CN111644191A - Nano WO3-g-C3N4-rGO heterojunction supported foam nickel photocatalytic material and preparation method thereof - Google Patents
Nano WO3-g-C3N4-rGO heterojunction supported foam nickel photocatalytic material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 74
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000006260 foam Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 38
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 109
- 238000010438 heat treatment Methods 0.000 claims description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- 239000012153 distilled water Substances 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 37
- 239000012265 solid product Substances 0.000 claims description 36
- 238000009210 therapy by ultrasound Methods 0.000 claims description 34
- 238000001354 calcination Methods 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 26
- 238000004321 preservation Methods 0.000 claims description 22
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000008247 solid mixture Substances 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 8
- 238000005215 recombination Methods 0.000 abstract description 8
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000000862 absorption spectrum Methods 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 41
- -1 polytetrafluoroethylene Polymers 0.000 description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003028 elevating effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
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- 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
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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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/10—Photocatalysts
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Abstract
The invention relates to the technical field of photocatalytic materials, and discloses a nano WO3‑g‑C3N4-the rGO heterojunction supported foam nickel photocatalytic material comprises the following formula raw materials and components: foamed nickel, nano boron-doped graphene carbon nitride, graphene oxide, sodium tungstate and Fe (NO)3)3. The nanometer WO3‑g‑C3N4The nano boron-doped graphene carbon nitride has a rich mesoporous structure and a large specific surface area, more photochemical active sites are exposed, and g-C is enhanced3N4The conductivity of the boron-doped graphene carbon nitride promotes the transmission of photo-generated electrons, the boron-doped graphene carbon nitride and the graphene oxide form a Schottky junction, the migration rate of the photo-generated electrons is improved, and the WO is doped by Fe3The ultraviolet-visible absorption spectrum generates red shift, the utilization rate of the photocatalyst to the light energy is widened, and WO3And g-C3N4Form Z-type heterojunction, and reduce g-C3N4And WO3Respectively generates the recombination of photo-generated electrons and holes, so that the photocatalytic material has excellent photocatalytic degradation activity.
Description
Technical Field
The present invention relates to a photocatalytic material technologyThe field is nano WO3-g-C3N4-rGO heterojunction supported foam nickel photocatalytic material and preparation method thereof.
Background
The water pollution is a phenomenon that the use value of water is reduced or lost due to harmful chemical substances to pollute the environment, China is a country with serious water shortage, the water occupancy of human lives is one fourth of the average water quantity in the world, 80% of China drinks shallow well and river water, wherein the water pollution serious bacteria exceed 75% of the sanitary standard, the water resource quality of China is continuously reduced in recent years, the water environment is continuously deteriorated, water shortage and accidents caused by pollution are continuously generated, not only is the factory stopped, the agricultural production is reduced or even totally recovered, but also the adverse social influence and the larger economic loss are caused, the sustainable development of the society is seriously threatened, the human survival is threatened, and the pollutants are mainly from domestic sewage, industrial wastewater and agricultural sewage which are discharged without treatment, and comprise acid, alkali, salt and heavy metal inorganic pollutants; organic pollutants such as halide, aromatic compound and organic dye, wherein the organic pollutants have high toxicity, can kill aquatic organisms to influence drinking water sources, can consume dissolved oxygen in water when organic matters in the sewage are decomposed by microorganisms to influence the lives of the aquatic organisms, and can be subjected to anaerobic decomposition after the dissolved oxygen in the water is exhausted to generate toxic gases such as hydrogen sulfide and mercaptan, so that the water quality is further deteriorated.
At present, the sewage treatment mainly comprises physical methods such as an adsorption method, a flocculation method and the like; biological methods such as microbial degradation; chemical methods such as oxidation reaction method, neutralization precipitation, etc.; the photocatalytic degradation is a new type of high-efficiency sewage treatment method, and is characterized by that it utilizes the light radiation on the semiconductor material or photocatalyst to produce free radical with strong activity in the reaction system, and utilizes the dispersion addition, substitution and electron transfer reactions between free radical and organic pollutant to degrade the pollutant into non-toxic or low-toxic small molecules3And graphite phase carbon nitrideg-C3N4Has good chemical stability and photocatalytic activity, has great application value in the aspects of photocatalytic hydrogen production, photocatalytic degradation and the like, but WO3The ultraviolet visible light absorption band of (1) is narrow, has photochemical activity only under ultraviolet light, has low photochemical responsiveness and utilization rate to visible light, and semiconductor WO3And g-C3N4The photo-generated electrons and holes generated under the light radiation are easy to recombine, and the performance of photodegradation of organic pollutants is greatly reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a nanometer WO3-g-C3N4A photocatalytic material of-rGO heterojunction supported foam nickel and a preparation method thereof, but WO is solved3The ultraviolet visible light has narrow absorption band and low photochemical responsiveness and utilization rate to the visible light, and simultaneously solves the problems of the semiconductor WO3And g-C3N4The generation of photo-generated electrons and holes under light irradiation is a problem of easy recombination.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: nano WO3-g-C3N4The photocatalytic material of the rGO heterojunction supported foam nickel comprises the following formula raw materials in parts by weight: 12-18 parts of foamed nickel, 21-37 parts of nano boron-doped graphene carbon nitride, 2-4 parts of graphene oxide, 48-55 parts of sodium tungstate and 1-2 parts of Fe (NO)3)3。
Preferably, the graphene oxide has a sheet diameter of 50-200nm and a thickness of 0.8-1.2 nm.
Preferably, the preparation method of the nano boron-doped graphene carbon nitride comprises the following steps:
(1) adding distilled water solvent, melamine and boric acid into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 50-60 deg.C for 20-40min, placing the reaction bottle in a constant temperature water bath, heating to 70-80 deg.C, stirring at uniform speed until distilled water is completely evaporated, placing the solid product in a planetary ball mill, the revolution speed is 580-620rpm, the ball milling is carried out for 6-12h, the solid mixture is placed in an atmosphere resistance furnace, and introducing nitrogen, heating to 520-.
Preferably, the melamine and boric acid species are present in a ratio of 35 to 45: 1.
Preferably, the ultrasonic treatment appearance includes the host computer, fixedly connected with principal base on the interior diapire of host computer, the inside movable mounting of principal base has the elevating platform, the outside of principal base is rotated and is connected with the clamping jaw, the inside of principal base and the top swing joint who is located the clamping jaw connecting axle have the pivot, slide and ratchet are installed in the outside of pivot, the top activity of principal base is pegged graft and is had the push pedal that corresponds with the slide, the top and the bottom of push pedal all are provided with the slope, install the driving lever that corresponds with the push pedal on the clamping jaw, the outside of elevating platform is provided with the rack that corresponds with the ratchet, install ultrasonic generrator on the interior roof of host computer, ultrasonic probe is installed to ultrasonic generrator's bottom, the.
Preferably, the nano WO3-g-C3N4The preparation method of the photocatalytic material with foam nickel loaded on the rGO heterojunction comprises the following steps:
(1) adding distilled water solvent, 12-18 parts of foamed nickel as a carrier, 21-37 parts of boron-doped graphene carbon nitride and 2-4 parts of graphene oxide into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 50-70 ℃ for 1-2h, wherein the ultrasonic frequency is 30-40KHz, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 160-180 ℃, reacting for 3-5h, performing reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare g-C3N4-rGO supported foamed nickel composite.
(2) Adding distilled water and g-C into a reaction bottle3N4-rGO supported foamed nickel composite material, 48-55 parts of sodium tungstate, 1-2 parts of Fe (NO)3)3Will bePlacing the reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 50-60 ℃ for 30-50min at the ultrasonic frequency of 30-40KHz, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1-2, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 190 ℃ for reaction for 15-20h, decompressing and concentrating the solution to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in an atmosphere resistance furnace at the heating rate of 2-4 ℃/min, heating to 420 ℃ for heat preservation and calcining for 2-3h, wherein the calcined product is the nano WO3-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the nanometer WO3-g-C3N4the-rGO heterojunction supported foam nickel photocatalytic material is prepared by taking boric acid as a boron source and preparing a thermal oxidation method, wherein the boron-doped graphene carbon nitride prepared by the method has a good nano structure and morphology, and g-C is doped under the boron doping effect3N4Rich mesoporous structure and developed porosity are formed, and g-C is increased3N4Specific surface area, exposing more photochemically active sites, and boron doping enhances g-C3N4The conductivity of the material promotes the transmission and migration of photo-generated electrons, reduces the recombination rate of the photo-generated electrons and holes,
the nanometer WO3-g-C3N4The g-C is prepared by a hydrothermal synthesis method by taking foamed nickel as a substrate of a photocatalyst3N4-rGO loading g-C3N4-rGO composite material, let g-C3N4And the rGO is uniformly dispersed and loaded on the surface of the foamed nickel, so that the phenomenon that photocatalytic active sites are reduced due to the agglomeration and aggregation of the boron-doped graphene carbon nitride and the graphene oxide is effectively reduced, the boron-doped graphene carbon nitride and the graphene oxide form a Schottky junction, and the graphene oxide is a transmission channel through which photoproduction electrons pass, so that the photo-induced electrons are improvedThe mobility rate of the generated electrons reduces the recombination rate of the photo-generated electrons and holes.
The nanometer WO3-g-C3N4Preparing a nano Fe-doped WO (tungsten oxide) photocatalytic material by an in-situ growth method through an rGO heterojunction supported foam nickel3Loaded to g-C3N4Over a large specific surface area, Fe doping makes WO3The ultraviolet-visible absorption spectrum of (A) is red-shifted to cause WO3Has good photochemical activity and photoresponse in a visible light range, widens the utilization rate of photocatalyst to light energy, and has good performance3And g-C3N4Forming a Z-type heterojunction with a matched band structure, g-C3N4Electron transition from conduction band to WO3In the valence band of (A) with WO3Valence band generating hole recombination, and g-C3N4Valence band generated holes and WO3The photo-generated electrons generated by the conduction band keep the position unchanged, and the g-C is effectively reduced3N4And WO3The photo-generated electrons and the holes are respectively compounded to generate a large amount of photo-generated electrons and holes, the photo-generated electrons and the holes react with water molecules and oxygen to generate hydroxyl free radicals and superoxide free radicals, and organic pollutants such as methyl orange, phenol and the like are subjected to oxidation reaction and degraded into non-toxic or low-toxic micromolecules.
Drawings
FIG. 1 is a schematic front view of the present invention;
FIG. 2 is a schematic view of the jaw installation of the present invention;
FIG. 3 is a perspective view of the connection structure of the clamping jaw and the rotating shaft;
FIG. 4 is a schematic view of the connection structure of the slide carriage and the push plate according to the present invention.
In the figure: 1. a host; 2. a main base; 3. a lifting platform; 4. a clamping jaw; 5. a rotating shaft; 6. a slide base; 7. pushing the plate; 8. a deflector rod; 9. a ratchet wheel; 10. a rack; 11. an ultrasonic generator; 12. an ultrasonic probe; 13. and (4) a bottle body.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: nano WO3-g-C3N4The photocatalytic material of the rGO heterojunction supported foam nickel comprises the following formula raw materials in parts by weight: 12-18 parts of foamed nickel, 21-37 parts of nano boron-doped graphene carbon nitride, 2-4 parts of graphene oxide, 48-55 parts of sodium tungstate and 1-2 parts of Fe (NO)3)3The graphene oxide has a sheet diameter of 50-200nm and a thickness of 0.8-1.2 nm.
The preparation method of the nano boron-doped graphene carbon nitride comprises the following steps:
(1) adding distilled water solvent, melamine and boric acid into a reaction bottle, wherein the mass ratio of the substances is 35-45:1, placing the reaction bottle into an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host, a main seat is fixedly connected on the inner bottom wall of the host, a lifting platform is movably arranged in the main seat, a clamping jaw is rotatably connected on the outer side of the main seat, a rotating shaft is movably connected in the main seat and positioned above a clamping jaw connecting shaft, a sliding seat and a ratchet wheel are arranged on the outer side of the rotating shaft, a push plate corresponding to the sliding seat is movably inserted in the top of the main seat, slopes are arranged at the top and the bottom of the push plate, a deflector rod corresponding to the push plate is arranged on the clamping jaw, a rack corresponding to the ratchet wheel is arranged on the outer side of the lifting platform, an ultrasonic generator is arranged on the inner top wall of the host, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a bottle body is arranged on, placing the reaction bottle in a constant-temperature water bath kettle, heating to 70-80 ℃, stirring at a constant speed until distilled water is completely evaporated, placing the solid product in a planetary ball mill, ball-milling at revolution speed of 580-plus-one 620rpm for 6-12h, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen at a heating rate of 3-5 ℃/min, heating to 520-plus-one 560 ℃, performing heat preservation and calcination for 2-3h, introducing ammonia into the atmosphere resistance furnace, heating to 600-plus-one 620 ℃, performing heat preservation and calcination for 1-2h, and rapidly cooling the calcined product to obtain the nano boron-doped graphene carbon nitride.
Nano WO3-g-C3N4The preparation method of the photocatalytic material with foam nickel loaded on the rGO heterojunction comprises the following steps:
(1) adding distilled water solvent, 12-18 parts of foam nickel as carrier and 21-37 parts of boron doping into a reaction bottlePlacing a reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2h at 50-70 ℃ with the ultrasonic frequency of 30-40KHz, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 160-180 ℃, reacting for 3-5h, performing reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare g-C3N4-rGO supported foamed nickel composite.
(2) Adding distilled water and g-C into a reaction bottle3N4-rGO supported foamed nickel composite material, 48-55 parts of sodium tungstate, 1-2 parts of Fe (NO)3)3Placing a reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 50-60 ℃ for 30-50min at the ultrasonic frequency of 30-40KHz, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1-2, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 170-190 ℃, reacting for 15-20h, decompressing and concentrating the solution to remove the solvent, washing the solid product with distilled water and fully drying, placing the solid product in an atmosphere resistance furnace at the heating rate of 2-4 ℃/min, heating to 390-420 ℃, performing heat preservation and calcination for 2-3h, wherein the calcination product is the nano WO3-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material.
Example 1
(1) Preparing a nano boron-doped graphene carbon nitride component 1: adding distilled water solvent, melamine and boric acid into a reaction bottle, wherein the mass ratio of the substances is 35:1, placing the reaction bottle into an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host, a main seat is fixedly connected on the inner bottom wall of the host, a lifting platform is movably arranged in the main seat, a clamping jaw is rotatably connected on the outer side of the main seat, a rotating shaft is movably connected in the main seat and positioned above a clamping jaw connecting shaft, a sliding seat and a ratchet wheel are arranged on the outer side of the rotating shaft, a push plate corresponding to the sliding seat is movably inserted in the top of the main seat, slopes are arranged at the top and the bottom of the push plate, a deflector rod corresponding to the push plate is arranged on the clamping jaw, a rack corresponding to the ratchet wheel is arranged on the outer side of the lifting platform, an ultrasonic generator is arranged on the inner top wall of the host, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed until distilled water is completely evaporated, placing the solid product in a planetary ball mill, carrying out ball milling at the revolution speed of 620rpm for 12h, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the heating rate of 5 ℃/min to 560 ℃, carrying out heat preservation and calcination for 3h, introducing ammonia into the atmosphere resistance furnace, heating to 620 ℃, carrying out heat preservation and calcination for 2h, and rapidly cooling the calcined product to obtain the nano boron-doped graphene carbon nitride component 1.
(2) Preparation of g-C3N4-rGO supported foamed nickel composite 1: adding distilled water solvent, 12 parts of foamed nickel as a carrier, 37 parts of boron-doped graphene carbon nitride component 1 and 2 parts of graphene oxide into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 70 ℃ for 2 hours with the ultrasonic frequency of 40KHz, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle into a reaction kettle heating box, heating to 180 ℃, reacting for 5 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, and fully drying to prepare g-C3N4-rGO supported foamed nickel composite 1.
(3) Preparation of Nano WO3-g-C3N4-rmo heterojunction supported nickel foam photocatalytic material 1: adding distilled water and g-C into a reaction bottle3N4rGO-loaded foamed nickel composite material 1, 48 parts of sodium tungstate and 1 part of Fe (NO)3)3Placing a reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 60 ℃ for 50min at the ultrasonic frequency of 40KHz, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 190 ℃, reacting for 20h, decompressing and concentrating the solution to remove the solvent, washing a solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, heating at the heating rate of 4 ℃/min, heating to 420 ℃, preserving heat and calcining for 2h, wherein the calcined product is the nano WO3-g-C3N4-rGO heterojunction supported nickel foamThe photocatalytic material 1 of (1).
Example 2
(1) Preparing a nano boron-doped graphene carbon nitride component 2: adding distilled water solvent, melamine and boric acid into a reaction bottle, wherein the mass ratio of the substances is 35:1, placing the reaction bottle into an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host, a main seat is fixedly connected on the inner bottom wall of the host, a lifting platform is movably arranged in the main seat, a clamping jaw is rotatably connected on the outer side of the main seat, a rotating shaft is movably connected in the main seat and positioned above a clamping jaw connecting shaft, a sliding seat and a ratchet wheel are arranged on the outer side of the rotating shaft, a push plate corresponding to the sliding seat is movably inserted in the top of the main seat, slopes are arranged at the top and the bottom of the push plate, a deflector rod corresponding to the push plate is arranged on the clamping jaw, a rack corresponding to the ratchet wheel is arranged on the outer side of the lifting platform, an ultrasonic generator is arranged on the inner top wall of the host, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed until distilled water is completely evaporated, placing the solid product in a planetary ball mill, carrying out ball milling at a revolution speed of 580 rpm for 12h, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at a heating rate of 5 ℃/min to 520 ℃, carrying out heat preservation and calcination for 3h, introducing ammonia into the atmosphere resistance furnace, heating to 620 ℃, carrying out heat preservation and calcination for 1 h, and rapidly cooling the calcined product to obtain the nano boron-doped graphene carbon nitride component 2.
(2) Preparation of g-C3N4-rGO supported foamed nickel composite 2: adding distilled water solvent, 13 parts of foamed nickel as a carrier, 33.5 parts of boron-doped graphene carbon nitride component 2 and 2.5 parts of graphene oxide into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 70 ℃ for 2 hours with the ultrasonic frequency of 30 KHz, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle into a reaction kettle heating box, heating to 180 ℃, reacting for 3 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water, fully drying, and preparing to obtain g-C3N4-rGO supported foamed nickel composite 2.
(3) Preparation of Nano WO3-g-C3N4-a photocatalytic material with foam nickel supported on rGO heterojunction 2: adding distilled water and g-C into a reaction bottle3N4-rGO supported nickel foam composite 2, 49.8 parts sodium tungstate, 1.2 parts Fe (NO)3)3Placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 60 ℃ for 50min at the ultrasonic frequency of 30 KHz, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1, stirring uniformly, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 190 ℃, reacting for 20h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, heating at the heating rate of 4 ℃/min, heating to 390 ℃, carrying out heat preservation and calcination for 3h, wherein the calcination product is the nano WO3-g-C3N4-a photocatalytic material 2 of nickel foam supported by rGO heterojunction.
Example 3
(1) Preparing a nano boron-doped graphene carbon nitride component 3: adding distilled water solvent, melamine and boric acid into a reaction bottle, wherein the mass ratio of the substances is 40:1, placing the reaction bottle into an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host, a main seat is fixedly connected on the inner bottom wall of the host, a lifting platform is movably arranged in the main seat, a clamping jaw is rotatably connected on the outer side of the main seat, a rotating shaft is movably connected in the main seat and positioned above a clamping jaw connecting shaft, a sliding seat and a ratchet wheel are arranged on the outer side of the rotating shaft, a push plate corresponding to the sliding seat is movably inserted in the top of the main seat, slopes are arranged at the top and the bottom of the push plate, a deflector rod corresponding to the push plate is arranged on the clamping jaw, a rack corresponding to the ratchet wheel is arranged on the outer side of the lifting platform, an ultrasonic generator is arranged on the inner top wall of the host, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 75 ℃, stirring at a constant speed until distilled water is completely evaporated, placing the solid product in a planetary ball mill, carrying out ball milling at the revolution speed of 600 rpm for 9 h, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the heating rate of 4 ℃/min to 540 ℃, carrying out heat preservation and calcination for 2.5 h, introducing ammonia into the atmosphere resistance furnace, heating to 610 ℃, carrying out heat preservation and calcination for 1.5 h, and rapidly cooling the calcined product to obtain the nano boron-doped graphene carbon nitride component 3.
(2) Preparation of g-C3N4-rGO supported foamed nickel composite 3: adding distilled water solvent, 15 parts of foamed nickel as a carrier, 30 parts of boron-doped graphene carbon nitride component 3 and 3 parts of graphene oxide into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 60 ℃ for 1.5 h, wherein the ultrasonic frequency is 35 KHz, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle into a reaction kettle heating box, heating to 170 ℃, reacting for 4 h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, fully drying, and preparing to obtain g-C3N4-rGO supported foamed nickel composite 3.
(3) Preparation of Nano WO3-g-C3N4-the photocatalytic material of nickel foam supported by rGO heterojunction 3: adding distilled water and g-C into a reaction bottle3N4-rGO supported nickel foam composite 3, 50.5 parts sodium tungstate, 1.5 parts Fe (NO)3)3Placing a reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 55 ℃ for 40min at the ultrasonic frequency of 35 KHz, dropwise adding hydrochloric acid to adjust the pH value of the solution to 2, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 180 ℃, reacting for 18 h, decompressing and concentrating the solution to remove the solvent, washing a solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace at the heating rate of 3 ℃/min, heating to 410 ℃, preserving heat and calcining for 3h, wherein the calcined product is the nano WO3-g-C3N4-a photocatalytic material 3 of nickel foam supported by rGO heterojunction.
Example 4
(1) Preparing a nano boron-doped graphene carbon nitride component 4: adding distilled water solvent, melamine and boric acid into a reaction bottle, wherein the mass ratio of the substances is 45:1, placing the reaction bottle into an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host, a main seat is fixedly connected on the inner bottom wall of the host, a lifting platform is movably arranged in the main seat, a clamping jaw is rotatably connected on the outer side of the main seat, a rotating shaft is movably connected in the main seat and positioned above a clamping jaw connecting shaft, a sliding seat and a ratchet wheel are arranged on the outer side of the rotating shaft, a push plate corresponding to the sliding seat is movably inserted in the top of the main seat, slopes are arranged at the top and the bottom of the push plate, a deflector rod corresponding to the push plate is arranged on the clamping jaw, a rack corresponding to the ratchet wheel is arranged on the outer side of the lifting platform, an ultrasonic generator is arranged on the inner top wall of the host, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed until distilled water is completely evaporated, placing the solid product in a planetary ball mill, carrying out ball milling at the revolution speed of 620rpm for 12h, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the heating rate of 5 ℃/min to 560 ℃, carrying out heat preservation and calcination for 3h, introducing ammonia into the atmosphere resistance furnace, heating to 620 ℃, carrying out heat preservation and calcination for 2h, and rapidly cooling the calcined product to obtain the nano boron-doped graphene carbon nitride component 4.
(2) Preparation of g-C3N4-rGO supported foamed nickel composite 4: adding distilled water solvent, 18 parts of foamed nickel as a carrier, 21 parts of boron-doped graphene carbon nitride component 4 and 4 parts of graphene oxide into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 70 ℃ for 2 hours with the ultrasonic frequency of 40KHz, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle into a reaction kettle heating box, heating to 180 ℃, reacting for 5 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the g-C3N4-rGO supported foamed nickel composite 4.
(3) Preparation of Nano WO3-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material 4: adding distilled water and g-C into a reaction bottle3N44 parts of rGO supported foamed nickel composite material, 55 parts of sodium tungstate and 2 parts of Fe (NO)3)3Placing the reaction bottle in an ultrasonic treatment instrument, and performing ultrasonic dispersion treatment at 60 deg.C for 50minDropwise adding hydrochloric acid to adjust the pH value of the solution to 2 at the ultrasonic frequency of 40KHz, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 190 ℃, reacting for 20 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, heating to 420 ℃, carrying out heat preservation and calcination for 3 hours at the heating rate of 4 ℃/min, wherein the calcination product is nano WO3-g-C3N4-a photocatalytic material 4 of nickel foam supported by rGO heterojunction.
Comparative example 1
(1) Preparing a nano boron-doped graphene carbon nitride component 1: adding distilled water solvent, melamine and boric acid into a reaction bottle, wherein the mass ratio of the substances is 45:1, placing the reaction bottle into an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host, a main seat is fixedly connected on the inner bottom wall of the host, a lifting platform is movably arranged in the main seat, a clamping jaw is rotatably connected on the outer side of the main seat, a rotating shaft is movably connected in the main seat and positioned above a clamping jaw connecting shaft, a sliding seat and a ratchet wheel are arranged on the outer side of the rotating shaft, a push plate corresponding to the sliding seat is movably inserted in the top of the main seat, slopes are arranged at the top and the bottom of the push plate, a deflector rod corresponding to the push plate is arranged on the clamping jaw, a rack corresponding to the ratchet wheel is arranged on the outer side of the lifting platform, an ultrasonic generator is arranged on the inner top wall of the host, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed until distilled water is completely evaporated, placing the solid product in a planetary ball mill, carrying out ball milling at a revolution speed of 580 rpm for 12h, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at a heating rate of 5 ℃/min to 560 ℃, carrying out heat preservation and calcination for 2h, introducing ammonia into the atmosphere resistance furnace, heating to 620 ℃, carrying out heat preservation and calcination for 1 h, and rapidly cooling the calcined product to obtain the nano boron-doped graphene carbon nitride component 1.
(2) Preparation of g-C3N4-rGO supported foamed nickel composite 1: distilled water solvent and 11 parts of foamed nickel are added into a reaction bottleThe preparation method comprises the steps of taking a carrier, 41 parts of boron-doped graphene carbon nitride component 1 and 1.5 parts of graphene oxide, placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 70 ℃ for 2 hours at the ultrasonic frequency of 40KHz, transferring a solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 180 ℃, reacting for 5 hours, carrying out reduced pressure concentration on the solution to remove a solvent, washing a solid product with distilled water, fully drying, and preparing to obtain g-C3N4-rGO supported foamed nickel composite 1.
(3) Preparation of Nano WO3-g-C3N4-rmo heterojunction supported nickel foam photocatalytic material 1: adding distilled water and g-C into a reaction bottle3N4rGO supported nickel foam composite material 1, 46 parts of sodium tungstate, 0.5 part of Fe (NO)3)3Placing a reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 60 ℃ for 50min at the ultrasonic frequency of 40KHz, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1, uniformly stirring, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 190 ℃, reacting for 20h, decompressing and concentrating the solution to remove the solvent, washing a solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, heating at the heating rate of 4 ℃/min, heating to 420 ℃, preserving heat and calcining for 3h, wherein the calcined product is the nano WO3-g-C3N4-a photocatalytic material 1 with a nickel foam supported by rGO heterojunction.
Comparative example 2
(1) Preparing a nano boron-doped graphene carbon nitride component 2: adding distilled water solvent, melamine and boric acid into a reaction bottle, wherein the mass ratio of the substances is 45:1, placing the reaction bottle into an ultrasonic treatment instrument, the ultrasonic treatment instrument comprises a host, a main seat is fixedly connected on the inner bottom wall of the host, a lifting platform is movably arranged in the main seat, a clamping jaw is rotatably connected on the outer side of the main seat, a rotating shaft is movably connected in the main seat and positioned above a clamping jaw connecting shaft, a sliding seat and a ratchet wheel are arranged on the outer side of the rotating shaft, a push plate corresponding to the sliding seat is movably inserted in the top of the main seat, slopes are arranged at the top and the bottom of the push plate, a deflector rod corresponding to the push plate is arranged on the clamping jaw, a rack corresponding to the ratchet wheel is arranged on the outer side of the lifting platform, an ultrasonic generator is arranged on the inner top wall of the host, an ultrasonic probe is arranged at the bottom of the ultrasonic generator, a bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed until distilled water is completely evaporated, placing the solid product in a planetary ball mill, carrying out ball milling at a revolution speed of 580 rpm for 12h, placing the solid mixture in an atmosphere resistance furnace, introducing nitrogen, heating at a heating rate of 5 ℃/min to 520 ℃, carrying out heat preservation and calcination for 3h, introducing ammonia into the atmosphere resistance furnace, heating to 620 ℃, carrying out heat preservation and calcination for 1 h, and rapidly cooling the calcined product to obtain the nano boron-doped graphene carbon nitride component 2.
(2) Preparation of g-C3N4-rGO supported foamed nickel composite 2: adding distilled water solvent, 19 parts of foamed nickel as a carrier, 16 parts of boron-doped graphene carbon nitride component 2 and 5 parts of graphene oxide into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 70 ℃ for 2 hours with the ultrasonic frequency of 30 KHz, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle into a reaction kettle heating box, heating to 180 ℃, reacting for 3 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the g-C3N4-rGO supported foamed nickel composite 2.
(3) Preparation of Nano WO3-g-C3N4-a photocatalytic material with foam nickel supported on rGO heterojunction 2: adding distilled water and g-C into a reaction bottle3N42 parts of rGO supported foamed nickel composite material, 57 parts of sodium tungstate and 3 parts of Fe (NO)3)3Placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 60 ℃ for 50min at the ultrasonic frequency of 40KHz, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1, stirring uniformly, transferring the solution into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a reaction kettle heating box, heating to 190 ℃, reacting for 15 h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product with distilled water, fully drying, placing the solid product in an atmosphere resistance furnace, heating at the temperature rise rate of 4 ℃/min, heating to 390 ℃, carrying out heat preservation and calcination for 3hThe calcined product is the nano WO3-g-C3N4-a photocatalytic material 2 of nickel foam supported by rGO heterojunction.
The photocatalytic materials in examples 1-4 and comparative examples 1-2 are subjected to photocatalytic hydrogen production performance test in a CEL-SPEH2 type photoelectrocatalytic water decomposition hydrogen production system, the solution is 10% triethanolamine aqueous solution, the mass fraction of the photocatalytic material is 0.2%, the concentration of a cocatalyst chloroplatinic acid is 0.5%, a 300W xenon lamp is used as a light source, and the test standard is GB/T26915-.
In summary, the nanometer WO3-g-C3N4the-rGO heterojunction supported foam nickel photocatalytic material is prepared by taking boric acid as a boron source and preparing a thermal oxidation method, wherein the boron-doped graphene carbon nitride prepared by the method has a good nano structure and morphology, and g-C is doped under the boron doping effect3N4Rich mesoporous structure and developed porosity are formed, and g-C is increased3N4Specific surface area, exposing more photochemically active sites, and boron doping enhances g-C3N4The conductivity of the material promotes the transmission and migration of photo-generated electrons, reduces the recombination rate of the photo-generated electrons and holes,
g-C is prepared by taking foamed nickel as a substrate of a photocatalyst through a hydrothermal synthesis method3N4-rGO loading g-C3N4-rGO composite material, let g-C3N4And the rGO is uniformly dispersed and loaded on the surface of the foamed nickel, so that the phenomenon that photocatalytic active sites are reduced due to the agglomeration and aggregation of the boron-doped graphene carbon nitride and the graphene oxide is effectively reduced, the boron-doped graphene carbon nitride and the graphene oxide form a Schottky junction, and the graphene oxide is a transmission channel through which photoproduction electrons pass, so that the migration rate of the photoproduction electrons is improved, and the recombination rate of the photoproduction electrons and holes is reduced.
Preparing the nano Fe-doped WO by an in-situ growth method3Loaded to g-C3N4Huge ratio tableIn area, Fe doping makes WO3The ultraviolet-visible absorption spectrum of (A) is red-shifted to cause WO3Has good photochemical activity and photoresponse in a visible light range, widens the utilization rate of photocatalyst to light energy, and has good performance3And g-C3N4Forming a Z-type heterojunction with a matched band structure, g-C3N4Electron transition from conduction band to WO3In the valence band of (A) with WO3Valence band generating hole recombination, and g-C3N4Valence band generated holes and WO3The photo-generated electrons generated by the conduction band keep the position unchanged, and the g-C is effectively reduced3N4And WO3The photo-generated electrons and the holes are respectively compounded to generate a large amount of photo-generated electrons and holes, the photo-generated electrons and the holes react with water molecules and oxygen to generate hydroxyl free radicals and superoxide free radicals, and organic pollutants such as methyl orange, phenol and the like are subjected to oxidation reaction and degraded into non-toxic or low-toxic micromolecules.
Claims (6)
1. Nano WO3-g-C3N4The photocatalytic material of the-rGO heterojunction supported foam nickel comprises the following formula raw materials and components in parts by weight, and is characterized in that: 12-18 parts of foamed nickel, 21-37 parts of nano boron-doped graphene carbon nitride, 2-4 parts of graphene oxide, 48-55 parts of sodium tungstate and 1-2 parts of Fe (NO)3)3。
2. A nano WO according to claim 13-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material characterized by: the graphene oxide has the sheet diameter of 50-200nm and the thickness of 0.8-1.2 nm.
3. A nano WO according to claim 13-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material characterized by: the preparation method of the nano boron-doped graphene carbon nitride comprises the following steps:
(1) adding melamine and boric acid into a distilled water solvent, placing the solution into an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 20-40min at 50-60 ℃, heating the solution to 70-80 ℃, stirring at a constant speed until distilled water is completely evaporated, placing a solid product into a planetary ball mill, carrying out ball milling for 6-12h at a revolution rotation speed of 580-620rpm, placing the solid mixture into an atmosphere resistance furnace, introducing nitrogen at a heating rate of 3-5 ℃/min, heating to 520-560 ℃, carrying out heat preservation and calcination for 2-3h, introducing ammonia into the atmosphere resistance furnace, heating to 600-620 ℃, carrying out heat preservation and calcination for 1-2h, and rapidly cooling the calcined product to obtain the nano boron-doped graphene carbon nitride.
4. A nano WO according to claim 33-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material characterized by: the mass ratio of melamine to boric acid is 35-45: 1.
5. A nano WO according to claim 33-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material characterized by: the ultrasonic treatment instrument comprises a main machine (1), a main seat (2) is fixedly connected to the inner bottom wall of the main machine (1), a lifting platform (3) is movably mounted inside the main seat (2), a clamping jaw (4) is rotatably connected to the outer side of the main seat (2), a rotating shaft (5) is movably connected to the inner portion of the main seat (2) and is positioned above a connecting shaft of the clamping jaw (4), a sliding seat (6) and a ratchet wheel (9) are mounted on the outer side of the rotating shaft (5), a push plate (7) corresponding to the sliding seat (6) is movably inserted into the top of the main seat (2), slopes are arranged at the top and the bottom of the push plate (7), a shift lever (8) corresponding to the push plate (7) is mounted on the clamping jaw (4), a rack (10) corresponding to the ratchet wheel (9) is arranged on the outer side of the lifting platform (3), an ultrasonic generator (11) is mounted on the inner top wall of the main machine (, the bottle body (13) is arranged at the top of the lifting platform (3).
6. A nano WO according to claim 13-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material characterized by: the nano WO3-g-C3N4-rGO heterojunctionThe preparation method of the foam nickel-loaded photocatalytic material comprises the following steps:
(1) adding 12-18 parts of foamed nickel serving as a carrier, 21-37 parts of boron-doped graphene carbon nitride and 2-4 parts of graphene oxide into a distilled water solvent, carrying out ultrasonic dispersion treatment on the solution at 50-70 ℃ for 1-2h, wherein the ultrasonic frequency is 30-40KHz, transferring the solution into a reaction kettle, heating to 160-180 ℃, reacting for 3-5h, removing the solvent from the solution, washing a solid product, and drying to prepare g-C3N4-rGO supported foamed nickel composite.
(2) g-C to distilled water solvent3N4-rGO supported foamed nickel composite material, 48-55 parts of sodium tungstate, 1-2 parts of Fe (NO)3)3Performing ultrasonic dispersion treatment on the solution at 50-60 ℃ for 30-50min at the ultrasonic frequency of 30-40KHz, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1-2, transferring the solution into a reaction kettle, heating to 190 ℃ at 170 ℃ for reaction for 15-20h, removing the solvent from the solution, washing a solid product, drying, placing the solid product in an atmosphere resistance furnace at the heating rate of 2-4 ℃/min, heating to 420 ℃ at 390 ℃ for heat preservation and calcination for 2-3h, wherein the calcination product is the nano WO3-g-C3N4-rGO heterojunction supported nickel foam photocatalytic material.
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| CN113387419A (en) * | 2021-06-29 | 2021-09-14 | 南华大学 | g-C3N4-Sn3O4-Ni electrode material and preparation method and application thereof |
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| CN112892589A (en) * | 2021-01-26 | 2021-06-04 | 华南农业大学 | Ag3PO4/BiPO4Modified 3D porous starch-rGO composite photocatalytic hydrogel and preparation method thereof |
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