CN112221529A - Bi-B doped SrWO4/Ba-g-C3N4Composite nitrogen-fixing photocatalyst and preparation method thereof - Google Patents
Bi-B doped SrWO4/Ba-g-C3N4Composite nitrogen-fixing photocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN112221529A CN112221529A CN202011258704.0A CN202011258704A CN112221529A CN 112221529 A CN112221529 A CN 112221529A CN 202011258704 A CN202011258704 A CN 202011258704A CN 112221529 A CN112221529 A CN 112221529A
- Authority
- CN
- China
- Prior art keywords
- srwo
- photocatalyst
- doped
- preparation
- srcl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 229910004415 SrWO4 Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 20
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910020350 Na2WO4 Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 70
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of photocatalytic application, and particularly relates to Bi-B doped SrWO4/Ba‑g‑C3N4The composite nitrogen-fixing photocatalyst and the preparation method thereof, the preparation method comprises the following steps: first, melamine, thiourea and Ba (OH)2Mixing the raw materials in a certain proportion, and calcining the mixture in a muffle furnace to obtain Ba-g-C3N4(ii) a With SrCl2·6H2O and Na2WO4·2H2O is taken as a raw material, trimethyl borate and BiCl are added3In Ba-g-C3N4Surface precipitation of (A) to obtain Bi-B doped SrWO4/Ba‑g‑C3N4A composite nitrogen fixation photocatalyst. The nitrogen fixation photocatalyst has high utilization rate of visible light and strong nitrogen fixation performance.
Description
Technical Field
The invention belongs to the technical field of photocatalytic application, and particularly relates to Bi-B doped SrWO4/Ba-g-C3N4A composite nitrogen-fixing photocatalyst and a preparation method thereof.
Background
Nitrogen plays a vital role in human life, and is an essential element in substances that maintain human survival, such as amino acids, proteins, pharmaceuticals, and fertilizers. The ammonia synthesized by taking nitrogen as a raw material is not only applied to chemical raw materials for producing nitrogen fertilizers and the like, but also can be used as fuel and hydrogen storage materials, and has great application in the field of energy sources. The synthesis process widely applied in the current ammonia synthesis industry is still Haber-Bosch method; because of N2The molecule belongs to nonpolar molecules, the activity is very low, and N ═ N triple bond has very strong chemical bond, the process of breaking the chemical bond to form ammonia has very large energy consumption, and Haber-Bosch method requires the reaction condition of high temperature (500-.
The photocatalytic nitrogen fixation is mainly based on semiconductor materials. The semiconductor material with proper forbidden band width can generate photocatalysis nitrogen fixation reaction by utilizing the solar illumination with the wavelength less than or equal to the forbidden band width. First, electrons in the valence band absorb light and can jump to the conduction band to generate photon-generated carriers, i.e., electron-hole pairs, and part of the carriers can migrate to the particle surface to undergo oxidation or reduction reactions with substances adsorbed on the surface of the semiconductor catalyst. Wherein the holes are adsorbed on OH on the surface of the catalyst-Or H2The O is oxidized to generate O2And H+Photo-generated electrons are adsorbed on the surface of the catalyst2And H in solution+Reduction reaction is carried out to generate NH3。
Disclosure of Invention
Aiming at the technical defects of low visible light utilization rate and poor nitrogen fixation performance of the existing nitrogen fixation photocatalyst, the invention provides Bi-B doped SrWO4/Ba-g-C3N4A composite nitrogen-fixing photocatalyst and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
Bi-B doped SrWO4/Ba-g-C3N4The preparation method of the composite nitrogen-fixing photocatalyst comprises the following steps:
the method comprises the following steps: mixing certain amount of melamine, thiourea and Ba (OH)2Uniformly mixing, placing into an aluminum oxide crucible, heating to 550 ℃ in a muffle furnace, calcining for 4-6h, cooling to room temperature, grinding the obtained block sample in a mortar for 30-40min to obtain powdery Ba-g-C3N4。
Step two: adding appropriate amount of SrCl2·6H2O and Na2WO4·2H2O is dissolved in ethylene glycol and then introduced into SrCl2·6H2Adding appropriate amount of trimethyl borate into O glycol solution, performing ultrasonic treatment for 10-15min, and slowly adding Na dropwise into the mixed solution in 50-60 deg.C water bath2WO4·2H2Continuously stirring the ethylene glycol solution of O for 20 to 30min after the dropwise addition is finished, and then adding the Ba-g-C prepared in the step one into the mixed solution3N4And a proper amount of BiCl3Ultrasonic treating for 5-8min, conveniently placing the mixed solution in a polytetrafluoroethylene-lined reaction kettle, preserving heat for 12-15h at the temperature of 180-200 ℃, cooling to room temperature, filtering the prepared sample, alternately washing the sample for 3 times by using absolute ethyl alcohol and deionized water, and freeze-drying the sample in a vacuum freeze dryer to obtain the Bi-B doped SrWO4/Ba-g-C3N4A composite nitrogen fixation photocatalyst.
The addition amount of the melamine in the step one is 4-6 g; the mass ratio of melamine to thiourea is 4.5:1-7:1, Ba (OH)2And thiourea in a ratio of 1:1.5 to 1:2.
SrCl in the second step2·6H2O and Ba-g-C3N4The mass ratio of the powder is 1:2.17-1: 2.8; SrCl2·6H2O and Na2WO4·2H2The mass ratio of O is 1:1-1:1.2, SrCl2·6H2The mass ratio of O to trimethyl borate is 1:4-1:6, BiCl3And SrCl2·6H2The mass ratio of O is 1:1.82-1: 2.46.
Preferably, in the first step, the temperature rise rate of the muffle furnace is 2 ℃/min, and the temperature drop rate is 3 ℃/min.
Preferably, SrCl in the second step2·6H2The concentration of O in ethylene glycol is 0.05g/ml, Na2WO4·2H2The concentration of O in glycol is 0.2 g/ml; na (Na)2WO4·2H2The dropping rate of the ethylene glycol solution of O was 1 ml/min.
The invention also provides another technical scheme, and the composite nitrogen fixation photocatalyst prepared by the method is shown in the specification, wherein SrWO4In Ba-g-C3N4The loading amount on the catalyst is 45-58 wt%; b in SrWO4In (1)The doping amount is 13.2-19.6 wt%, Bi is in SrWO4Wherein the doping amount is 21.4-28.9 wt%.
The invention also provides application of the photocatalyst prepared by the preparation method in nitrogen fixation.
Has the advantages that:
(1) in g-C3N4In the preparation process of (3), an alkali metal compound Ba (OH)2Mixing with raw materials at a certain ratio, and adding into the mixture at g-C3N4Defect doping sites are introduced into a bulk phase, so that the forbidden bandwidth is reduced, and the g-C prepared by alkali assistance3N4The energy band structure of the prepared material is optimized and adjusted, and the capture and conversion efficiency of solar energy is improved. While Ba (OH)2Ba can also be doped in g-C3N4In the method, the potential of the doped material is changed, which is beneficial to generating O2And H+。
(2)SrWO4Also has better photocatalysis capability, can replace partial oxygen atoms on one hand after B is doped, and on the other hand, the composite material is compounded with the hybrid orbit of the oxygen atoms, thereby effectively reducing SrWO4The forbidden band width of (c).
(3) Bi in SrWO4The doping increases the oxygen vacancy and improves SrWO4Nitrogen fixation ability of the compound. And SrWO4The matrix of (A) is g-C3N4The method effectively inhibits the recombination of photo-generated electrons and hole pairs and effectively improves the photocatalytic efficiency. In general, the material prepared by the invention can greatly improve the photocatalytic nitrogen fixation capability after being compounded.
Drawings
FIG. 1 is an X-ray diffraction pattern of example 1;
FIG. 2 is a graph showing the nitrogen fixation performance characteristics of example 1 and comparative examples 1 to 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The method comprises the following steps: 4g of melamine, 0.89g of thiourea and 1.34g of Ba (OH)2Uniformly mixing, placing into an aluminum oxide crucible, heating to 550 ℃ in a muffle furnace, calcining for 4-6h, cooling to room temperature, grinding the obtained block sample in a mortar for 30-40min to obtain powdery Ba-g-C3N4。
Step two: 1.1g of SrCl2·6H2O and 1.64g of Na2WO4·2H2O is dissolved in 22ml and 8.2ml of ethylene glycol respectively, and then is added to SrCl2·6H2Adding 2.58g trimethyl borate into O glycol solution, performing ultrasonic treatment for 10-15min, and adding Na dropwise into the mixed solution at a speed of 1ml/min in a water bath at 50-60 deg.C2WO4·2H2Adding ethylene glycol solution of O, stirring for 20-30min, and adding 2.4g of Ba-g-C into the mixed solution3N4And 0.6g of BiCl3Ultrasonic treating for 5-8min, conveniently placing the mixed solution in a polytetrafluoroethylene-lined reaction kettle, preserving heat for 12-15h at the temperature of 180-200 ℃, cooling to room temperature, filtering the prepared sample, alternately washing the sample for 3 times by using absolute ethyl alcohol and deionized water, and freeze-drying the sample in a vacuum freeze dryer to obtain the Bi-B doped SrWO4/Ba-g-C3N4A composite nitrogen fixation photocatalyst.
Example 2
The method comprises the following steps: 6g of melamine, 0.86g of thiourea and 0.97g of Ba (OH)2Uniformly mixing, placing into an aluminum oxide crucible, heating to 550 ℃ in a muffle furnace, calcining for 4-6h, cooling to room temperature, grinding the obtained block sample in a mortar for 30-40min to obtain powdery Ba-g-C3N4。
Step two: 1.29g of SrCl2·6H2O and 1.59g of Na2WO4·2H2O is dissolved in 25.8ml and 8ml of ethylene glycol respectively, and then added to SrCl2·6H2Adding 2.02g trimethyl borate into the glycol solution of O, and performing ultrafiltrationAfter the sound is radiated for 10-15min, Na is dripped into the mixed solution in a water bath at the temperature of 50-60 ℃ at the speed of 1ml/min2WO4·2H2Adding ethylene glycol solution of O, stirring for 20-30min, and adding Ba-g-C3.6 g into the mixed solution3N4And 0.53g of BiCl3Ultrasonic treating for 5-8min, conveniently placing the mixed solution in a polytetrafluoroethylene-lined reaction kettle, preserving heat for 12-15h at the temperature of 180-200 ℃, cooling to room temperature, filtering the prepared sample, alternately washing the sample for 3 times by using absolute ethyl alcohol and deionized water, and freeze-drying the sample in a vacuum freeze dryer to obtain the Bi-B doped SrWO4/Ba-g-C3N4A composite nitrogen fixation photocatalyst.
Example 3
The method comprises the following steps: 5g of melamine, 1.1g of thiourea and 1.57g of Ba (OH)2Uniformly mixing, placing into an aluminum oxide crucible, heating to 550 ℃ in a muffle furnace, calcining for 4-6h, cooling to room temperature, grinding the obtained block sample in a mortar for 30-40min to obtain powdery Ba-g-C3N4。
Step two: 1.36g of SrCl2·6H2O and 1.97g of Na2WO4·2H2O was dissolved in 27.2ml and 9.8ml of ethylene glycol, respectively, and then added to SrCl2·6H2Adding 2.95g trimethyl borate into O glycol solution, performing ultrasonic treatment for 10-15min, and adding Na dropwise into the mixed solution at a speed of 1ml/min in a water bath at 50-60 deg.C2WO4·2H2Adding ethylene glycol solution of O, stirring for 20-30min, and adding 3g of Ba-g-C into the mixed solution3N4And 0.72g of BiCl3Ultrasonic treating for 5-8min, conveniently placing the mixed solution in a polytetrafluoroethylene-lined reaction kettle, preserving heat for 12-15h at the temperature of 180-200 ℃, cooling to room temperature, filtering the prepared sample, alternately washing the sample for 3 times by using absolute ethyl alcohol and deionized water, and freeze-drying the sample in a vacuum freeze dryer to obtain the Bi-B doped SrWO4/Ba-g-C3N4A composite nitrogen fixation photocatalyst.
Example 4
The method comprises the following steps: 5.6g of melamine, 1.2g of thiourea and 1.8g of Ba: (OH)2Uniformly mixing, placing into an aluminum oxide crucible, heating to 550 ℃ in a muffle furnace, calcining for 4-6h, cooling to room temperature, grinding the obtained block sample in a mortar for 30-40min to obtain powdery Ba-g-C3N4。
Step two: 1.54g of SrCl2·6H2O and 2.23g of Na2WO4·2H2O was dissolved in 30.8ml and 11.2ml of ethylene glycol, respectively, and then added to SrCl2·6H2Adding 3.6g trimethyl borate into O glycol solution, performing ultrasonic treatment for 10-15min, and adding Na dropwise into the mixed solution at a speed of 1ml/min in a water bath at 50-60 deg.C2WO4·2H2Adding ethylene glycol solution of O, stirring for 20-30min, and adding Ba-g-C3.4 g into the mixed solution3N4And 0.81g of BiCl3Ultrasonic treating for 5-8min, conveniently placing the mixed solution in a polytetrafluoroethylene-lined reaction kettle, preserving heat for 12-15h at the temperature of 180-200 ℃, cooling to room temperature, filtering the prepared sample, alternately washing the sample for 3 times by using absolute ethyl alcohol and deionized water, and freeze-drying the sample in a vacuum freeze dryer to obtain the Bi-B doped SrWO4/Ba-g-C3N4A composite nitrogen fixation photocatalyst.
Comparative example 1
The method comprises the following steps: uniformly mixing 4g of melamine and 0.89g of thiourea, putting the mixture into an aluminum oxide crucible, heating the mixture to 550 ℃ in a muffle furnace, calcining the mixture for 4 to 6 hours, cooling the mixture to room temperature, and grinding the obtained block sample in a mortar for 30 to 40min to obtain powdery g-C3N4。
Step two: 1.1g of SrCl2·6H2O and 1.64g of Na2WO4·2H2Dissolving O in 22ml and 8.2ml ethylene glycol respectively, and adding Na dropwise into the mixed solution at a speed of 1ml/min in a water bath at 50-60 deg.C2WO4·2H2Adding ethylene glycol solution of O, stirring for 20-30min, and adding 2.4g of Ba-g-C into the mixed solution3N4And performing ultrasonic treatment for 5-8min, placing the mixed solution in a reaction kettle with polytetrafluoroethylene lining, keeping the temperature at 180-200 deg.C for 12-15h, and cooling to room temperatureThen the prepared sample is filtered and alternately washed for 3 times by absolute ethyl alcohol and deionized water, and then the sample is placed in a vacuum freeze dryer for freeze-drying to prepare SrWO4/g-C3N4The photocatalyst was used as comparative example 1.
Comparative example 2
5g of melamine, 1.1g of thiourea and 1.57g of Ba (OH)2Uniformly mixing, placing into an aluminum oxide crucible, heating to 550 ℃ in a muffle furnace, calcining for 4-6h, cooling to room temperature, grinding the obtained block sample in a mortar for 30-40min to obtain powdery Ba-g-C3N4The photocatalyst was used as comparative example 2.
Fig. 1 is an XRD pattern of example 1, and it can be found that the sample exhibits two distinct diffraction characteristic peaks at 2 θ of 13.0 ° and 27.4 °, respectively corresponding to g-C3N4The (100) crystal face and the (002) crystal face of the graphite phase carbon nitride show that the graphite phase carbon nitride is successfully prepared. Diffraction peaks at 18.1 °, 45.2 ° and 55.8 ° 2 θ are SrWO4The (101) crystal plane, (204) crystal plane, and the (312) crystal plane of (a). The XRD patterns confirmed the successful preparation of the composite catalyst.
FIG. 2 is a graph showing the nitrogen fixation performance of example 1 and comparative examples 1 to 2, measured according to the Nager reagent colorimetry, according to the following specific method: 0.05g of the catalyst prepared in example 1 and comparative examples 1 to 2 was placed in 100ml of deionized water under a full spectrum light simulated by a xenon lamp, and then nitrogen gas was continuously introduced into the water for 1 hour, and the yield of each sample was measured. From the figure, it can be seen that SrWO prepared in example 14/Ba-g-C3N4The nitrogen fixation performance of the photocatalyst is excellent and can reach 92 mu mol g at most-1·h-1Compared with SrWO of comparative examples 1-24/g-C3N4And Ba-g-C3N4The nitrogen fixation performance of the compound is far inferior to that of the compound in example 1.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.
Claims (7)
1. Bi-B doped SrWO4/Ba-g-C3N4The preparation method of the composite nitrogen-fixing photocatalyst is characterized by comprising the following steps:
the method comprises the following steps: mixing certain amount of melamine, thiourea and Ba (OH)2Uniformly mixing, placing into an aluminum oxide crucible, heating to 550 ℃ in a muffle furnace, calcining for 4-6h, cooling to room temperature, grinding the obtained block sample in a mortar for 30-40min to obtain powdery Ba-g-C3N4；
Step two: adding appropriate amount of SrCl2·6H2O and Na2WO4·2H2O is dissolved in ethylene glycol and then added to SrCl2·6H2Adding appropriate amount of trimethyl borate into O glycol solution, performing ultrasonic treatment for 10-15min, and slowly adding Na dropwise into the mixed solution in 50-60 deg.C water bath2WO4·2H2Continuously stirring the ethylene glycol solution of O for 20 to 30min after the dropwise addition is finished, and then adding the Ba-g-C prepared in the step one into the mixed solution3N4And a proper amount of BiCl3Ultrasonic treating for 5-8min, conveniently placing the mixed solution in a polytetrafluoroethylene-lined reaction kettle, preserving heat for 12-15h at the temperature of 180-200 ℃, cooling to room temperature, filtering the prepared sample, alternately washing the sample for 3 times by using absolute ethyl alcohol and deionized water, and freeze-drying the sample in a vacuum freeze dryer to obtain the Bi-B doped SrWO4/Ba-g-C3N4A composite nitrogen fixation photocatalyst.
2. The Bi-B doped SrWO of claim 14/Ba-g-C3N4The preparation method of the composite nitrogen-fixing photocatalyst is characterized in that in the first step, the mass ratio of melamine to thiourea is 4.5:1-7:1, and Ba (OH)2And thiourea in a ratio of 1:1.5 to 1: 2; SrCl in the second step2·6H2O and Ba-g-C3N4The mass ratio of the powder is 1:2.17-1: 2.8; SrCl2·6H2O and Na2WO4·2H2Of OThe ratio of the amount of the substance is 1:1-1:1.2, SrCl2·6H2The mass ratio of O to trimethyl borate is 1:4-1:6, BiCl3And SrCl2·6H2The mass ratio of O is 1:1.82-1: 2.46.
3. The Bi-B doped SrWO of claim 14/Ba-g-C3N4The preparation method of the composite nitrogen-fixing photocatalyst is characterized in that the addition amount of melamine in the step one is 4-6 g.
4. The Bi-B doped SrWO of claim 14/Ba-g-C3N4The preparation method of the composite nitrogen-fixing photocatalyst is characterized in that in the first step, the temperature rise rate of the muffle furnace is 2 ℃/min, and the temperature drop rate is 3 ℃/min.
5. The Bi-B doped SrWO of claim 14/Ba-g-C3N4The preparation method of the composite nitrogen-fixing photocatalyst is characterized in that SrCl is adopted in the second step2·6H2The concentration of O in ethylene glycol is 0.05g/ml, Na2WO4·2H2The concentration of O in glycol is 0.2 g/ml; na (Na)2WO4·2H2The dropping rate of the ethylene glycol solution of O was 1 ml/min.
6. A Bi-B doped SrWO according to any of claims 1 to 54/Ba-g-C3N4The photocatalyst prepared by the preparation method of the composite nitrogen-fixing photocatalyst is characterized in that SrWO4In Ba-g-C3N4The loading amount on the catalyst is 45-58 wt%; b in SrWO4Wherein the doping amount is 13.2-19.6 wt%, Bi is in SrWO4Wherein the doping amount is 21.4-28.9 wt%.
7. Bi-B doped SrWO4/Ba-g-C3N4The photocatalyst prepared by the preparation method of the composite nitrogen fixation photocatalyst is applied to nitrogen fixation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011258704.0A CN112221529A (en) | 2020-11-12 | 2020-11-12 | Bi-B doped SrWO4/Ba-g-C3N4Composite nitrogen-fixing photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011258704.0A CN112221529A (en) | 2020-11-12 | 2020-11-12 | Bi-B doped SrWO4/Ba-g-C3N4Composite nitrogen-fixing photocatalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112221529A true CN112221529A (en) | 2021-01-15 |
Family
ID=74123824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011258704.0A Withdrawn CN112221529A (en) | 2020-11-12 | 2020-11-12 | Bi-B doped SrWO4/Ba-g-C3N4Composite nitrogen-fixing photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112221529A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198514A (en) * | 2021-05-19 | 2021-08-03 | 南京信息工程大学 | Bi modified g-C3N4Photocatalyst material and nitrogen fixation performance thereof |
| CN113333010A (en) * | 2021-05-29 | 2021-09-03 | 安徽大学 | Efficient photocatalyst nitrogen-doped SrMoO4Preparation method of (1) |
-
2020
- 2020-11-12 CN CN202011258704.0A patent/CN112221529A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198514A (en) * | 2021-05-19 | 2021-08-03 | 南京信息工程大学 | Bi modified g-C3N4Photocatalyst material and nitrogen fixation performance thereof |
| CN113333010A (en) * | 2021-05-29 | 2021-09-03 | 安徽大学 | Efficient photocatalyst nitrogen-doped SrMoO4Preparation method of (1) |
| CN113333010B (en) * | 2021-05-29 | 2022-02-18 | 安徽大学 | Photocatalyst nitrogen-doped SrMoO4Preparation method of (1) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112169819B (en) | g-C 3 N 4 /(101)-(001)-TiO 2 Preparation method and application of composite material | |
| CN107376971B (en) | Synthetic method of graphite-like carbon nitride/molybdenum disulfide nano composite material | |
| CN112221529A (en) | Bi-B doped SrWO4/Ba-g-C3N4Composite nitrogen-fixing photocatalyst and preparation method thereof | |
| CN113522336B (en) | Aluminum monatomic-loaded nitrogen-doped carbon material, and preparation method and application thereof | |
| CN113457711B (en) | Graphite-phase carbon nitride-loaded magnesium monoatomic composite material, preparation method thereof and method for preparing hydrogen peroxide through photocatalysis | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN112295576A (en) | Cs3Bi2Br9/TiO2Perovskite heterojunction, preparation method thereof and application of perovskite heterojunction in photocatalytic toluene oxidation | |
| CN111330615A (en) | Nano bismuth oxychloride/carbon nitride composite material and preparation method and application thereof | |
| CN115178288B (en) | Ni-Ni 2 P/g-C 3 N 4 Photocatalyst and preparation method thereof | |
| CN111790431A (en) | With Al2O3Modified g-C3N4Preparation method of photocatalytic material | |
| CN114289036B (en) | Sulfide photocatalyst containing rare earth elements and preparation method and application thereof | |
| CN111943152B (en) | Photocatalyst and method for synthesizing ammonia by photocatalysis | |
| CN111151275A (en) | MoS2/Mo2C Complex, MoS2/Mo2C/CdS composite material and preparation method and application thereof | |
| CN111151238B (en) | Bismuth vanadate heterojunction BiVO4/Bi25VO40Material, preparation method and application thereof | |
| CN104549274A (en) | Method for preparing composite nanometer titanium dioxide photocatalytic material | |
| CN111647167A (en) | Novel metal organic framework material Zn-MOF, and synthesis method and application thereof | |
| CN112295577B (en) | Cs3Bi2Br9/TiO2Application of perovskite heterojunction in photocatalytic degradation of MBT (molybdenum disulfide) | |
| CN115069290A (en) | Nitrogen-defect-containing porous carbon nitride-loaded monoatomic copper catalyst, preparation method thereof and application thereof in light nitrogen fixation | |
| CN112371120B (en) | High-dispersion platinum modified metal ion doped semiconductor photocatalyst, preparation method and application thereof | |
| CN114950295A (en) | Preparation of Cu by gas-solid reaction 3 Method of P | |
| CN110237836B (en) | Molybdenum modified zirconium dioxide material and preparation method and application thereof | |
| CN114669289A (en) | Synthesis method of carbon quantum dot/ZnO composite photocatalyst | |
| CN110560140A (en) | Weak luminescence g-C3N4Photocatalyst and preparation method and application thereof | |
| CN112547107A (en) | alpha-Fe2O3/Ni@2D g-C3N4Process for preparing catalyst | |
| CN117427643B (en) | Photocatalytic material based on graphite-phase carbon nitride and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210115 |
|
| WW01 | Invention patent application withdrawn after publication |