; the cavity in the middle of the inner wall and the outer wall of the annular basin body is provided with a porous partition plate, and a gas one-way valve is arranged above the porous partition plate; when in use, the photocatalyst is uniformly dispersed on the filter membrane and is placed on the porous partition board together, the nutrient solution or water for plant growth is poured into the basin body, and the liquid level is higher than the bottom end of the inner wall and lower than the porous partition board. The device is integrated with photocatalysis nitrogen fixation and plant cultivation, can uniformly and continuously provide nitrogen fertilizer nutrition for plant growth, does not need to additionally add nitrogen source, can meet the normal growth of plants, can also achieve low-carbon saving and reduce the use of fertilizer.
Description
Technical Field
The invention belongs to the technical field of plant hydroponics devices, and particularly relates to a photocatalysis nitrogen fixation plant hydroponics growing device.
Background
Ammonia/nitrate is one of the important raw materials in the 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 other aspects. The industrial production mainly adopts the Haber-Bosch process to hydrogenate nitrogen to produce ammonia at high temperature and high pressure, and then uses Ostwald to hydrogenate ammonia (NH) 4 + ) Conversion to Nitrate (NO) 3 - ). The above processes consume large amounts of energy and are accompanied by large amounts of 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, can selectively activate part of the bonds, in the field of photocatalysis, e.g. photolysis of water, CO 2 Reduction, N 2 There are many applications in reduction and the like. Accordingly, scientists have been devoted to research into the ability to produce nitrogen fertilizer dispersedly in a planting area using nitrogen and water (or air) as raw materials and solar energy as energy.
The reported catalyst mainly adopts noble metals such as Pd, pt, rh and the like, and has the advantages of high price, complex reaction system, difficult enrichment of products after reaction and the likeProblems. Furthermore, there is NO patent or literature currently available for in situ photocatalytic nitrate (NO 3 - ) The system is introduced into a nutrient solution cultivation system, a device for cultivating plants through in-situ nitrogen fixation can be successfully designed, a high-efficiency nitrogen fixation catalyst is designed, an effectively absorbable and utilizable nitrate nitrogen fertilizer is provided for plant growth, and the system is a key problem of popularization and application of a photocatalysis nitrate production system in the agronomic field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention designs a photocatalysis nitrogen fixation plant hydroponic growth device which is used for photocatalysis nitrogen fixation direct supply plant growth. The device is integrated with photocatalysis nitrogen fixation and plant cultivation, the vanadium doped tungsten oxide photocatalyst converts nitrogen in the air into nitric oxide at normal temperature and normal pressure under sunlight, generated nitric oxide and oxygen in the air enter water to react to generate nitrate radical, a gas one-way valve in the device can supplement air consumed by the reaction, the purpose of uniformly and continuously providing nitrogen fertilizer nutrition for plant growth is achieved, no additional nitrogen source is needed, normal growth of plants can be met, low carbon and saving can be achieved, and fertilizer use is reduced.
The photocatalysis nitrogen fixation plant water planting growth device is an annular transparent basin body, and the middle cavity is used for plant growth; the bottom end of the inner wall of the annular transparent basin body is not connected with the bottom of the basin body; the top ends of the inner wall and the outer wall of the annular transparent basin body are sealed by a cover plate; the cavity in the middle of the inner wall and the outer wall of the annular basin body is provided with a porous partition plate, and a gas one-way valve is arranged above the porous partition plate; when in use, the photocatalyst is uniformly dispersed on the filter membrane and is placed on the porous partition board together, the nutrient solution or water for plant growth is poured into the basin body, and the liquid level is higher than the bottom end of the inner wall and lower than the porous partition board.
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, performing solvothermal reaction for 10-12 hours at 160-200 ℃, centrifugally washing, and performing vacuum drying to obtain 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 mole amount of the soluble tungsten salt.
The specific operation of uniformly dispersing the photocatalyst on the filter membrane is as follows: dispersing the photocatalyst by water ultrasonic, then carrying out suction filtration by using a filter membrane to obtain the photocatalyst which is uniformly dispersed on the filter membrane, and drying 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 with plant cultivation, and reduces nitrogen transportation cost. The nitrogen fixation reaction condition is mild, under the sunlight, air is used as a reactant, and the reaction can be carried out at normal temperature and normal pressure without H 2 The energy consumption is reduced, and the environment is friendly.
(2) The components of the solution after the reaction are non-toxic to plants, products can be continuously enriched, and the concentration is regulated according to the nitrogen requirements of different growth stages to carry out comprehensive management, so that the normal growth of crops can be met, low carbon and saving can be achieved, and the waste of fertilizer can be reduced.
(3) The catalyst is easy to synthesize and has low cost. The vanadium in the catalyst is highly dispersed in a single atom state, and the active site on the surface of the catalyst is highly exposed, so that the adsorption and activation of nitrogen are facilitated, and meanwhile, the separation of photon-generated carriers and the oxidation reaction of nitrogen are promoted by adjusting the energy band structure of the catalyst; meanwhile, the loaded monodisperse metal is used as a new nitrogen adsorption site and an active site, which is favorable for NOR reaction, and obviously improves the photocatalytic nitrogen fixation performance.
Drawings
FIG. 1 is a schematic diagram of the overall sectional structure of a photocatalytic nitrogen fixation plant hydroponic growing device of the invention; wherein, 1, the middle cavity; 2. an outer wall; 3. an inner wall; 4. a cover plate; 5. a separator plate with holes; 6. a gas check valve; 7. a photocatalyst.
FIG. 2 is a sample V-W prepared in example 1 18 O 49 XRD pattern of (b);
FIG. 3 is a sample V-W prepared in example 1 18 O 49 HRTEM images of (a);
FIG. 4 is a sample V-W prepared in example 1 18 O 49 EDX maps of (a);
FIG. 5 is a graph showing comparison of growth of a water-cultured canola plant with no light catalyst in example 1;
FIG. 6 is a graph showing the fresh weight and dry weight comparison of a water-cultivated canola plant with no catalyst of example 1;
FIG. 7 is a graph showing the comparison of nitrogen content test of a water-cultured canola plant with no light catalyst in example 1.
Detailed Description
[ example 1 ]
Referring to FIG. 1, the main body of the photocatalysis nitrogen fixation plant water planting growth device designed in the embodiment is an annular quartz basin body, the total height of the basin body is 155mm, the inner diameter of the basin body is 150mm, the outer diameter of the basin 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 basin body; the top ends of the inner wall and the outer wall of the annular quartz basin body are sealed by adopting a fully transparent quartz glass cover plate; a porous partition board is arranged at one quarter of the upper part of the cavity between the inner wall and the outer wall, and the porous partition board is made of quartz sand cores; a gas one-way valve is arranged above the porous partition board, and the gas direction of the gas one-way valve enters the device from the outside; uniformly dispersing the photocatalyst on the filter membrane, placing the filter membrane on a porous partition plate, and adding 400mL of nitrogen-free Hoagland nutrient solution into the basin 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 was dispersed in 75ml of absolute ethanol, and 1.982mg of VCl was weighed 3 Adding the mixed solution (the molar ratio of vanadium to tungsten is 0.05), stirring for 40min, and putting into a polytetrafluoroethylene reaction kettle for solvothermal reaction at 200 ℃ for 12h. After cooling to room temperature, washing with absolute ethanol, vacuum drying at 27 ℃ to obtain atomically dispersed vanadium atom doped tungsten oxide, and recording the obtained sample as V-W 18 O 49 。
50mg V-W 18 O 49 The photocatalyst was ultrasonically dispersed in 20mL of ultrapure water, and the resulting suspension was suction-filtered with a filter membrane (glass fiber membrane, outer diameter 169mm, inner diameter 155mm, pore diameter 0.2 μm) to uniformly disperse the photocatalyst on the membrane, dried at 60℃for 12 hours, and then placed on a porous separator.
As shown in FIG. 2, W 18 O 49 And V-W 18 O 49 One-to-one correspondence of XRD patterns and standard card diffraction peaks.
As shown in FIG. 3, W 18 O 49 After being loaded by the V with atomic-level dispersion, the morphology of the nano-wire is not obviously changed, the nano-wire is still an ultrafine nano-wire, and the particle size is uniform.
As shown in FIG. 4, W, O, V element is present in the atomically dispersed vanadium atom doped tungsten oxide and V element is W 18 O 49 The surface is uniformly dispersed.
The photocatalytic nitrogen fixation plant water planting growth device is placed under simulated sunlight for irradiation for 12 hours, the solution in the device is taken, nitrate ions generated by ion chromatography detection are used, and the yield is calculated to be 33.34 mu mol g -1 h -1 。
The photocatalysis nitrogen fixation plant water planting growth device is used for vegetable cultivation: transferring germinated rape (Suzhou green) into the middle cavity of the device, and performing other management on the rape in the same day as the management, and supplementing water every day; after 10 days, the rape is picked off and the index is determined: the fresh mass of the single plant is measured by adopting an electronic balance, and then the fresh plant is deactivated for 15min at 105 ℃, dried to constant weight at 75 ℃, and then the dry mass and the total nitrogen content thereof are measured. The same test was performed on the obtained canola plants under the same cultivation conditions, with the plant hydroponic growth apparatus without photocatalyst added as a comparison.
As shown in FIG. 5, the addition of a photocatalyst may promote plant growth. As shown in FIGS. 6 and 7, the fresh weight, dry weight and total nitrogen content of the photocatalytic canola oil obtained by adding the photocatalyst are higher than those obtained by not adding the photocatalyst. Illustrating the nitrogen fertilizer (NO) produced by the nitrogen fixation method 3 - ) Can be absorbed and utilized by crops, and can improve the vegetable yield.
Comparative example 1
100mg of tungsten chloride and 75mL of absolute ethyl alcohol are mixed, stirred for 30 minutes, and then placed in a polytetrafluoroethylene reaction kettle for treatment at 200 ℃ for 12 hours. After cooling to room temperature, washing with absolute ethanol, and vacuum drying at 27 ℃ to obtain the photocatalyst W 18 O 49 . Will W 18 O 49 Alternative example 1 the results of the nitrate ion test of the photocatalyst in the photocatalytic nitrogen fixing plant hydroponics growing device are shown in table 1.
Comparative example 2
100mg of tungsten chloride was dispersed in 75ml of absolute ethanol, and then 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, and placing into a polytetrafluoroethylene reaction kettle for treatment at 200 ℃ for 12h. After cooling to room temperature, washing with absolute ethyl alcohol, and vacuum drying at 27 ℃ to obtain Ti-W material 18 O 49 . Ti-W 18 O 49 Alternative example 1 the results of the nitrate ion test of the photocatalyst in the photocatalytic nitrogen fixing plant hydroponics growing device are shown in table 1.
[ comparative example 3 ]
100mg of tungsten chloride was dispersed in 75ml of absolute ethanol, and then 1mg of CrCl was weighed 3 Adding the mixed solution (the mole ratio of chromium and tungsten oxide in chromium chloride is 0.05), stirring for 40min, and placing into a polytetrafluoroethylene reaction kettle for treatment at 200 ℃ for 12h. After cooling to room temperature, washing with absolute ethanol, and vacuum drying at 27 ℃ to obtain chromium/tungsten oxide material, wherein the prepared sample is named Cr-W 18 O 49 . Cr-W 18 O 49 Alternative example 1 the results of the nitrate ion test of the photocatalyst in the photocatalytic nitrogen fixing plant hydroponics growing device are shown in table 1.
[ comparative example 4 ]
TiO is mixed with 2 Alternative example 1 the results of the nitrate ion test of the photocatalyst in the photocatalytic nitrogen fixing plant hydroponics growing device are shown in table 1.
Comparative example 5
1.0g of TiO is weighed 2 In a tube furnace, in H 2 Calcination under Ar atmosphere, reduction calcinationThe temperature was 500 ℃, the flow rate of the reducing gas was 80mL/min, the heating rate was 5 ℃/min, and the time was 2h. After the roasting is finished, H is introduced 2 Ar was cooled to room temperature and the sample obtained was designated H-TiO 2 . H-TiO 2 Alternative example 1 the results of the nitrate ion test of the photocatalyst in the photocatalytic nitrogen fixing plant hydroponics growing device are shown in table 1.
[ comparative example 6 ]
1.0g of TiO is weighed 2 And 1wt.% of corresponding mass RuCl 3 To 30ml of ultrapure water was added and stirring was continued at 60℃for 2 hours. After drying, in H 2 calcining/Ar in a tubular furnace atmosphere, wherein the temperature of the reduction roasting is 500 ℃, the flow rate of the reducing gas is 80mL/min, the heating rate is 5 ℃/min, and the time is 2h. After the roasting is finished, H is introduced 2 Ar is cooled to room temperature, and the obtained sample is recorded as Ru/H-TiO 2 . Ru/H-TiO 2 Alternative example 1 the results of the nitrate ion test of the photocatalyst in the photocatalytic nitrogen fixing plant hydroponics growing device are shown in table 1.
TABLE 1 photocatalytic Nitrogen fixation reaction results
Claims (4)
1. A photocatalysis nitrogen fixation plant hydroponic growth device is characterized in that the device is an annular transparent basin body, and a middle cavity is used for plant growth; the bottom end of the inner wall of the annular transparent basin body is not connected with the bottom of the basin body; the top ends of the inner wall and the outer wall of the annular transparent basin body are sealed by a cover plate; the cavity in the middle of the inner wall and the outer wall of the annular transparent basin body is provided with a porous partition plate, and a gas one-way valve is arranged above the porous partition plate; when in use, the photocatalyst is uniformly dispersed on the filter membrane and is placed on the porous partition board together, the nutrient solution or water for plant growth is poured into the basin body, and the liquid level is higher than the bottom end of the inner wall and lower than the porous partition board; 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, performing solvothermal reaction for 10-12 hours at 160-200 ℃, centrifugally washing, and performing vacuum drying to obtain vanadium-atom-doped tungsten oxide;
the specific operation of uniformly dispersing the photocatalyst on the filter membrane is as follows: dispersing the photocatalyst by water ultrasonic, then carrying out suction filtration by using a filter membrane to obtain the photocatalyst which is uniformly dispersed on the filter membrane, and drying for use.
2. The photocatalytic nitrogen fixation plant hydroponic growth device according to claim 1, wherein the soluble tungsten salt and the soluble vanadium salt are one or more of nitrate, sulfate and chloride respectively.
3. The photocatalytic nitrogen fixing plant hydroponics growing apparatus of claim 1, wherein the alcohol solvent is ethanol and/or propanol.
4. The photocatalytic nitrogen fixation plant hydroponic growth device according to claim 1, 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 mole amount of the soluble tungsten salt.
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