CN114042471A - Visible light response type Zn2TiO4/g-C3N4Heterojunction material and application thereof - Google Patents
Visible light response type Zn2TiO4/g-C3N4Heterojunction material and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 230000004298 light response Effects 0.000 title claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 83
- 229910003080 TiO4 Inorganic materials 0.000 claims abstract description 69
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 65
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- ICXVJVVYSULERR-UHFFFAOYSA-L dichlorozinc hexahydrate Chemical compound O.O.O.O.O.O.Cl[Zn]Cl ICXVJVVYSULERR-UHFFFAOYSA-L 0.000 claims description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- DJSKLKQRHSKRDZ-UHFFFAOYSA-N zinc dioxido(oxo)titanium Chemical compound [Zn+2].[O-][Ti]([O-])=O DJSKLKQRHSKRDZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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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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Abstract
The invention discloses a visible light response Zn2TiO4/g‑C3N4Heterojunction materials and applications thereof. The preparation method comprises the following steps: zinc titanate Zn2TiO4Adding the powder and melamine powder into deionized water, firstly carrying out ultrasonic treatment for 1h, and then stirring for 12h to form uniform dispersion liquid; drying the obtained dispersion liquid to obtain a precursor; placing the obtained precursor in a muffle furnace for high-temperature calcination to obtain Zn2TiO4/g‑C3N4A heterojunction material. In the invention, g-C3N4With Zn2TiO4Compounding to successfully prepare the visible light response Zn2TiO4/g‑C3N4Heterojunction material, and the catalyst is applied to photocatalysis nitrogen fixation to produce ammonia. The results show that Zn is produced2TiO4/g‑C3N4The heterojunction material has better photocatalysis nitrogen fixation and ammonia production performance, is simple to operate, has a popularization effect on photocatalysis green synthesis ammonia, and has the advantages of energy conservation and environmental protection.
Description
Technical Field
The invention belongs to the technical field of synthesis of photocatalytic materials, relates to a visible light response type catalyst, and particularly relates to graphite carbon nitride (g-C)3N4) With zinc titanate (Zn)2TiO4) Visible light response type Zn formed by compounding2TiO4/g-C3N4Heterojunction materials and their use in nitrogen fixation.
Background
N2As a raw material for ammonia synthesis, N is abundant in earth2The molecule is nonpolar, the nitrogen-nitrogen triple bond has 945kJ/mol of bond energy, and the first bond dissociation energy is high, the nucleophilicity to proton is weak, and the reduction is extremely difficult. At present, the artificial nitrogen fixation is mainly carried out by a haber method, the reaction conditions are harsh, the artificial nitrogen fixation needs to be carried out at high temperature and high pressure, the energy consumption is high, and simultaneously, a large amount of CO is accompanied2And (5) discharging. Therefore, from the viewpoint of cost control and environmental protection, it is of great significance to study artificial nitrogen fixation under mild conditions. In recent years, scientists find that the solar energy is used as a driving force in the nitrogen fixation reaction process to replace the harsh conditions of high temperature and high pressure in the haber reaction, but the efficiency of the catalytic reaction is far lower than the expectation of people. Therefore, the development of a high-efficiency, environment-friendly and mild-technical photocatalytic material is attracting more and more attention.
The existing photocatalysis nitrogen fixation technology has a plurality of difficulties: 1) catalyst pair N due to limited surface defects2The adsorption activation amount of (A) is insufficient; 2) the photon-generated carriers are easy to recombine; 3) the oxidation capability to water is weak and protons required for the nitrogen fixation reaction cannot be provided. g-C3N4The material is a newly grown organic semiconductor material and has wide application in the field of photocatalysis. But due to C3N4The photogenerated carriers are easy to recombine, and have limited surface defects and poorer water oxidation capability. Researchers are currently working through a variety of means (e.g., building semiconductors)Bulk heterojunction, noble metal loading, metal or nonmetal doping, sacrificial agent addition, etc.), the g-C is improved3N4Utilization of photogenerated carriers of, for N2Adsorption activation ability and water oxidation ability. However, the photocatalytic nitrogen fixation cannot get rid of organic capture agents or sacrificial agents (such as ethanol and the like), and the production cost is high and the energy consumption is large.
Disclosure of Invention
Aiming at the high temperature, high pressure and large amount of CO existing in the commonly adopted Haber method ammonia synthesis technology2The invention aims to provide a visible light response type Zn2TiO4/g-C3N4Heterojunction materials and their use in nitrogen fixation.
The technical scheme adopted by the invention is as follows: visible light response type Zn2TiO4/g-C3N4The preparation method of the heterojunction material comprises the following steps: zinc titanate Zn2TiO4Adding the powder and melamine powder into deionized water, firstly carrying out ultrasonic treatment for 1h, and then stirring for 12h to form uniform dispersion liquid; drying the obtained dispersion liquid to obtain a precursor; placing the obtained precursor in a muffle furnace for high-temperature calcination to obtain Zn2TiO4/g-C3N4A heterojunction material.
Preferably, one of the above visible-light responsive Zn2TiO4/g-C3N4Heterojunction material, zinc titanate Zn by mass ratio2TiO4Melamine is 1:1 to 1: 10.
Preferably, one of the above visible-light responsive Zn2TiO4/g-C3N4And (3) calcining the heterojunction material at 600 ℃ for 2 h.
Preferably, one of the above visible-light responsive Zn2TiO4/g-C3N4Heterojunction material, said zinc titanate Zn2TiO4The preparation method of the powder comprises the following steps: dissolving zinc salt in absolute ethyl alcohol, adding glacial acetic acid, stirring at room temperature for 30 minutes, and dropwise adding titanium into the obtained mixed solutionStirring tetra-n-butyl acetate for 30min, aging the obtained solution, and drying overnight to obtain an intermediate product; placing the obtained intermediate product in a muffle furnace, calcining at the high temperature of 600 ℃ for 2h in the air environment, cooling to room temperature, grinding to obtain zinc titanate Zn2TiO4And (3) powder.
Preferably, one of the above visible-light responsive Zn2TiO4/g-C3N4The heterojunction material, the zinc salt is zinc nitrate hexahydrate or zinc chloride hexahydrate.
Preferably, one of the above visible-light responsive Zn2TiO4/g-C3N4The aging time of the heterojunction material is 24 hours.
The invention provides visible light response Zn2TiO4/g-C3N4The heterojunction material is applied to catalyzing nitrogen fixation and ammonia production under the irradiation of visible light.
Preferably, the method is as follows: under the conditions of normal temperature and normal pressure, Zn is added2TiO4/g-C3N4Dissolving the heterojunction material in methanol water solution, and performing ultrasonic dispersion uniformly to obtain dispersion liquid; under the irradiation of visible light, nitrogen N is introduced into the dispersion liquid at a certain speed2Catalyzing nitrogen fixation to produce ammonia.
The invention has the beneficial effects that:
1. in the invention, g-C3N4With Zn2TiO4Compounding to successfully prepare the visible light response Zn2TiO4/g-C3N4Heterojunction material, and the catalyst is applied to photocatalysis nitrogen fixation to produce ammonia. The results show that Zn is produced2TiO4/g-C3N4The heterojunction material has better photocatalysis nitrogen fixation and ammonia production performance, is simple to operate, has a popularization effect on photocatalysis green synthesis ammonia, and has the advantages of energy conservation and environmental protection.
2. Zn prepared by the method of the present invention2TiO4/g-C3N4The composite material and the heterojunction promote the separation of photo-generated electron-hole pairs, so that the photo-generated electron-hole pairs have stronger photocatalytic reduction capability and participate in catalytic reactionAnd can adsorb and degrade organic pollutant to raise photocatalytic activity. The composite photocatalyst is an effective way for improving the visible light catalytic activity of the composite photocatalyst, and Zn is used2TiO4With non-metallic catalysts g-C3N4The heterojunction formed by compounding can greatly promote the transmission of photo-generated electrons and holes, thereby remarkably improving the visible light responsiveness of the catalyst and increasing the visible light catalytic activity. Experimental results show that the catalyst prepared by the invention has better photocatalytic nitrogen fixation and ammonia production performance, is simple to operate, has the advantages of energy conservation and environmental protection, and has great development and application prospects in the aspect of photocatalytic green synthesis of ammonia.
Drawings
FIG. 1 shows a visible light response type Zn prepared by the invention2TiO4/g-C3N4XRD pattern of the heterojunction material.
FIG. 2 shows the visible light response Zn prepared in different proportions2TiO4/g-C3N4The nitrogen fixation activity of the heterojunction material is compared with that of the shown diagram.
FIG. 3 shows the visible light response Zn prepared according to different proportions2TiO4/g-C3N4The nitrogen fixation efficiency of the heterojunction material is compared with that of the graph.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1 visible light responsive Zn2TiO4/g-C3N4The preparation method of the heterojunction material (I) comprises the following steps:
1. preparation of pure sample g-C3N4
Spreading 1g of melamine in a quartz crucible covered with a cover, heating to 600 ℃ at a heating rate of 5 ℃/min, heating for 2h under the protection of nitrogen, cooling to room temperature, grinding into powder, and collecting for later use.
2. Preparation of pure Zn2TiO4
0.874g of hexahydrateDissolving zinc nitrate in 10ml of absolute ethyl alcohol, adding 2ml of glacial acetic acid, stirring at room temperature for 30min, dropwise adding 1ml of tetra-n-butyl titanate into the obtained mixed solution, continuously stirring for 30min, aging the obtained solution for 24h, and drying at 80 ℃ overnight to obtain an intermediate product; placing the obtained intermediate product in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min in an air environment, calcining at high temperature for 2h in the air environment, cooling to room temperature, and grinding to obtain zinc titanate Zn2TiO4And (3) powder.
3. Preparing visible light response type Zn2TiO4/g-C3N4Heterojunction material
1) Adding 0.2g of zinc titanate powder and 0.2g of melamine powder into 10ml of deionized water, firstly carrying out ultrasonic treatment for 1 hour, and then stirring for 12 hours to form uniform dispersion liquid; drying the obtained dispersion liquid at 80 ℃ overnight to obtain a precursor; placing the obtained precursor in a muffle furnace, calcining at 600 ℃ for 2h to obtain Zn with the mass ratio of zinc titanate to melamine being 1:12TiO4/g-C3N4A heterojunction material.
2) Adding 0.2g of zinc titanate powder and 1.0g of melamine powder into 10ml of deionized water, firstly carrying out ultrasonic treatment for 1 hour, and then stirring for 12 hours to form uniform dispersion liquid; drying the obtained dispersion liquid at 80 ℃ overnight to obtain a precursor; placing the obtained precursor in a muffle furnace, calcining at 600 ℃ for 2h to obtain Zn with the mass ratio of zinc titanate to melamine being 1:52TiO4/g-C3N4A heterojunction material.
3) Adding 0.2g of zinc titanate powder and 2.0g of melamine powder into 10ml of deionized water, firstly carrying out ultrasonic treatment for 1 hour, and then stirring for 12 hours to form uniform dispersion liquid; drying the obtained dispersion liquid at 80 ℃ overnight to obtain a precursor; placing the obtained precursor in a muffle furnace, calcining at 600 ℃ for 2h to obtain Zn with the mass ratio of zinc titanate to melamine being 1:102TiO4/g-C3N4A heterojunction material.
(II) detection
FIG. 1 is a drawing showing the preparation of a pure sample g-C3N4Pure Zn sample2TiO4And Zn prepared in different mass ratios2TiO4/g-C3N4The result of the XRD pattern of the heterojunction material shows that Zn is successfully synthesized2TiO4/g-C3N4A heterojunction material.
Example 2 Zn2TiO4/g-C3N4The application method of the heterojunction material in catalyzing nitrogen fixation under the irradiation of visible light comprises the following steps:
50mL of an aqueous methanol solution (0.001mol/L) was placed in a vessel at room temperature under normal pressure, and 50mg of each of the pure samples g-C prepared in example 1 was added3N4Pure Zn sample2TiO4And Zn prepared in different mass ratios2TiO4/g-C3N4And (5) carrying out ultrasonic treatment on the heterojunction material for 10min to obtain dispersion liquid. Under the condition of visible light irradiation, nitrogen N is introduced into the container at the speed of 10mL/min2And after reacting for 180min, taking clear liquid, and measuring the ammonia production efficiency by adopting a nano reagent spectrophotometry. The results are shown in FIGS. 2 and 3.
As can be seen from FIG. 2, Zn2TiO4/g-C3N4The ammonia yield of the heterojunction material is obviously higher than that of pure Zn2TiO4And g-C3N4. As pure g-C3N4As a catalyst, ammonia was produced at a concentration of 42.82. mu. mol/L under irradiation with visible light. As pure Zn2TiO4As a catalyst, ammonia was produced at a concentration of 20.97. mu. mol/L under irradiation with visible light. Zn with mass ratio of 1:12TiO4/g-C3N4The heterojunction material is a catalyst, and the concentration of generated ammonia is 121.24 mu mol/L under the irradiation of visible light. Zn with mass ratio of 1:52TiO4/g-C3N4The heterojunction material is a catalyst, and the concentration of generated ammonia is 199.07 mu mol/L under the irradiation of visible light. Zn with mass ratio of 1:102TiO4/g-C3N4The heterojunction material is a catalyst, and the concentration of generated ammonia is 136.79 mu mol/L under the irradiation of visible light.
As can be seen from FIG. 3, pure Zn2TiO4And pure g-C3N4The nitrogen fixation efficiency of the nitrogen-containing material is obviously lower than that of Zn2TiO4/g-C3N4Nitrogen fixation efficiency of the heterojunction material. Under the irradiation of visible light, g-C is taken as a pure sample3N4The nitrogen fixation efficiency of the catalyst is 14.47 mu mol/L/h, and pure Zn is used2TiO4Zn serving as a catalyst and having nitrogen fixation efficiency of 5.38 mu mol/L/h in a mass ratio of 1:12TiO4/g-C3N4The heterojunction material is a catalyst, the nitrogen fixation efficiency is 38.79 mu mol/L/h, and the mass ratio of Zn to N is 1:52TiO4/g-C3N4The heterojunction material is a catalyst, the nitrogen fixation efficiency is 60.10 mu mol/L/h, and the mass ratio of Zn to N is 1:102TiO4/g-C3N4The heterojunction material is a catalyst, the nitrogen fixation efficiency is 43.97 mu mol/L/h, and Zn with the mass ratio of 1:5 can be seen2TiO4/g-C3N4The nitrogen fixation performance of the heterojunction material is the best.
Claims (8)
1. Visible light response type Zn2TiO4/g-C3N4The heterojunction material is characterized in that the preparation method comprises the following steps: zinc titanate Zn2TiO4Adding the powder and melamine powder into deionized water, firstly carrying out ultrasonic treatment for 1h, and then stirring for 12h to form uniform dispersion liquid; drying the obtained dispersion liquid to obtain a precursor; placing the obtained precursor in a muffle furnace for high-temperature calcination to obtain Zn2TiO4/g-C3N4A heterojunction material.
2. The visible light-responsive Zn according to claim 12TiO4/g-C3N4A heterojunction material characterized in that zinc titanate Zn is present in a mass ratio2TiO4Melamine is 1:1 to 1: 10.
3. The visible light-responsive Zn according to claim 12TiO4/g-C3N4A heterojunction material, characterized in that said high-temperature calcination is carried out at 600 ℃ for 2 h.
4. According to claims 1, 2A visible light responsive Zn as described in (1) or (3)2TiO4/g-C3N4A heterojunction material, characterized in that said zinc titanate Zn2TiO4The preparation method of the powder comprises the following steps: dissolving zinc salt in absolute ethyl alcohol, adding glacial acetic acid, stirring at room temperature for 30 minutes, dropwise adding tetra-n-butyl titanate into the obtained mixed solution, continuously stirring for 30 minutes, aging the obtained solution, and drying overnight to obtain an intermediate product; placing the obtained intermediate product in a muffle furnace, calcining at the high temperature of 600 ℃ for 2h in the air environment, cooling to room temperature, grinding to obtain zinc titanate Zn2TiO4And (3) powder.
5. The visible-light-responsive Zn according to claim 42TiO4/g-C3N4A heterojunction material, wherein said zinc salt is zinc nitrate hexahydrate or zinc chloride hexahydrate.
6. The visible-light-responsive Zn according to claim 42TiO4/g-C3N4Heterojunction material characterized in that the aging time is 24 h.
7. A visible light responsive Zn according to claim 1, 2 or 32TiO4/g-C3N4The heterojunction material is applied to catalyzing nitrogen fixation and ammonia production under the irradiation of visible light.
8. Use according to claim 7, characterized in that the method is as follows: under the conditions of normal temperature and normal pressure, Zn is added2TiO4/g-C3N4Dissolving the heterojunction material in methanol water solution, and performing ultrasonic dispersion uniformly to obtain dispersion liquid; introducing nitrogen N into the dispersion liquid under the irradiation of visible light2Catalyzing nitrogen fixation to produce ammonia.
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|---|---|---|---|---|
| CN114558561A (en) * | 2022-03-15 | 2022-05-31 | 辽宁大学 | Preparation method and application of zinc titanate oxygen-containing defect photocatalyst |
| CN114570352A (en) * | 2022-03-31 | 2022-06-03 | 辽宁大学 | W18O49/ZnTiO3Nitrogen fixation photocatalyst and preparation method and application thereof |
| CN114789049A (en) * | 2022-03-25 | 2022-07-26 | 辽宁大学 | Preparation method and application of cerium oxide and zinc titanate composite photocatalyst |
| CN116020496A (en) * | 2023-01-03 | 2023-04-28 | 辽宁大学 | BiOI/Zn with discrete structure 2 TiO 4 Heterojunction nanofiber photocatalyst and preparation method and application thereof |
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| CN114558561A (en) * | 2022-03-15 | 2022-05-31 | 辽宁大学 | Preparation method and application of zinc titanate oxygen-containing defect photocatalyst |
| CN114558561B (en) * | 2022-03-15 | 2023-12-08 | 辽宁大学 | Preparation method and application of zinc titanate oxygen-containing defect photocatalyst |
| CN114789049A (en) * | 2022-03-25 | 2022-07-26 | 辽宁大学 | Preparation method and application of cerium oxide and zinc titanate composite photocatalyst |
| CN114789049B (en) * | 2022-03-25 | 2023-04-07 | 辽宁大学 | Preparation method and application of cerium oxide and zinc titanate composite photocatalyst |
| CN114570352A (en) * | 2022-03-31 | 2022-06-03 | 辽宁大学 | W18O49/ZnTiO3Nitrogen fixation photocatalyst and preparation method and application thereof |
| CN116020496A (en) * | 2023-01-03 | 2023-04-28 | 辽宁大学 | BiOI/Zn with discrete structure 2 TiO 4 Heterojunction nanofiber photocatalyst and preparation method and application thereof |
| CN116020496B (en) * | 2023-01-03 | 2024-05-10 | 辽宁大学 | BiOI/Zn with discrete structure2TiO4Heterojunction nanofiber photocatalyst and preparation method and application thereof |
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