CN115069291B - Ni/VN/g-C 3 N 4 Composite photocatalyst, preparation method and application thereof - Google Patents
Ni/VN/g-C 3 N 4 Composite photocatalyst, preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 47
- 238000000227 grinding Methods 0.000 claims description 44
- 239000004570 mortar (masonry) Substances 0.000 claims description 31
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 29
- 239000012498 ultrapure water Substances 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 229910052573 porcelain Inorganic materials 0.000 claims description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 7
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 7
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000003426 co-catalyst Substances 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- 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
- C01B2203/10—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
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Ni/VN/g-C 3 N 4 The preparation method of the composite photocatalyst comprises the following steps: preparation of porous sheet-like g-C 3 N 4 Powder; preparing NiV-LDH powder; will g-C 3 N 4 The powder is matched with NiV-LDH powder, and then is fully and uniformly mixed and then is calcined and carbonized at high temperature to prepare Ni/VN/g-C 3 N 4 A photocatalyst; the invention provides a brand new metal Ni and VN composite as g-C 3 N 4 Noble metal free co-catalyst g-C 3 N 4 Is a typical porous nano-sheet structure, can effectively increase the number of active sites of the composite photocatalyst, and the metal nickel plays a role of a charge transfer bridge in the composite photocatalyst due to good metal conductivity, so that g-C can be rapidly carried out 3 N 4 The electrons on the valence band are transferred to VN, which, in its co-effort, greatly increases Ni/VN/g-C 3 N 4 The charge separation efficiency and the transmission efficiency of the composite photocatalyst are improved, so that the hydrogen production performance of the composite photocatalyst is improved; the preparation method has the advantages of simple process flow, easily controlled conditions, lower production cost and easy industrialized production.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a photocatalytic material, and in particular relates to a Ni/VN/g-C3N4 composite photocatalyst, and a preparation method and application thereof.
Background
With the increasing energy crisis and environmental problems, the development of renewable and clean energy sources to replace fossil fuels is also becoming more and more urgent. Hydrogen is considered a promising alternative to fossil fuels due to its high energy density and zero emissions. In recent years, solar-driven semiconductor photocatalytic decomposition of water to hydrogen has been considered as an ideal method for solving the global environmental and energy problems. Accordingly, various photocatalysts have been developed to alleviate these troublesome problems. To date, researchers have been working on the preparation of hydrogen evolution photocatalysts using earth-rich materials.
Graphitized carbon nitride (g-C) 3 N 4 ) Is a stable polymeric photocatalyst, which is considered as an attractive candidate material for direct production of hydrogen in water using solar energy due to its high stability, non-toxicity, abundance and excellent optical properties. But original g-C 3 N 4 The high photoinduced charge recombination rate and the lack of absorption above 460nm are still not ideal in practical application. Then, it is necessary to use the pure g-C 3 N 4 The co-catalyst is loaded thereon to achieve efficient space charge separation. Pt is known to have the greatest work function and lowest overpotential, at H 2 The best candidate co-catalyst for capturing electrons in the photocatalytic reaction is produced. In view of the versatility and low cost of the cocatalysts, noble metal based cocatalysts are too scarce and expensive to be used for large scale energy production. The support of the cocatalyst not only promotes charge separation, but also can reduce the activation energy or overpotential of the reaction. It is therefore highly desirable to pursue a co-catalyst that is free of noble metals and has high activity.
Vanadium nitride is a nitride with nitrogen atoms occupying interstitial positions in a vanadium metal lattice, has good conductivity and stable chemical property, and is resistant to chemical corrosion. And as a catalyst promoter of CdS, the catalyst has very obvious improvement on the photocatalytic hydrogen production performance of CdS, but the high surface energy of VN can cause aggregation in the preparation process, thereby causing a great deal of loss of active sites and greatly reducing the energy consumption of VNThe chance of the electrolytes coming into contact, thus making their catalytic activity less desirable. Therefore, the necessary method should be explored to enrich the d electron density of VN. In addition, non-noble metals such as Co or Ni have also been found to be effective in generating H on various semiconductor photocatalysts 2 The superfine Ni nano particles loaded on the Graphene Oxide (GO) sheet have higher photocatalytic performance. There is no current improvement in g-C 3 N 4 Construction of Ni/VN/g-C by the efficiency of photocatalytic Hydrogen production 3 N 4 Study report of the system.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a Ni/VN/g-C 3 N 4 The composite photocatalyst, the preparation method and the application thereof are used for preparing the composite catalyst which effectively improves the hydrogen production efficiency of photocatalysis, and has simple process and low cost.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
Ni/VN/g-C 3 N 4 The preparation method of the composite photocatalyst comprises the following steps:
step one, preparing porous flaky g-C 3 N 4 Powder;
mixing (0.5-5) mmol of nickel chloride hexahydrate, (1-3) mmol of vanadium chloride, (1-5) mmol of urea, (0.1-3) mmole CTAB and (0.005-0.02) g of polydiallyl dimethyl ammonium chloride to obtain mixed powder C, adding 30-100 mL of ultrapure water, performing ultrasonic treatment for 60-150 min, fully stirring, rapidly pouring the mixed solution into a 100mL reaction kettle, putting into an oven which is preheated to 120-200 ℃, preserving heat for 12-24 h, naturally cooling to room temperature after finishing, taking out the reaction kettle, centrifuging, washing, drying and grinding the solution to obtain solid D, namely NiV-LDH;
step three, taking (0.2-3) g of solid D and (1-12) g of porous flaky g-C 3 N 4 Mixing the powder, placing the mixture into 30-90 mL of ultrapure water, performing ultrasonic treatment for 60-240 min, fully stirring, centrifuging to obtain precipitate, drying and grinding to obtain powder E;
step four, powder E, N, N' -methylenebisacrylProportioning the amide and the dicyandiamide according to the mass ratio of 1 (0.5-6) (1-8), placing the mixture in a tube furnace, heating the tube furnace to 500-700 ℃ at the speed of 2-10 ℃/min under the argon atmosphere, preserving heat for 2-5 h, taking out and grinding after the product is naturally cooled to room temperature, thus obtaining Ni/VN/g-C 3 N 4 A photocatalyst.
The invention also has the following technical characteristics:
preferably, in the step one, the porous sheet-shaped g-C 3 N 4 The preparation method of the powder comprises the following steps:
s1, placing 8-16 g of melamine into a white porcelain boat, placing the white porcelain boat into a tubular furnace, heating to 450-600 ℃ at a heating rate of 2-10 ℃/min under the protection of argon, preserving heat for 2-4 hours, naturally cooling a sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and grinding to obtain yellow powder A, namely a block g-C 3 N 4 ；
S2, taking 5-10 g of block g-C 3 N 4 Adding into a beaker filled with 10mL of ultrapure water, carrying out ultrasonic treatment for 30-90 min, finally placing the beaker into a white porcelain boat, placing the porcelain boat into a tube furnace, heating to 350-550 ℃ at a heating rate of 2-10 ℃/min under an oxygen atmosphere, preserving heat for 30-120 min, naturally cooling the sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and grinding to obtain yellow powder B, namely porous flaky g-C 3 N 4 。
Further, grinding in the step S1 is carried out for 20-60 min by adopting a mortar; the grinding in S2 is grinding for 20-90 min in a mortar.
Preferably, the full stirring in the second step is stirring for 60-250 min by adopting a magnetic stirrer.
Preferably, the washing agent in the second step is washed three times or more with ultrapure water and absolute ethanol respectively.
Preferably, the drying in the second step and the third step is carried out in a vacuum drying oven for 8-26 hours.
Preferably, the grinding in the second step, the third step and the fourth step is grinding for 30-120 min by using a mortar.
Preferably, the full stirring in the step three is carried out by placing on a magnetic stirrer for stirring for 10-24 hours.
The invention also protects the Ni/VN/g-C prepared by the method 3 N 4 Composite photocatalyst and its application in photocatalytic hydrogen production.
Compared with the prior art, the invention has the following technical effects:
the invention provides a brand new metal Ni and VN composite as g-C 3 N 4 Noble metal-free co-catalyst and preparation method thereof, g-C 3 N 4 Is a typical porous nano-platelet structure, g-C 3 N 4 The holes on the surface of the nano-sheet can effectively increase the number of active sites of the composite photocatalyst, when the sunlight irradiates g-C 3 N 4 When the electron in the valence band is excited to the conduction band, VN has good electron adsorption capacity due to the unique electron structure, and can well attract g-C 3 N 4 The accumulated photo-generated electrons on the conductive belt, while the metallic nickel plays a role of a charge transfer 'bridge' in the conductive belt due to good metal conductivity, and can rapidly transfer g-C 3 N 4 The electrons on the valence band are transferred to VN, which, in its co-effort, greatly increases Ni/VN/g-C 3 N 4 The charge separation efficiency and the transmission efficiency of the composite photocatalyst are improved, so that the hydrogen production performance of the composite photocatalyst is improved;
the invention is used for preparing Ni/VN/g-C 3 N 4 In the process of compounding the photocatalytic material, a solid phase sintering method is adopted, so that hetero-phase atoms are prevented from being introduced in the compounding process, and the NiV-LDH and the g-C are prepared before carbonization 3 N 4 The composite photocatalyst is firm in growth, simple in process flow, easy to control in conditions, low in production cost and easy to realize industrial production.
Drawings
FIG. 1 is a Ni/VN/g-C prepared in example 1 of the present invention 3 N 4 X-ray diffraction analysis of (2);
FIG. 2 is a Ni/VN/g-C prepared in example 1 of the present invention 3 N 4 Scanning electron microscope at 500 nm;
FIG. 3 is a diagram of N prepared in example 1 of the present inventioni/VN/g-C 3 N 4 Hydrogen production performance graph under visible light.
Detailed Description
The following examples illustrate the invention in further detail.
Example 1:
step one, preparing porous flaky g-C 3 N 4 Powder;
s1, placing 12g of melamine into a white porcelain boat, placing the white porcelain boat into a tube furnace, heating to 550 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat for 4 hours, naturally cooling a sample to room temperature along with the furnace after the completion of the heating, taking out the sample, placing the sample into a mortar, and grinding for 50 minutes to obtain yellow powder A, namely a block g-C 3 N 4 ；
S2, taking 8g of block g-C 3 N 4 Adding into a beaker filled with 10mL of ultrapure water, performing ultrasonic treatment for 40min, placing the beaker into a tubular furnace, heating to 400 ℃ at a heating rate of 4 ℃/min under an oxygen atmosphere, preserving heat for 60min, naturally cooling the sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and grinding the sample in a mortar for 40min to obtain yellow powder B, namely porous flaky g-C 3 N 4 。
Mixing 3mmol of nickel chloride hexahydrate, 1mmol of vanadium chloride, 2mmol of urea, 0.5mmol of CTAB and 0.005g of polydiallyl dimethyl ammonium chloride to obtain mixed powder C, adding 40mL of ultrapure water, performing ultrasonic treatment for 70min, placing the mixed solution on a magnetic stirrer to stir for 80min, rapidly pouring the mixed solution into a 100mL of reaction kettle, placing the reaction kettle into a baking oven which is preheated to 160 ℃, preserving heat for 12h, naturally cooling to room temperature after finishing, taking out the reaction kettle, centrifuging the solution, respectively washing the solution for more than three times by adopting the ultrapure water and absolute ethyl alcohol, drying the solution at 80 ℃ for 24h in a vacuum drying oven, and grinding the solution for 60min by adopting a mortar to obtain solid D, namely NiV-LDH;
step three, 2g of solid D and 7g of porous flaky g-C are taken 3 N 4 Mixing the powder, placing in 30mL ultra-pure water, performing ultrasonic treatment for 60min, placing on a magnetic stirrer, stirring for 14h, centrifuging to obtain precipitate, drying in a vacuum drying oven for 24h, and grinding with a mortar for 60min to obtain the final productPowder E;
step four, proportioning powder E, N, N' -methylenebisacrylamide and dicyandiamide according to the mass ratio of 1:0.6:4, placing the mixture into a tube furnace, heating the tube furnace to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, preserving heat for 2 hours, taking out the product after the product is naturally cooled to room temperature, and grinding the product for 40 minutes by using a mortar to obtain Ni/VN/g-C 3 N 4 A photocatalyst.
Ni/VN/g-C using Lab Solar 6A model equipment pair 3 N 4 And (5) testing the photocatalytic effect. The specific test process comprises weighing 50mg of composite photocatalyst and 10mL of xylooligosaccharide, sequentially placing into a glass reaction vessel filled with 90mL of ultrapure water, and illuminating for 4 hours.
FIG. 1 is a Ni/VN/g-C prepared in example 1 3 N 4 X-ray diffraction analysis of (2); wherein the abscissa is 2 theta angle and the ordinate is absorption intensity. g-C at 13 DEG and 27 DEG respectively 3 N 4 (100) and (002) planes, and Ni/VN/g-C 3 N 4 Can also accurately correspond to Ni PDF#04-0850 and VN PDF#35-0768, which shows that Ni/VN/g-C is successfully prepared 3 N 4 A composite photocatalyst;
FIG. 2 is a Ni/VN/g-C prepared in example 1 3 N 4 Scanning electron microscope at 500 nm; from FIG. 2, it is evident that Ni-VN is a sheet structure smaller than carbon nitride and uniformly dispersed in g-C 3 N 4 On the nanosheets;
FIG. 3 is Ni/VN/g-C prepared in example 1 3 N 4 As can be seen from FIG. 3, the catalyst has excellent hydrogen production performance and stable hydrogen production rate, and the hydrogen production amount of four hours can reach 1669 mu mol/g.
Example 2:
step one, preparing porous flaky g-C 3 N 4 Powder;
s1, placing 10g of melamine into a white porcelain boat, placing the white porcelain boat into a tube furnace, heating to 600 ℃ at a heating rate of 10 ℃/min under the protection of argon, preserving heat for 2 hours, naturally cooling a sample to room temperature along with the furnace after the completion of the heating, taking out the sample, placing the sample into a mortar, grinding for 60 minutes to obtain yellow powder A,i.e. block g-C 3 N 4 ；
S2, taking 10g of block g-C 3 N 4 Adding into a beaker filled with 10mL of ultrapure water, performing ultrasonic treatment for 30min, placing the beaker into a white porcelain boat, placing the porcelain boat into a tubular furnace, heating to 550 ℃ at a heating rate of 2 ℃/min under an oxygen atmosphere, preserving heat for 60min, naturally cooling the sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and placing the sample into a mortar for grinding for 40min to obtain yellow powder B, namely porous flaky g-C 3 N 4 。
Mixing 3mmol of nickel chloride hexahydrate, 1mmol of vanadium chloride, 4mmol of urea, 2mmol of CTAB and 0.01g of polydiallyl dimethyl ammonium chloride to obtain mixed powder C, adding 60mL of ultrapure water, performing ultrasonic treatment for 60min, placing the mixed solution on a magnetic stirrer for stirring for 60min, rapidly pouring the mixed solution into a 100mL reaction kettle, placing the reaction kettle into a baking oven which is preheated to 140 ℃, preserving heat for 14h, naturally cooling to room temperature, taking out the reaction kettle, centrifuging the solution, respectively washing the solution with ultrapure water and absolute ethyl alcohol for more than three times, placing the solution into a vacuum drying oven for drying for 18h, and grinding the solution with a mortar for 40min to obtain solid D, namely NiV-LDH;
step three, 1g of solid D and 2g of porous flaky g-C are taken 3 N 4 Mixing the powder, placing the powder into 30mL of ultrapure water, performing ultrasonic treatment for 60min, placing the powder on a magnetic stirrer for stirring for 14h, centrifuging to obtain a precipitate, placing the precipitate into a vacuum drying oven for drying for 18h, and grinding the precipitate by using a mortar for 50min to obtain powder E;
step four, proportioning powder E, N, N' -methylenebisacrylamide and dicyandiamide according to the mass ratio of 1:2:6, placing the mixture into a tube furnace, heating the tube furnace to 550 ℃ at the speed of 5 ℃/min under the argon atmosphere, preserving heat for 3 hours, taking out the product after naturally cooling the product to room temperature, and grinding the product for 60 minutes by adopting a mortar to obtain Ni/VN/g-C 3 N 4 A photocatalyst.
Example 3:
step one, preparing porous flaky g-C 3 N 4 Powder;
s1, placing 14g of melamine into a white porcelain boat, placing the white porcelain boat into a tube furnace, and heating the white porcelain boat to a temperature of 6 ℃ per minute under the protection of argonPreserving heat at 600deg.C for 2h, naturally cooling the sample to room temperature with the furnace, taking out the sample, grinding in a mortar for 40min to obtain yellow powder A, i.e. block g-C 3 N 4 ；
S2, taking 8g of block g-C 3 N 4 Adding into a beaker filled with 10mL of ultrapure water, performing ultrasonic treatment for 60min, placing the beaker into a tubular furnace, heating to 500 ℃ at a heating rate of 6 ℃/min under an oxygen atmosphere, preserving heat for 80min, naturally cooling the sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and grinding the sample in a mortar for 40min to obtain yellow powder B, namely porous flaky g-C 3 N 4 。
Mixing 3mmol of nickel chloride hexahydrate, 2mmol of vanadium chloride, 4mmol of urea, 1.2mmol of CTAB and 0.02g of polydiallyl dimethyl ammonium chloride to obtain mixed powder C, adding 60mL of ultrapure water, performing ultrasonic treatment for 60min, placing the mixed solution on a magnetic stirrer for stirring for 120min, rapidly pouring the mixed solution into a 100mL of reaction kettle, placing the reaction kettle into a baking oven which is preheated to 160 ℃, preserving heat for 16h, naturally cooling to room temperature after finishing, taking out the reaction kettle, centrifuging the solution, respectively washing the solution for more than three times by adopting the ultrapure water and absolute ethyl alcohol, drying the solution in a vacuum drying oven for 18h, and grinding the solution by adopting a mortar for 60min to obtain a solid D, namely NiV-LDH;
step three, 1g of solid D and 6g of porous flaky g-C are taken 3 N 4 Mixing the powder, placing the powder into 40mL of ultrapure water, performing ultrasonic treatment for 60min, placing the powder on a magnetic stirrer for stirring for 10h, centrifuging to obtain a precipitate, placing the precipitate into a vacuum drying oven for drying for 18h, and grinding the precipitate by using a mortar for 40min to obtain powder E;
step four, proportioning powder E, N, N' -methylenebisacrylamide and dicyandiamide in a mass ratio of 1:2:4, placing the mixture in a tube furnace, heating the tube furnace to 650 ℃ at a speed of 5 ℃/min under argon atmosphere, preserving heat for 3 hours, taking out the product after naturally cooling the product to room temperature, and grinding the product for 40 minutes by adopting a mortar to obtain Ni/VN/g-C 3 N 4 A photocatalyst.
Example 4:
step one, preparing porous flaky g-C 3 N 4 Powder;
s1, placing 8g of melamine into a white porcelain boat, placing the white porcelain boat into a tube furnace, heating to 450 ℃ at a heating rate of 2 ℃/min under the protection of argon, preserving heat for 3 hours, naturally cooling a sample to room temperature along with the furnace after the completion of the heating, taking out the sample, placing the sample into a mortar, and grinding for 20 minutes to obtain yellow powder A, namely a block g-C 3 N 4 ；
S2, taking 5g of block g-C 3 N 4 Adding into a beaker filled with 10mL of ultrapure water, performing ultrasonic treatment for 80min, placing the beaker into a tubular furnace, heating to 350 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving heat for 120min, naturally cooling the sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and grinding the sample in a mortar for 20min to obtain yellow powder B, namely porous flaky g-C 3 N 4 。
Mixing 0.5mmol of nickel chloride hexahydrate, 3mmol of vanadium chloride, 1mmol of urea, 0.1mmol of CTAB and 0.02 mmol of polydiallyl dimethyl ammonium chloride to obtain mixed powder C, adding 30mL of ultrapure water, performing ultrasonic treatment for 90min, placing on a magnetic stirrer to stir for 180min, rapidly pouring the mixed solution into a 100mL reaction kettle, placing into a baking oven which is preheated to 120 ℃, preserving heat for 20h, naturally cooling to room temperature, taking out the reaction kettle, centrifuging the solution, respectively washing the solution with ultrapure water and absolute ethyl alcohol for more than three times, placing into a vacuum drying oven to dry for 8h, and grinding with a mortar for 30min to obtain solid D, namely NiV-LDH;
step three, taking 3g of solid D and 1g of porous flaky g-C 3 N 4 Mixing the powder, placing the powder into 60mL of ultrapure water, performing ultrasonic treatment for 120min, placing the powder on a magnetic stirrer for stirring for 20h, centrifuging to obtain a precipitate, placing the precipitate into a vacuum drying oven for drying for 8h, and grinding the precipitate by using a mortar for 30min to obtain powder E;
step four, proportioning powder E, N, N' -methylenebisacrylamide and dicyandiamide according to the mass ratio of 1:0.5:8, placing the mixture into a tube furnace, heating the tube furnace to 500 ℃ at the speed of 2 ℃/min under the argon atmosphere, preserving heat for 4 hours, taking out the product after the product is naturally cooled to room temperature, and grinding the product for 30 minutes by using a mortar to obtain Ni/VN/g-C 3 N 4 A photocatalyst.
Example 5:
step one, preparing porous flaky g-C 3 N 4 Powder;
s1, placing 16g of melamine into a white porcelain boat, placing the white porcelain boat into a tube furnace, heating to 500 ℃ at a heating rate of 8 ℃/min under the protection of argon, preserving heat for 3 hours, naturally cooling a sample to room temperature along with the furnace after the completion of the heating, taking out the sample, placing the sample into a mortar, and grinding for 30 minutes to obtain yellow powder A, namely a block g-C 3 N 4 ；
S2, taking 6g of block g-C 3 N 4 Adding into a beaker filled with 10mL of ultrapure water, performing ultrasonic treatment for 90min, placing the beaker into a tubular furnace, heating to 450 ℃ at a heating rate of 10 ℃/min under an oxygen atmosphere, preserving heat for 30min, naturally cooling the sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and grinding the sample in a mortar for 90min to obtain yellow powder B, namely porous flaky g-C 3 N 4 。
Mixing 5mmol of nickel chloride hexahydrate, 1mmol of vanadium chloride, 5mmol of urea, 3mmol of CTAB and 0.01g of polydiallyl dimethyl ammonium chloride to obtain mixed powder C, adding 100mL of ultrapure water, performing ultrasonic treatment for 150min, placing the mixed solution on a magnetic stirrer to stir for 250min, rapidly pouring the mixed solution into a 100mL of reaction kettle, placing the reaction kettle into a baking oven which is preheated to 200 ℃, preserving heat for 24h, naturally cooling to room temperature, taking out the reaction kettle, centrifuging the solution, respectively washing the solution with ultrapure water and absolute ethyl alcohol for more than three times, placing the solution into a vacuum drying oven to dry for 26h, and grinding the solution with a mortar for 120min to obtain solid D, namely NiV-LDH;
step three, taking 0.2g of solid D and 12g of porous flaky g-C 3 N 4 Mixing the powder, placing the powder into 90mL of ultrapure water, performing ultrasonic treatment for 240min, placing the powder on a magnetic stirrer for stirring for 24h, centrifuging to obtain a precipitate, placing the precipitate into a vacuum drying oven for drying for 26h, and grinding the precipitate by using a mortar for 120min to obtain powder E;
step four, proportioning powder E, N, N' -methylene bisacrylamide and dicyandiamide according to the mass ratio of 1:6:1, placing the mixture into a tube furnace, heating the tube furnace to 700 ℃ at the speed of 10 ℃/min under the argon atmosphere, preserving heat for 5 hours, and taking out after the product is naturally cooled to room temperatureGrinding with mortar for 120min to obtain Ni/VN/g-C 3 N 4 A photocatalyst.
Claims (9)
1. Ni/VN/g-C 3 N 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps:
step one, preparing porous flaky g-C 3 N 4 Powder;
mixing (0.5-5) mmol of nickel chloride hexahydrate, (1-3) mmol of vanadium chloride, (1-5) mmol of urea, (0.1-3) mmole CTAB and (0.005-0.02) g of polydiallyl dimethyl ammonium chloride to obtain mixed powder C, adding 30-100 mL of ultrapure water, performing ultrasonic treatment for 60-150 min, fully stirring, rapidly pouring the mixed solution into a 100mL reaction kettle, putting into an oven which is preheated to 120-200 ℃, preserving heat for 12-24 h, naturally cooling to room temperature after finishing, taking out the reaction kettle, centrifuging, washing, drying and grinding the solution to obtain solid D, namely NiV-LDH;
step three, taking (0.2-3) g of solid D and (1-12) g of porous flaky g-C 3 N 4 Mixing the powder, placing the mixture into 30-90 mL of ultrapure water, performing ultrasonic treatment for 60-240 min, fully stirring, centrifuging to obtain precipitate, drying and grinding to obtain powder E;
step four, proportioning powder E, N, N' -methylene bisacrylamide and dicyandiamide according to the mass ratio of 1 (0.5-6) (1-8), placing the mixture into a tube furnace, heating the tube furnace to 500-700 ℃ at the speed of 2-10 ℃/min under the argon atmosphere, preserving heat for 2-5 hours, taking out and grinding after the product is naturally cooled to room temperature, thus obtaining Ni/VN/g-C 3 N 4 A photocatalyst;
porous sheet-shaped g-C in the step one 3 N 4 The preparation method of the powder comprises the following steps:
s1, placing 8-16 g of melamine into a white porcelain boat, placing the white porcelain boat into a tubular furnace, heating to 450-600 ℃ at a heating rate of 2-10 ℃/min under the protection of argon, preserving heat for 2-4 hours, naturally cooling a sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and grinding to obtain yellow powder A, namely a block g-C 3 N 4 ；
S2, taking 5-10 g of block g-C 3 N 4 Adding into a beaker filled with 10mL of ultrapure water, carrying out ultrasonic treatment for 30-90 min, finally placing the beaker into a white porcelain boat, placing the porcelain boat into a tube furnace, heating to 350-550 ℃ at a heating rate of 2-10 ℃/min under an oxygen atmosphere, preserving heat for 30-120 min, naturally cooling the sample to room temperature along with the furnace after the completion of the heating, taking out the sample, and grinding to obtain yellow powder B, namely porous flaky g-C 3 N 4 。
2. Ni/VN/g-C according to claim 1 3 N 4 The preparation method of the composite photocatalyst is characterized in that grinding in S1 is carried out in a mortar for 20-60 min; the grinding in S2 is grinding for 20-90 min in a mortar.
3. Ni/VN/g-C according to claim 1 3 N 4 The preparation method of the composite photocatalyst is characterized in that the full stirring in the second step is stirring for 60-250 min by adopting a magnetic stirrer.
4. Ni/VN/g-C according to claim 1 3 N 4 The preparation method of the composite photocatalyst is characterized in that the lotion in the second step is washed for more than three times by adopting ultrapure water and absolute ethyl alcohol respectively.
5. Ni/VN/g-C according to claim 1 3 N 4 The preparation method of the composite photocatalyst is characterized in that the drying in the second step and the third step is that the composite photocatalyst is put into a vacuum drying oven to be dried for 8-26 hours.
6. Ni/VN/g-C according to claim 1 3 N 4 The preparation method of the composite photocatalyst is characterized in that grinding in the second step, the third step and the fourth step is grinding for 30-120 min by adopting a mortar.
7. Ni/VN/g-C according to claim 1 3 N 4 A preparation method of a composite photocatalyst,the method is characterized in that the full stirring in the step three is carried out by placing the mixture on a magnetic stirrer for stirring for 10-24 hours.
8. Ni/VN/g-C prepared by the method according to any one of claims 1-7 3 N 4 A composite photocatalyst.
9. A Ni/VN/g-C as in claim 8 3 N 4 The application of the composite photocatalyst in the photocatalytic hydrogen production.
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| CN112354553A (en) * | 2020-10-09 | 2021-02-12 | 深圳技术大学 | g-C3N4Preparation method of p-n homojunction photocatalyst and preparation method of hydrogen |
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| CN112354553A (en) * | 2020-10-09 | 2021-02-12 | 深圳技术大学 | g-C3N4Preparation method of p-n homojunction photocatalyst and preparation method of hydrogen |
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