WO2021072818A1 - Preparation method for and application of bismuth tungstate-graphene-conductive hydrogel - Google Patents

Preparation method for and application of bismuth tungstate-graphene-conductive hydrogel Download PDF

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WO2021072818A1
WO2021072818A1 PCT/CN2019/115252 CN2019115252W WO2021072818A1 WO 2021072818 A1 WO2021072818 A1 WO 2021072818A1 CN 2019115252 W CN2019115252 W CN 2019115252W WO 2021072818 A1 WO2021072818 A1 WO 2021072818A1
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graphene
preparation
bismuth tungstate
tungstate
bismuth
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Chinese (zh)
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刘璞
魏子晔
李振邦
王建兴
刘才超
杨国伟
石磊
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中山大学
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • This application belongs to the technical field of electrolysis catalyst research and development, and in particular relates to a preparation method and application of bismuth tungstate-graphene-conductive hydrogel.
  • Renewable energy includes solar energy, wind energy, hydrogen energy, and biomass energy.
  • Hydrogen energy is a clean and renewable dye.
  • the combustion of hydrogen can provide three times the energy compared to ordinary fossil fuels.
  • the product is pollution-free, has zero pollutant emissions, and can be recycled. Since the water electrolysis technology was first reported, this method has received extensive attention and research. Part of the oversupply of electricity can be used to split water to produce hydrogen, which can be used as a direct supply of primary energy, and hydrogen can also be stored for secondary energy applications such as fuel cells.
  • the cathode hydrogen evolution reaction (HER, hydrogen evolution reaction) of electrolyzed water has a high kinetic potential.
  • the traditional HER reaction needs to be carried out at a higher overpotential and consumes too much electrical energy, so it is necessary to find a suitable one.
  • the catalyst reduces the electric potential and improves the efficiency of hydrogen precipitation.
  • Platinum-based precious metals are the most ideal electrocatalysts for HER, but platinum-based materials are limited by their high price and low reserves, and there are relatively large limitations in their applications.
  • the layered structure of bismuth tungstate (Bi 2 WO 6 ) can promote the separation of photogenerated electrons and holes, it is also conducive to the transport of ions between layers, and has good physical and chemical properties, such as iron Electricity, pyroelectricity, photodegradation, piezoelectricity, nonlinear dielectric polarization and luminescence properties, etc.
  • a single Bi 2 WO 6 has shortcomings in photodegradation, its visible light response range is limited, and the recombination rate of photogenerated electrons and holes is relatively high. At the same time, after the electrolysis reaction is completed, the catalyst cannot be recovered, resulting in waste of the catalyst and environmental pollution.
  • the present application provides a preparation method and application of bismuth tungstate-graphene-conductive hydrogel, which is used to solve the problems in the prior art for the cathodic hydrogen evolution reaction of electrolyzed water and the degradation of environmental pollution.
  • the catalyst has the technical defects of poor catalytic performance and unrecoverable.
  • This application provides a preparation method of bismuth tungstate-graphene-conductive hydrogel, the preparation method is:
  • Step 1 Hydrothermal reaction to prepare bismuth tungstate: sodium tungstate, bismuth nitrate and CTAB are mixed and dissolved in water, stirred and then hydrothermally reacted. After the hydrothermal reaction is completed, they are washed and dried sequentially to obtain lamellar tungstic acid bismuth;
  • Step 2 Ultrasonic peeling: the lamellae are dissolved and then ultrasonically peeled to obtain dispersed two-dimensional bismuth tungstate nanosheets;
  • Step 3 Preparation of graphene quantum dots: After the graphene is dissolved, laser processing is performed to obtain graphene quantum dots;
  • Step 4 Laser ablation composite: the dispersed two-dimensional bismuth tungstate nanosheets are mixed with the graphene quantum dots to perform laser ablation composite to obtain graphene-bismuth tungstate;
  • Step 5 Cross-linking polymerization: graphene-bismuth tungstate, acrylamide solution, cross-linking agent and initiator are mixed to polymerize to obtain the fifth product;
  • Step 6 Aniline immersion: the fifth product is mixed with the aniline solution, and the sixth product is obtained by standing still;
  • Step 7 Secondary polymerization: The sixth product is mixed with the initiator solution and polymerized to obtain a conductive hydrogel product of bismuth tungstate-graphene-polyacrylamide-polyaniline.
  • the feed ratio of bismuth tungstate, graphene, acrylamide and aniline is (0.01 ⁇ 0.05):(0.003 ⁇ 0.015):(1 ⁇ 5):(0.1 ⁇ 0.5) in mole parts.
  • the preparation method further includes: removing impurities;
  • the method for removing impurities is: the crude conductive hydrogel obtained in step 7 is allowed to stand still in water to obtain a pure product.
  • the temperature of the hydrothermal reaction is 120-160°C, and the time of the hydrothermal reaction is 18-24h;
  • the frequency of the ultrasonic dispersion is 20-25 KHz, and the time of the ultrasonic dispersion is 1 to 3 h.
  • the processing time of the laser treatment is 1 to 3 hours
  • the laser wavelength of the laser treatment is 10 to 760 nm
  • the pulse frequency of the laser treatment is 10 to 100 Hz
  • the single pulse of the laser treatment The energy is 200 ⁇ 500mJ.
  • the action time of the laser ablation recombination is 30-60 min
  • the laser wavelength of the laser ablation recombination is 10 to 760 nm
  • the pulse frequency of the laser ablation recombination is 10-100 Hz
  • the laser ablation recombination The combined single pulse energy is 20-50mJ.
  • the concentration of the acrylamide solution is 1 to 5 mol/L, and the solvent of the acrylamide solution is deionized water;
  • the concentration of the aniline solution is 0.3 to 1.5 mol/L, and the solvent of the aniline solution is selected from any one or more of hydrochloric acid and deionized water;
  • step 7 the molar ratio of the initiator to acrylamide is 1: (200-600).
  • the initiator is selected from any one or more of ammonium persulfate, potassium persulfate and N,N,N′,N′-tetramethylethylenediamine;
  • the crosslinking agent is selected from any one or more of N,N-methylenebisacrylamide, azobisisobutyronitrile and N,N'-diisopropylbisacrylamide.
  • the polymerization method is: water bath/oil bath heating polymerization at 60-80°C for 10-30 minutes;
  • step 6 the standing temperature is room temperature, and the standing time is 6-12h;
  • step 7 the polymerization method is: standing for polymerization at room temperature for 4 to 8 hours.
  • the application also provides an application of the product obtained by the preparation method described in any one of the above in the electrolysis catalyst.
  • this application provides a method for preparing bismuth tungstate-graphene-conductive hydrogel, which includes: preparing bismuth tungstate by hydrothermal reaction, ultrasonic peeling, preparing graphene quantum dots, laser ablation composite, cross-linking Union polymerization, aniline immersion and secondary polymerization.
  • the application also provides an application of the product obtained by the above preparation method in an electrolysis catalyst.
  • graphene quantum dots are introduced to increase active sites of bismuth tungstate to improve electrocatalytic performance; further, combined with conductive gel, based on the electrical properties and three-dimensional structure of conductive gel, The bismuth tungstate-graphene is further uniformly dispersed to prevent agglomeration of the catalyst, increase the catalytic area of the catalyst, and the gel is easy to recover after the catalysis is completed.
  • the preparation method and application of bismuth tungstate-graphene-conductive hydrogel provided in the present application solve the problem of poor catalytic performance and unrecyclable catalysts used in the cathode hydrogen evolution reaction of electrolyzed water in the prior art. Technical flaws.
  • Fig. 1 is a schematic flow chart of a method for preparing bismuth tungstate-graphene-conductive hydrogel provided by the present application
  • Example 2 is a schematic diagram of the result of linear scanning the volt-ampere curve in Example 4.
  • Example 3 is a schematic diagram of the degradation efficiency of the organic dye Rh B by the prepared bismuth tungstate-graphene-conductive hydrogel and the reference substance in Example 5;
  • Figure 1 is designated as the abstract drawing.
  • This application provides a method for preparing bismuth tungstate-graphene-conductive hydrogel and its application, which is used to solve the problem of poor catalytic performance and unrecyclable catalyst used in the cathode hydrogen evolution reaction of electrolyzed water in the prior art. Of technical defects.
  • Step 1 Weigh out 1mmol of sodium tungstate (Na 2 WO 4 ⁇ 2H 2 O), 2mmol of bismuth nitrate (Bi(NO 3 ) 3 ⁇ 5H 2 O) and 0.05g of CTAB, mix them and dissolve in 80ml of deionized water at 60°C , Stir at 500r/min for 30min until uniform, transfer to a hydrothermal kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 120°C, and the time of the hydrothermal reaction is 20h. After the hydrothermal reaction is completed, the lamellar bismuth tungstate is obtained by successive washing and drying; wherein the washing method is washing with water and ethanol 3 times, and the drying method is: drying at 60°C for 10 hours.
  • Step 2 Take 400 mg of bismuth tungstate obtained in the previous step, dissolve it in 200 ml of deionized water, and ultrasonically peel off after dissolution to obtain dispersed two-dimensional bismuth tungstate nanosheets; wherein the frequency of ultrasonic dispersion is 20KHz, and the time of ultrasonic dispersion For 1h.
  • Step 3 Weigh 5mg of graphene and dissolve it in 10ml of deionized water, and disperse the graphene by ultrasonic dispersion at 53KHz for 10min to fully dissolve the graphene; after dissolution, perform laser treatment with a wavelength of 532nm, a pulse frequency of 10Hz, and a single pulse energy of 200mJ for 3h , Get graphene quantum dots.
  • Step 4 Take 5ml of the dispersed two-dimensional bismuth tungstate nanosheets obtained in step 2 and mix with the graphene quantum dot solution obtained in step 3.
  • the ultrasonic dispersion method can be used to make the two fully mixed .
  • the mass ratio of the dispersed two-dimensional bismuth tungstate nanosheets to the graphene quantum dots is 2:1.
  • Step 5 Prepare 1mol/L acrylamide (AM) solution, then add graphene-bismuth tungstate, crosslinking agent and initiator (0.05mol/L) to mix uniformly, polymerize at 60°C water bath temperature for 30min, and get transparent The jelly-like hydrogel is the fifth product.
  • the crosslinking agent is N,N-methylenebisacrylamide
  • the initiator is ammonium persulfate; the molar feed ratio of acrylamide, crosslinking agent and initiator is 1:0.005:0.05.
  • Step 6 The fifth product is immersed in a hydrochloric acid (aniline concentration of 1.5 mol/L) solution containing aniline (ANI) and allowed to stand at room temperature for 6 hours to allow the aniline monomer to enter the fifth product, which is the sixth product.
  • a hydrochloric acid aniline concentration of 1.5 mol/L
  • aniline aniline
  • Step 7 The sixth product is immersed in the initiator aqueous solution, and the aniline monomer is polymerized at room temperature for 4 hours to form the crude bismuth tungstate-graphene-PAM-PANI conductive hydrogel, and the obtained crude conductive hydrogel is placed in a large amount The oligomer and unreacted aniline monomer are removed from the deionized water to obtain a pure polyacrylamide-polyaniline composite hydrogel product.
  • the initiator is ammonium persulfate; the molar feed ratio of the initiator to the aniline in step two is 1:1.
  • the feed ratio of bismuth tungstate, graphene, acrylamide, and aniline is 0.03:0.003:5:0.1 in terms of parts by mole.
  • Step 1 Weigh out 1mmol of sodium tungstate (Na 2 WO 4 ⁇ 2H 2 O), 2mmol of bismuth nitrate (Bi(NO 3 ) 3 ⁇ 5H 2 O) and 0.05g of CTAB, mix them and dissolve in 80ml of deionized water at 70°C , Stir at 800r/min for 10 minutes until uniform, transfer to a hydrothermal kettle for hydrothermal reaction, where the temperature of the hydrothermal reaction is 130°C, and the time of the hydrothermal reaction is 24h. After the hydrothermal reaction is completed, the lamellar bismuth tungstate is obtained by successive washing and drying; wherein the washing method is washing with water and ethanol 3 times, and the drying method is: drying at 60°C for 10 hours.
  • Step 2 Take 400 mg of the lamella bismuth tungstate obtained in the previous step, dissolve it in 200ml deionized water, and ultrasonically peel off after dissolution to obtain dispersed two-dimensional bismuth tungstate nanosheets; wherein the frequency of ultrasonic dispersion is 25KHz, and the time of ultrasonic dispersion For 2h.
  • Step 3 Weigh 10mg of graphene and dissolve it in 10ml of deionized water, and disperse the graphene by ultrasonic dispersion at 53KHz for 10min to fully dissolve the graphene; after dissolution, laser treatment with a wavelength of 10nm, a pulse frequency of 100Hz, and a single pulse energy of 300mJ for 2h , Get graphene quantum dots.
  • Step 4 Take 5ml of the dispersed two-dimensional bismuth tungstate nanosheets obtained in step 2 and mix with the graphene quantum dot solution obtained in step 3.
  • the ultrasonic dispersion method can be used to make the two fully mixed .
  • the mass ratio of the dispersed two-dimensional bismuth tungstate nanosheets to the graphene quantum dots is 1:1.
  • Step 5 Prepare 3mol/L acrylamide (AM) solution, then add graphene-bismuth tungstate, cross-linking agent and initiator (0.05mol/L) to mix uniformly, polymerize at 60°C water bath temperature for 30min, get transparent
  • the jelly-like hydrogel is the fifth product.
  • the crosslinking agent is azobisisobutyl cyanide
  • the initiator is potassium persulfate; the molar feed ratio of acrylamide, crosslinking agent and initiator is 1:0.01:0.1.
  • Step 6 The fifth product is immersed in a hydrochloric acid (aniline concentration of 0.3 mol/L) solution containing aniline (ANI), and allowed to stand at room temperature for 10 hours to allow the aniline monomer to enter the fifth product, which is the sixth product.
  • a hydrochloric acid aniline concentration of 0.3 mol/L
  • aniline aniline
  • Step 7 The sixth product is immersed in the initiator aqueous solution, and the aniline monomer is polymerized at room temperature for 6 hours to form the crude bismuth tungstate-graphene-PAM-PANI conductive hydrogel, and the obtained crude conductive hydrogel is placed in a large amount The oligomers and unreacted aniline monomers are removed from the deionized water to obtain pure bismuth tungstate-graphene-conductive hydrogel product.
  • the initiator is potassium persulfate; the molar feed ratio of the initiator to the aniline in step 6 is 1:1.
  • the feed ratio of bismuth tungstate, graphene, acrylamide, and aniline is 0.055:0.015:1:0.2 in terms of parts by mole.
  • Step 1 Weigh out 1mmol of sodium tungstate (Na 2 WO 4 ⁇ 2H 2 O), 2mmol of bismuth nitrate (Bi(NO 3 ) 3 ⁇ 5H 2 O) and 0.05g of CTAB, mix them and dissolve in 80ml of deionized water at 80°C , Stir at a speed of 1000r/min for 20 minutes until uniform, transfer to a hydrothermal kettle for hydrothermal reaction, where the temperature of the hydrothermal reaction is 160°C, and the time of the hydrothermal reaction is 18h. After the hydrothermal reaction is completed, the lamellar bismuth tungstate is obtained by successive washing and drying; wherein the washing method is washing with water and ethanol 3 times, and the drying method is: drying at 60°C for 10 hours.
  • the washing method is washing with water and ethanol 3 times
  • the drying method is: drying at 60°C for 10 hours.
  • Step 2 Take 400 mg of bismuth tungstate obtained in the previous step, dissolve it in 200 ml of deionized water, and ultrasonically peel off after dissolution to obtain dispersed two-dimensional bismuth tungstate nanosheets; wherein the frequency of ultrasonic dispersion is 22KHz, and the time of ultrasonic dispersion For 3h.
  • Step 3 Weigh 20mg of graphene and dissolve it in 10ml of deionized water, and dissolve the graphene by ultrasonic dispersion at a frequency of 53KHz for 10min to fully dissolve the graphene; after dissolution, perform laser treatment with a wavelength of 760nm, a pulse frequency of 30Hz, and a single pulse energy of 500mJ for 1h , Get graphene quantum dots.
  • Step 4 Take 5ml of the dispersed two-dimensional bismuth tungstate nanosheets obtained in step 2 and mix with the graphene quantum dot solution obtained in step 3.
  • the ultrasonic dispersion method can be used to make the two fully mixed .
  • the mass ratio of the dispersed two-dimensional bismuth tungstate nanosheets to the graphene quantum dots is 2:1.
  • Step 5 Prepare 5mol/L acrylamide (AM) solution, then add graphene-bismuth tungstate, cross-linking agent and initiator (0.05mol/L) to mix uniformly, polymerize at 80°C water bath temperature for 30min, get transparent
  • the jelly-like hydrogel is the fifth product.
  • the crosslinking agent is N,N'-diisopropyl bisacrylamide
  • the initiator is N,N,N',N'-tetramethylethylenediamine
  • acrylamide, crosslinking agent and initiator The molar feed ratio of the agent is 1:0.02:0.2.
  • Step 6 The first product is immersed in a hydrochloric acid (aniline concentration of 1 mol/L) solution containing aniline (ANI), and allowed to stand at room temperature for 12 hours to allow the aniline monomer to enter the fifth product, which is the sixth product.
  • a hydrochloric acid aniline concentration of 1 mol/L
  • aniline aniline
  • Step 7 The sixth product is immersed in the initiator aqueous solution, and the aniline monomer is polymerized at room temperature for 8 hours to form the crude bismuth tungstate-graphene-PAM-PANI conductive hydrogel, and the obtained crude conductive hydrogel is placed in a large amount The oligomers and unreacted aniline monomers are removed from the deionized water to obtain pure bismuth tungstate-graphene-conductive hydrogel product.
  • the initiator is N,N,N',N'-tetramethylethylenediamine; the molar feed ratio of the initiator to the aniline in step six is 1:1.
  • the feed ratio of bismuth tungstate, graphene, acrylamide, and aniline is 0.01:0.01:3:0.5 in terms of parts by mole.
  • the high-efficiency and high-purity synthesis of bismuth tungstate is firstly performed, but at this time, the prepared bismuth tungstate has a lamellar structure, and its stacking is serious and cannot be effectively catalyzed.
  • step two with the help of ultrasound, the aggregated bismuth tungstate is sonicated to effectively disperse it, and dispersed two-dimensional bismuth tungstate nanosheets are obtained, which increases the exposed area of bismuth tungstate and provides more More active area.
  • the obtained graphene quantum dots are zero-dimensional few-layer graphene materials, which are at the nanometer level in three dimensions, that is, graphene quantum dots can exhibit some unique properties, such as strong quantum Confinement effect, edge effect, good electron transfer ability and up-conversion luminescence characteristics, etc.; at the same time, graphene quantum dots also have good characteristics of non-toxicity and low price.
  • graphene quantum dots and two-dimensional tungstic acid Combined with bismuth nanosheets graphene quantum dots can be used as active sites to improve the catalytic activity of two-dimensional bismuth tungstate.
  • step five the prepared bismuth tungstate-graphene is incorporated into the three-dimensional structure of polyacrylamide.
  • aniline is further introduced and polymerized, and the conductive hydrogel is used as a catalyst carrier, which can not only achieve The uniform dispersion of the catalyst increases the active area of the catalyst; at the same time, the conductive hydrogel also has good electrical properties, and it combines with the catalyst to form a force-electric combined catalytic system, which further comprehensively improves the catalytic performance of the catalyst.
  • the gel-like carrier facilitates the recovery of the catalyst after use, and realizes the recovery and reuse of the catalyst.
  • This example is a specific example for measuring the catalytic performance of the graphene-bismuth tungstate-conductive hydrogel prepared in Examples 1 to 3.
  • the control catalyst used is bismuth tungstate powder.
  • the reference electrode is a saturated calomel electrode
  • counter electrode is a graphite electrode
  • 0.5mol L - 1 H 2 SO 4 solution is the electrolyte.
  • LSV linear sweep voltammetry
  • This example is a specific example for measuring the catalytic performance of the graphene-bismuth tungstate-hydrogel prepared in Examples 1 to 3.
  • the control used is bismuth tungstate without graphene quantum dots -Hydrogel catalytic system for photodegradation of rhodamine B.
  • the products prepared have a gel-like structure.
  • the gel prepared by the present invention is convenient and quick to recover, and can achieve rapid catalyst recovery. Easy to recycle.
  • this application provides a method for preparing bismuth tungstate-graphene-conductive hydrogel, which includes: preparing bismuth tungstate by hydrothermal reaction, ultrasonic stripping, preparing graphene quantum dots, laser ablation composite, cross-linking Union polymerization, aniline immersion and secondary polymerization.
  • the application also provides an application of the product obtained by the above preparation method in an electrolysis catalyst.
  • graphene quantum dots are introduced to increase active sites of bismuth tungstate to improve electrocatalytic performance; further, combined with conductive gel, based on the electrical properties and three-dimensional structure of conductive gel, The bismuth tungstate-graphene is further uniformly dispersed to prevent agglomeration of the catalyst, increase the catalytic area of the catalyst, and the gel is easy to recover after the catalysis is completed.
  • the preparation method and application of bismuth tungstate-graphene-conductive hydrogel provided by the present application solve the problem of poor catalytic performance and unrecyclable catalysts used in the cathode hydrogen evolution reaction of electrolyzed water in the prior art. Technical defects.

Abstract

The present application relates to the technical field of electrolytic catalyst research and development, and in particular relates to a preparation method for and application of bismuth tungstate-graphene-conductive hydrogel. The present application provides a method for preparing bismuth tungstate-graphene-conductive hydrogel, comprising: preparation of bismuth tungstate by hydrothermal reaction, ultrasonic peeling, preparation of graphene quantum dots, laser ablation compounding, cross-linking polymerization, aniline immersion, and secondary polymerization. The present application also provides application of the product obtained by the preparation method in an electrolysis catalyst. The introduction of graphene quantum dots increases the active sites of bismuth tungstate so as to improve electrocatalytic performance, and the combination with conductive gel enables the bismuth tungstate-graphene to be further dispersed uniformly, so as to prevent agglomeration of the catalyst, increase the catalytic area of the catalyst, and facilitate the recovery of the gel after the catalysis is completed, such that the technical defect in the prior art that the catalyst used for photoelectric degradation or the cathode hydrogen evolution reaction of electrolyzed water has poor catalytic performance and cannot be recovered.

Description

一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用Preparation method and application of bismuth tungstate-graphene-conductive hydrogel
本申请要求于2019年10月15日提交中国专利局、申请号为201910980260.2、申请名称为“一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application requires the priority of the Chinese patent application submitted to the Chinese Patent Office on October 15, 2019, the application number is 201910980260.2, and the application title is "A preparation method and application of bismuth tungstate-graphene-conductive hydrogel" Right, the entire contents of which are incorporated in this application by reference.
技术领域Technical field
本申请属于电解催化剂研发技术领域，尤其涉及一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用。This application belongs to the technical field of electrolysis catalyst research and development, and in particular relates to a preparation method and application of bismuth tungstate-graphene-conductive hydrogel.
背景技术Background technique
环境与能源问题是人类面临的一重大问题，为了实现人类资源的可持续发展，我们需要致力于发展清洁能源***，减少污染物排放以保护生态环境。可再生能源包括有太阳能、风能、氢能、生物能等。Environmental and energy issues are a major issue facing mankind. In order to achieve the sustainable development of human resources, we need to devote ourselves to the development of a clean energy system and reduce pollutant emissions to protect the ecological environment. Renewable energy includes solar energy, wind energy, hydrogen energy, and biomass energy.
氢能是一种清洁的可再生染料，氢气的燃烧能够提供相较于一般化石燃料三倍的能量，同时产物无污染，具有零污染物排放，可循环利用等优点。自电解水技术被首次报道以来，该方法已经得到了广泛的关注与研究。利用供过于求的部分电能实现分解水产生氢气，可作为一次能源直接供应使用，同时也可将氢气存储用于燃料电池等二次能源应用领域。Hydrogen energy is a clean and renewable dye. The combustion of hydrogen can provide three times the energy compared to ordinary fossil fuels. At the same time, the product is pollution-free, has zero pollutant emissions, and can be recycled. Since the water electrolysis technology was first reported, this method has received extensive attention and research. Part of the oversupply of electricity can be used to split water to produce hydrogen, which can be used as a direct supply of primary energy, and hydrogen can also be stored for secondary energy applications such as fuel cells.
技术问题technical problem
但是，电解水的阴极析氢反应(HER,hydrogen evolution reaction)具有较高的动力学势垄，导致传统的HER反应需要在较高的过电势下进行，消耗过高的电能，所以需要寻找合适的催化剂降低电势，提高氢气析出效率。铂基贵金属是HER最为理想的电催化剂，但铂基材料受限于价格昂贵，储量低等问题，在应用上存在着较大的限制。However, the cathode hydrogen evolution reaction (HER, hydrogen evolution reaction) of electrolyzed water has a high kinetic potential. As a result, the traditional HER reaction needs to be carried out at a higher overpotential and consumes too much electrical energy, so it is necessary to find a suitable one. The catalyst reduces the electric potential and improves the efficiency of hydrogen precipitation. Platinum-based precious metals are the most ideal electrocatalysts for HER, but platinum-based materials are limited by their high price and low reserves, and there are relatively large limitations in their applications.
现有技术中，由于钨酸铋(Bi 2WO 6)的层状结构能够能促进光生电子－空穴的分离，也有利于离子在层间的传输，具有较好的物理化学性能，如铁电、热释电、光降解、压电、非线性介电极化和发光性能 等。然而，单一的Bi 2WO 6在光降解中存在着不足，它的可见光响应范围有限，光生电子与空穴的复合率较高。同时，在电解反应结束后，无法将催化剂回收，造成了催化剂的浪费及带来环境污染。 In the prior art, because the layered structure of bismuth tungstate (Bi 2 WO 6 ) can promote the separation of photogenerated electrons and holes, it is also conducive to the transport of ions between layers, and has good physical and chemical properties, such as iron Electricity, pyroelectricity, photodegradation, piezoelectricity, nonlinear dielectric polarization and luminescence properties, etc. However, a single Bi 2 WO 6 has shortcomings in photodegradation, its visible light response range is limited, and the recombination rate of photogenerated electrons and holes is relatively high. At the same time, after the electrolysis reaction is completed, the catalyst cannot be recovered, resulting in waste of the catalyst and environmental pollution.
因此，研发出一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用，用于解决现有技术中，用于电解水阴极析氢反应的催化剂，存在着催化性能差及无法回收的的技术缺陷，成为了本领域技术人员亟待解决的问题。Therefore, a method for preparing bismuth tungstate-graphene-conductive hydrogel and its application have been developed to solve the problem of poor catalytic performance and unrecoverable catalysts used in the cathode hydrogen evolution reaction of electrolyzed water in the prior art. The technical shortcoming of has become an urgent problem to be solved by those skilled in the art.
发明内容Summary of the invention
有鉴于此，本申请提供了一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用，用于解决现有技术中，用于电解水阴极析氢反应及用于环境污染降解的的催化剂存在着催化性能差及无法回收的的技术缺陷。In view of this, the present application provides a preparation method and application of bismuth tungstate-graphene-conductive hydrogel, which is used to solve the problems in the prior art for the cathodic hydrogen evolution reaction of electrolyzed water and the degradation of environmental pollution. The catalyst has the technical defects of poor catalytic performance and unrecoverable.
本申请提供了一种钨酸铋-石墨烯-导电水凝胶的制备方法，所述制备方法为：This application provides a preparation method of bismuth tungstate-graphene-conductive hydrogel, the preparation method is:
步骤一、水热反应制备钨酸铋：钨酸钠、硝酸铋与CTAB混和后溶于水中，搅拌后进行水热反应，所述水热反应结束后依次经洗涤和干燥，得片层钨酸铋；Step 1. Hydrothermal reaction to prepare bismuth tungstate: sodium tungstate, bismuth nitrate and CTAB are mixed and dissolved in water, stirred and then hydrothermally reacted. After the hydrothermal reaction is completed, they are washed and dried sequentially to obtain lamellar tungstic acid bismuth;
步骤二、超声剥离：所述片层钨酸铋溶解后超声剥离，得分散二维钨酸铋纳米片；Step 2. Ultrasonic peeling: the lamellae are dissolved and then ultrasonically peeled to obtain dispersed two-dimensional bismuth tungstate nanosheets;
步骤三、石墨烯量子点制备：石墨烯溶解后，激光处理，得石墨烯量子点；Step 3. Preparation of graphene quantum dots: After the graphene is dissolved, laser processing is performed to obtain graphene quantum dots;
步骤四、激光溶蚀复合：所述分散二维钨酸铋纳米片与所述石墨烯量子点混合，进行激光溶蚀复合，得石墨烯-钨酸铋；Step 4. Laser ablation composite: the dispersed two-dimensional bismuth tungstate nanosheets are mixed with the graphene quantum dots to perform laser ablation composite to obtain graphene-bismuth tungstate;
步骤五、交联聚合：石墨烯-钨酸铋、丙烯酰胺溶液、交联剂与引发剂混合后，聚合得第五产物；Step 5. Cross-linking polymerization: graphene-bismuth tungstate, acrylamide solution, cross-linking agent and initiator are mixed to polymerize to obtain the fifth product;
步骤六、苯胺浸入：所述第五产物与苯胺溶液混合，静置得第六产物；Step 6. Aniline immersion: the fifth product is mixed with the aniline solution, and the sixth product is obtained by standing still;
步骤七、二次聚合：所述第六产物与引发剂溶液混合，聚合得钨酸铋-石墨烯-聚丙烯酰胺-聚苯胺导电水凝胶产品。Step 7. Secondary polymerization: The sixth product is mixed with the initiator solution and polymerized to obtain a conductive hydrogel product of bismuth tungstate-graphene-polyacrylamide-polyaniline.
优选地，以摩尔份计，钨酸铋、石墨烯、丙烯酰胺及苯胺的投料比为(0.01～0.05):(0.003～0.015):(1～5):(0.1～0.5)。Preferably, the feed ratio of bismuth tungstate, graphene, acrylamide and aniline is (0.01～0.05):(0.003～0.015):(1～5):(0.1～0.5) in mole parts.
优选地，所述制备方法还包括：除杂；Preferably, the preparation method further includes: removing impurities;
所述除杂的方法为：步骤七所得导电水凝胶粗品于水中静置得纯品。The method for removing impurities is: the crude conductive hydrogel obtained in step 7 is allowed to stand still in water to obtain a pure product.
优选地，步骤一中，所述水热反应的温度为120～160℃，所述水热反应的时间为18～24h；Preferably, in step 1, the temperature of the hydrothermal reaction is 120-160°C, and the time of the hydrothermal reaction is 18-24h;
步骤二中，所述超声分散的频率为20～25KHz，所述超声分散的时间为1～3h。In the second step, the frequency of the ultrasonic dispersion is 20-25 KHz, and the time of the ultrasonic dispersion is 1 to 3 h.
优选地，步骤三中，所述激光处理的处理时间为1～3h，所述激光处理的激光波长为10～760nm，所述激光处理的脉冲频率为10～100Hz，所述激光处理的单脉冲能量为200～500mJ。Preferably, in step 3, the processing time of the laser treatment is 1 to 3 hours, the laser wavelength of the laser treatment is 10 to 760 nm, the pulse frequency of the laser treatment is 10 to 100 Hz, and the single pulse of the laser treatment The energy is 200～500mJ.
优选地，步骤四中，所述激光溶蚀复合的作用时间为30～60min，所述激光溶蚀复合的激光波长为10～760nm，所述激光溶蚀复合的脉冲频率为10～100Hz，所述激光溶蚀复合的单脉冲能量为20～50mJ。Preferably, in step 4, the action time of the laser ablation recombination is 30-60 min, the laser wavelength of the laser ablation recombination is 10 to 760 nm, the pulse frequency of the laser ablation recombination is 10-100 Hz, and the laser ablation recombination The combined single pulse energy is 20-50mJ.
优选地，步骤五中，所述丙烯酰胺溶液的浓度为1～5mol/L，所述丙烯酰胺溶液的溶剂为去离子水；Preferably, in step 5, the concentration of the acrylamide solution is 1 to 5 mol/L, and the solvent of the acrylamide solution is deionized water;
步骤六中，所述苯胺溶液的浓度为0.3～1.5mol/L，所述苯胺溶液的溶剂选自：盐酸、去离子水中的任何一种或多种；In step 6, the concentration of the aniline solution is 0.3 to 1.5 mol/L, and the solvent of the aniline solution is selected from any one or more of hydrochloric acid and deionized water;
步骤七中，所述引发剂与丙烯酰胺的摩尔比为1:(200～600)。In step 7, the molar ratio of the initiator to acrylamide is 1: (200-600).
优选地，所述引发剂选自：过硫酸铵、过硫酸钾以及N,N,N′,N′-四甲基乙二胺中的任何一种或多种；Preferably, the initiator is selected from any one or more of ammonium persulfate, potassium persulfate and N,N,N′,N′-tetramethylethylenediamine;
所述交联剂选自：N，N-亚甲基双丙烯酰胺、偶氮二异丁氰以及N,N′-二异丙基双丙烯酰胺中的任何一种或多种。The crosslinking agent is selected from any one or more of N,N-methylenebisacrylamide, azobisisobutyronitrile and N,N'-diisopropylbisacrylamide.
优选地，步骤一中，所述聚合的方法为：60～80℃条件下水浴/油浴加热聚合10～30min；Preferably, in step 1, the polymerization method is: water bath/oil bath heating polymerization at 60-80°C for 10-30 minutes;
步骤六中，所述静置的温度为室温，所述静置的时间为6～12h；In step 6, the standing temperature is room temperature, and the standing time is 6-12h;
步骤七中，所述聚合的方法为：室温条件下静置聚合4～8h。In step 7, the polymerization method is: standing for polymerization at room temperature for 4 to 8 hours.
本申请还提供了一种包括以上任意一项所述的制备方法得到的产品在电解催化剂中的应用。The application also provides an application of the product obtained by the preparation method described in any one of the above in the electrolysis catalyst.
综上所述，本申请提供了一种钨酸铋-石墨烯-导电水凝胶的制备方法，为：水热反应制备钨酸铋、超声剥离、石墨烯量子点制备、激光溶蚀复合、交联聚合、苯胺浸及二次聚合。本申请还提供了一种上述制备方法得到的产品在电解催化剂中的应用。本申请提供的技术方案中，通过引入石墨烯量子点，增加钨酸铋的活性位点以提高电催化性能；进一步地，与导电凝胶结合，基于导电凝胶的电学性能及三维结构，使钨酸铋-石墨烯进一步均匀分散，防止催化剂团聚，增大催化剂的催化面积，并且凝胶在催化完成后，回收方便。本申请提供的一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用，解决了现有技术中，用于电解水阴极析氢反应的催化剂，存在着催化性能差及无法回收的的技术缺陷。In summary, this application provides a method for preparing bismuth tungstate-graphene-conductive hydrogel, which includes: preparing bismuth tungstate by hydrothermal reaction, ultrasonic peeling, preparing graphene quantum dots, laser ablation composite, cross-linking Union polymerization, aniline immersion and secondary polymerization. The application also provides an application of the product obtained by the above preparation method in an electrolysis catalyst. In the technical solution provided in this application, graphene quantum dots are introduced to increase active sites of bismuth tungstate to improve electrocatalytic performance; further, combined with conductive gel, based on the electrical properties and three-dimensional structure of conductive gel, The bismuth tungstate-graphene is further uniformly dispersed to prevent agglomeration of the catalyst, increase the catalytic area of the catalyst, and the gel is easy to recover after the catalysis is completed. The preparation method and application of bismuth tungstate-graphene-conductive hydrogel provided in the present application solve the problem of poor catalytic performance and unrecyclable catalysts used in the cathode hydrogen evolution reaction of electrolyzed water in the prior art. Technical flaws.
附图说明Description of the drawings
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。In order to more clearly describe the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only These are the embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on the provided drawings without creative work.
图1本申请提供的一种钨酸铋-石墨烯-导电水凝胶的制备方法的流程示意图；Fig. 1 is a schematic flow chart of a method for preparing bismuth tungstate-graphene-conductive hydrogel provided by the present application;
图2为实施例4中，线性扫描伏安曲线的结果示意图；2 is a schematic diagram of the result of linear scanning the volt-ampere curve in Example 4;
图3为实施例5中，所制得的钨酸铋-石墨烯-导电水凝胶与对照品对有机染料Rh B降解效率的结果示意图；3 is a schematic diagram of the degradation efficiency of the organic dye Rh B by the prepared bismuth tungstate-graphene-conductive hydrogel and the reference substance in Example 5;
其中，指定图1为摘要附图。Among them, Figure 1 is designated as the abstract drawing.
具体实施方式Detailed ways
本申请提供了一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用，用于解决现有技术中，用于电解水阴极析氢反应的催化剂，存在着催化性能差及无法回收的的技术缺陷。This application provides a method for preparing bismuth tungstate-graphene-conductive hydrogel and its application, which is used to solve the problem of poor catalytic performance and unrecyclable catalyst used in the cathode hydrogen evolution reaction of electrolyzed water in the prior art. Of technical defects.
下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of this application.
为了更详细说明本申请，下面结合实施例对本申请提供的一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用，进行具体地描述。In order to explain this application in more detail, the following describes the preparation method and application of a bismuth tungstate-graphene-conductive hydrogel provided in this application in detail with reference to examples.
实施例1Example 1
步骤一、称取1mmol钨酸钠(Na 2WO 4·2H 2O)、2mmol硝酸铋(Bi(NO 3) 3·5H 2O)与0.05gCTAB混和后溶于80ml去离子水中，于60℃、以500r/min的转速搅拌30min至均匀，转移至水热釜进行水热反应，其中，水热反应的温度为120℃，水热反应的时间为20h。水热反应结束后，依次经洗涤和干燥，得片层钨酸铋；其中，洗涤的方法为水和乙醇分别洗涤3次，干燥的方法为：60℃干燥10h。 Step 1. Weigh out 1mmol of sodium tungstate (Na 2 WO 4 ·2H 2 O), 2mmol of bismuth nitrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.05g of CTAB, mix them and dissolve in 80ml of deionized water at 60℃ , Stir at 500r/min for 30min until uniform, transfer to a hydrothermal kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 120°C, and the time of the hydrothermal reaction is 20h. After the hydrothermal reaction is completed, the lamellar bismuth tungstate is obtained by successive washing and drying; wherein the washing method is washing with water and ethanol 3 times, and the drying method is: drying at 60°C for 10 hours.
步骤二、取上一步所得片层钨酸铋400mg，溶于200ml去离子水中，待溶解后超声剥离，得分散二维钨酸铋纳米片；其中，超声分散的频率为20KHz，超声分散的时间为1h。Step 2. Take 400 mg of bismuth tungstate obtained in the previous step, dissolve it in 200 ml of deionized water, and ultrasonically peel off after dissolution to obtain dispersed two-dimensional bismuth tungstate nanosheets; wherein the frequency of ultrasonic dispersion is 20KHz, and the time of ultrasonic dispersion For 1h.
步骤三、称取5mg石墨烯溶于10ml去离子水中，以53KHz的频率超声分散10min使石墨烯充分溶解；溶解后，用波长为532nm、脉冲频率为10Hz、单脉冲能量为200mJ进行激光处理3h，得石墨烯量子点。Step 3. Weigh 5mg of graphene and dissolve it in 10ml of deionized water, and disperse the graphene by ultrasonic dispersion at 53KHz for 10min to fully dissolve the graphene; after dissolution, perform laser treatment with a wavelength of 532nm, a pulse frequency of 10Hz, and a single pulse energy of 200mJ for 3h , Get graphene quantum dots.
步骤四、取步骤二所得分散二维钨酸铋纳米片5ml与步骤三所得石墨烯量子点溶液混合，在实际制备时，为使得二者充分混合，可使用超声分散的方法使二者充分混合。混合均匀后，进行激光溶蚀复合，其中，激光溶蚀复合的作用时间为60min，激光溶蚀复合的激光波长 为10nm，所述激光溶蚀复合的脉冲频率为100Hz，所述激光溶蚀复合的单脉冲能量为10mJ，得石墨烯-钨酸铋。本步骤中，分散二维钨酸铋纳米片与石墨烯量子点的质量比为2:1。Step 4. Take 5ml of the dispersed two-dimensional bismuth tungstate nanosheets obtained in step 2 and mix with the graphene quantum dot solution obtained in step 3. In the actual preparation, in order to make the two fully mixed, the ultrasonic dispersion method can be used to make the two fully mixed . After mixing uniformly, perform laser ablation recombination, where the action time of the laser ablation recombination is 60 min, the laser wavelength of the laser ablation recombination is 10 nm, the pulse frequency of the laser ablation recombination is 100 Hz, and the single pulse energy of the laser ablation recombination is 10mJ, get graphene-bismuth tungstate. In this step, the mass ratio of the dispersed two-dimensional bismuth tungstate nanosheets to the graphene quantum dots is 2:1.
步骤五、配制1mol/L的丙烯酰胺(AM)溶液，后加入石墨烯-钨酸铋、交联剂及引发剂(0.05mol/L)混合均匀，在60℃水浴温度下聚合30min，得到透明的果冻状水凝胶，即为第五产物。本步骤中，交联剂为N,N-亚甲基双丙烯酰胺，引发剂为过硫酸铵；丙烯酰胺、交联剂与引发剂的摩尔投料比为1:0.005:0.05。Step 5. Prepare 1mol/L acrylamide (AM) solution, then add graphene-bismuth tungstate, crosslinking agent and initiator (0.05mol/L) to mix uniformly, polymerize at 60℃ water bath temperature for 30min, and get transparent The jelly-like hydrogel is the fifth product. In this step, the crosslinking agent is N,N-methylenebisacrylamide, and the initiator is ammonium persulfate; the molar feed ratio of acrylamide, crosslinking agent and initiator is 1:0.005:0.05.
步骤六、第五产物浸入含有苯胺(ANI)的盐酸(苯胺浓度1.5mol/L)溶液中，于室温条件下静置6h，使苯胺单体进入第五产物，即为第六产物。Step 6. The fifth product is immersed in a hydrochloric acid (aniline concentration of 1.5 mol/L) solution containing aniline (ANI) and allowed to stand at room temperature for 6 hours to allow the aniline monomer to enter the fifth product, which is the sixth product.
步骤七、第六产物浸入引发剂的水溶液中，于室温条件下4h引发苯胺单体聚合，形成钨酸铋-石墨烯-PAM-PANI导电水凝胶粗品，所得导电水凝胶粗品置于大量的去离子水中，去除低聚物及未反应的苯胺单体，得纯净聚丙烯酰胺-聚苯胺复合水凝胶产品。本步骤中，引发剂为过硫酸铵；引发剂与步骤二中苯胺的摩尔投料比为1:1。Step 7. The sixth product is immersed in the initiator aqueous solution, and the aniline monomer is polymerized at room temperature for 4 hours to form the crude bismuth tungstate-graphene-PAM-PANI conductive hydrogel, and the obtained crude conductive hydrogel is placed in a large amount The oligomer and unreacted aniline monomer are removed from the deionized water to obtain a pure polyacrylamide-polyaniline composite hydrogel product. In this step, the initiator is ammonium persulfate; the molar feed ratio of the initiator to the aniline in step two is 1:1.
本实施例中，以摩尔份计，钨酸铋、石墨烯、丙烯酰胺及苯胺的投料比为0.03:0.003:5:0.1。In this embodiment, the feed ratio of bismuth tungstate, graphene, acrylamide, and aniline is 0.03:0.003:5:0.1 in terms of parts by mole.
实施例2Example 2
步骤一、称取1mmol钨酸钠(Na 2WO 4·2H 2O)、2mmol硝酸铋(Bi(NO 3) 3·5H 2O)与0.05gCTAB混和后溶于80ml去离子水中，于70℃、以800r/min的转速搅拌10min至均匀，转移至水热釜进行水热反应，其中，水热反应的温度为130℃，水热反应的时间为24h。水热反应结束后，依次经洗涤和干燥，得片层钨酸铋；其中，洗涤的方法为水和乙醇分别洗涤3次，干燥的方法为：60℃干燥10h。 Step 1. Weigh out 1mmol of sodium tungstate (Na 2 WO 4 ·2H 2 O), 2mmol of bismuth nitrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.05g of CTAB, mix them and dissolve in 80ml of deionized water at 70℃ , Stir at 800r/min for 10 minutes until uniform, transfer to a hydrothermal kettle for hydrothermal reaction, where the temperature of the hydrothermal reaction is 130°C, and the time of the hydrothermal reaction is 24h. After the hydrothermal reaction is completed, the lamellar bismuth tungstate is obtained by successive washing and drying; wherein the washing method is washing with water and ethanol 3 times, and the drying method is: drying at 60°C for 10 hours.
步骤二、取上一步所得片层钨酸铋400mg，溶于200ml去离子水中，待溶解后超声剥离，得分散二维钨酸铋纳米片；其中，超声分散的频率为25KHz，超声分散的时间为2h。Step 2. Take 400 mg of the lamella bismuth tungstate obtained in the previous step, dissolve it in 200ml deionized water, and ultrasonically peel off after dissolution to obtain dispersed two-dimensional bismuth tungstate nanosheets; wherein the frequency of ultrasonic dispersion is 25KHz, and the time of ultrasonic dispersion For 2h.
步骤三、称取10mg石墨烯溶于10ml去离子水中，以53KHz的频率超声分散10min使石墨烯充分溶解；溶解后，用波长为10nm、脉冲频率为100Hz、单脉冲能量为300mJ进行激光处理2h，得石墨烯量子点。Step 3. Weigh 10mg of graphene and dissolve it in 10ml of deionized water, and disperse the graphene by ultrasonic dispersion at 53KHz for 10min to fully dissolve the graphene; after dissolution, laser treatment with a wavelength of 10nm, a pulse frequency of 100Hz, and a single pulse energy of 300mJ for 2h , Get graphene quantum dots.
步骤四、取步骤二所得分散二维钨酸铋纳米片5ml与步骤三所得石墨烯量子点溶液混合，在实际制备时，为使得二者充分混合，可使用超声分散的方法使二者充分混合。混合均匀后，进行激光溶蚀复合，其中，激光溶蚀复合的作用时间为45min，激光溶蚀复合的激光波长为532nm，所述激光溶蚀复合的脉冲频率为10Hz，所述激光溶蚀复合的单脉冲能量为50mJ，得石墨烯-钨酸铋。本步骤中，分散二维钨酸铋纳米片与石墨烯量子点的质量比为1:1。Step 4. Take 5ml of the dispersed two-dimensional bismuth tungstate nanosheets obtained in step 2 and mix with the graphene quantum dot solution obtained in step 3. In the actual preparation, in order to make the two fully mixed, the ultrasonic dispersion method can be used to make the two fully mixed . After mixing uniformly, perform laser ablation recombination, where the action time of the laser ablation recombination is 45 min, the laser wavelength of the laser ablation recombination is 532 nm, the pulse frequency of the laser ablation recombination is 10 Hz, and the single pulse energy of the laser ablation recombination is 50mJ, graphene-bismuth tungstate is obtained. In this step, the mass ratio of the dispersed two-dimensional bismuth tungstate nanosheets to the graphene quantum dots is 1:1.
步骤五、配制3mol/L的丙烯酰胺(AM)溶液，后加入石墨烯-钨酸铋、交联剂及引发剂(0.05mol/L)混合均匀，在60℃水浴温度下聚合30min，得到透明的果冻状水凝胶，即为第五产物。本步骤中，交联剂为偶氮二异丁氰，引发剂为过硫酸钾；丙烯酰胺、交联剂与引发剂的摩尔投料比为1:0.01:0.1。Step 5. Prepare 3mol/L acrylamide (AM) solution, then add graphene-bismuth tungstate, cross-linking agent and initiator (0.05mol/L) to mix uniformly, polymerize at 60℃ water bath temperature for 30min, get transparent The jelly-like hydrogel is the fifth product. In this step, the crosslinking agent is azobisisobutyl cyanide, and the initiator is potassium persulfate; the molar feed ratio of acrylamide, crosslinking agent and initiator is 1:0.01:0.1.
步骤六、第五产物浸入含有苯胺(ANI)的盐酸(苯胺浓度0.3mol/L)溶液中，于室温条件下静置10h，使苯胺单体进入第五产物，即为第六产物。Step 6. The fifth product is immersed in a hydrochloric acid (aniline concentration of 0.3 mol/L) solution containing aniline (ANI), and allowed to stand at room temperature for 10 hours to allow the aniline monomer to enter the fifth product, which is the sixth product.
步骤七、第六产物浸入引发剂的水溶液中，于室温条件下6h引发苯胺单体聚合，形成钨酸铋-石墨烯-PAM-PANI导电水凝胶粗品，所得导电水凝胶粗品置于大量的去离子水中，去除低聚物及未反应的苯胺单体，得纯净钨酸铋-石墨烯-导电水凝胶产品。本步骤中，引发剂为过硫酸钾；引发剂与步骤六中苯胺的摩尔投料比为1:1。Step 7. The sixth product is immersed in the initiator aqueous solution, and the aniline monomer is polymerized at room temperature for 6 hours to form the crude bismuth tungstate-graphene-PAM-PANI conductive hydrogel, and the obtained crude conductive hydrogel is placed in a large amount The oligomers and unreacted aniline monomers are removed from the deionized water to obtain pure bismuth tungstate-graphene-conductive hydrogel product. In this step, the initiator is potassium persulfate; the molar feed ratio of the initiator to the aniline in step 6 is 1:1.
本实施例中，以摩尔份计，钨酸铋、石墨烯、丙烯酰胺及苯胺的投料比为0.055:0.015:1:0.2。In this embodiment, the feed ratio of bismuth tungstate, graphene, acrylamide, and aniline is 0.055:0.015:1:0.2 in terms of parts by mole.
实施例3Example 3
步骤一、称取1mmol钨酸钠(Na 2WO 4·2H 2O)、2mmol硝酸铋 (Bi(NO 3) 3·5H 2O)与0.05gCTAB混和后溶于80ml去离子水中，于80℃、以1000r/min的转速搅拌20min至均匀，转移至水热釜进行水热反应，其中，水热反应的温度为160℃，水热反应的时间为18h。水热反应结束后，依次经洗涤和干燥，得片层钨酸铋；其中，洗涤的方法为水和乙醇分别洗涤3次，干燥的方法为：60℃干燥10h。 Step 1. Weigh out 1mmol of sodium tungstate (Na 2 WO 4 ·2H 2 O), 2mmol of bismuth nitrate (Bi(NO 3 ) 3 ·5H 2 O) and 0.05g of CTAB, mix them and dissolve in 80ml of deionized water at 80℃ , Stir at a speed of 1000r/min for 20 minutes until uniform, transfer to a hydrothermal kettle for hydrothermal reaction, where the temperature of the hydrothermal reaction is 160°C, and the time of the hydrothermal reaction is 18h. After the hydrothermal reaction is completed, the lamellar bismuth tungstate is obtained by successive washing and drying; wherein the washing method is washing with water and ethanol 3 times, and the drying method is: drying at 60°C for 10 hours.
步骤二、取上一步所得片层钨酸铋400mg，溶于200ml去离子水中，待溶解后超声剥离，得分散二维钨酸铋纳米片；其中，超声分散的频率为22KHz，超声分散的时间为3h。Step 2. Take 400 mg of bismuth tungstate obtained in the previous step, dissolve it in 200 ml of deionized water, and ultrasonically peel off after dissolution to obtain dispersed two-dimensional bismuth tungstate nanosheets; wherein the frequency of ultrasonic dispersion is 22KHz, and the time of ultrasonic dispersion For 3h.
步骤三、称取20mg石墨烯溶于10ml去离子水中，以53KHz的频率超声分散10min使石墨烯充分溶解；溶解后，用波长为760nm、脉冲频率为30Hz、单脉冲能量为500mJ进行激光处理1h，得石墨烯量子点。Step 3. Weigh 20mg of graphene and dissolve it in 10ml of deionized water, and dissolve the graphene by ultrasonic dispersion at a frequency of 53KHz for 10min to fully dissolve the graphene; after dissolution, perform laser treatment with a wavelength of 760nm, a pulse frequency of 30Hz, and a single pulse energy of 500mJ for 1h , Get graphene quantum dots.
步骤四、取步骤二所得分散二维钨酸铋纳米片5ml与步骤三所得石墨烯量子点溶液混合，在实际制备时，为使得二者充分混合，可使用超声分散的方法使二者充分混合。混合均匀后，进行激光溶蚀复合，其中，激光溶蚀复合的作用时间为30min，激光溶蚀复合的激光波长为532nm，所述激光溶蚀复合的脉冲频率为50Hz，所述激光溶蚀复合的单脉冲能量为40mJ，得石墨烯-钨酸铋。本步骤中，分散二维钨酸铋纳米片与石墨烯量子点的质量比为2:1。Step 4. Take 5ml of the dispersed two-dimensional bismuth tungstate nanosheets obtained in step 2 and mix with the graphene quantum dot solution obtained in step 3. In the actual preparation, in order to make the two fully mixed, the ultrasonic dispersion method can be used to make the two fully mixed . After mixing uniformly, perform laser ablation recombination, where the action time of the laser ablation recombination is 30 min, the laser wavelength of the laser ablation recombination is 532 nm, the pulse frequency of the laser ablation recombination is 50 Hz, and the single pulse energy of the laser ablation recombination is 40mJ, graphene-bismuth tungstate is obtained. In this step, the mass ratio of the dispersed two-dimensional bismuth tungstate nanosheets to the graphene quantum dots is 2:1.
步骤五、配制5mol/L的丙烯酰胺(AM)溶液，后加入石墨烯-钨酸铋、交联剂及引发剂(0.05mol/L)混合均匀，在80℃水浴温度下聚合30min，得到透明的果冻状水凝胶，即为第五产物。本实施例中，交联剂为N,N′-二异丙基双丙烯酰胺，引发剂为N,N,N′,N′-四甲基乙二胺；丙烯酰胺、交联剂与引发剂的摩尔投料比为1:0.02:0.2。Step 5. Prepare 5mol/L acrylamide (AM) solution, then add graphene-bismuth tungstate, cross-linking agent and initiator (0.05mol/L) to mix uniformly, polymerize at 80℃ water bath temperature for 30min, get transparent The jelly-like hydrogel is the fifth product. In this embodiment, the crosslinking agent is N,N'-diisopropyl bisacrylamide, and the initiator is N,N,N',N'-tetramethylethylenediamine; acrylamide, crosslinking agent and initiator The molar feed ratio of the agent is 1:0.02:0.2.
步骤六、第一产物浸入含有苯胺(ANI)的盐酸(苯胺浓度1mol/L)溶液中，于室温条件下静置12h，使苯胺单体进入第五产物，即为第六产物。Step 6. The first product is immersed in a hydrochloric acid (aniline concentration of 1 mol/L) solution containing aniline (ANI), and allowed to stand at room temperature for 12 hours to allow the aniline monomer to enter the fifth product, which is the sixth product.
步骤七、第六产物浸入引发剂的水溶液中，于室温条件下8h引发苯胺单体聚合，形成钨酸铋-石墨烯-PAM-PANI导电水凝胶粗品，所得导电水凝胶粗品置于大量的去离子水中，去除低聚物及未反应的苯胺单体，得纯净钨酸铋-石墨烯-导电水凝胶产品。本步骤中，引发剂为N,N,N′,N′-四甲基乙二胺；引发剂与步骤六中苯胺的摩尔投料比为1：1。Step 7. The sixth product is immersed in the initiator aqueous solution, and the aniline monomer is polymerized at room temperature for 8 hours to form the crude bismuth tungstate-graphene-PAM-PANI conductive hydrogel, and the obtained crude conductive hydrogel is placed in a large amount The oligomers and unreacted aniline monomers are removed from the deionized water to obtain pure bismuth tungstate-graphene-conductive hydrogel product. In this step, the initiator is N,N,N',N'-tetramethylethylenediamine; the molar feed ratio of the initiator to the aniline in step six is 1:1.
本实施例中，以摩尔份计，钨酸铋、石墨烯、丙烯酰胺及苯胺的投料比为0.01:0.01:3:0.5。In this embodiment, the feed ratio of bismuth tungstate, graphene, acrylamide, and aniline is 0.01:0.01:3:0.5 in terms of parts by mole.
在实施例1～3提供的制备方法中，首先进行钨酸铋的高效高纯合成，但此时，所制得的钨酸铋为片层结构，其堆叠较为严重，无法进行有效催化。在步骤二中，借助超声作用，对聚集态的钨酸铋进行超声，使其得到有效的分散，得到了分散的二维钨酸铋纳米片，增加了钨酸铋的暴露面积，提供了更多的活性面积。In the preparation methods provided in Examples 1 to 3, the high-efficiency and high-purity synthesis of bismuth tungstate is firstly performed, but at this time, the prepared bismuth tungstate has a lamellar structure, and its stacking is serious and cannot be effectively catalyzed. In step two, with the help of ultrasound, the aggregated bismuth tungstate is sonicated to effectively disperse it, and dispersed two-dimensional bismuth tungstate nanosheets are obtained, which increases the exposed area of bismuth tungstate and provides more More active area.
步骤三中，所制得的石墨烯量子点是零维的少层石墨烯材料，在三个维度均处于纳米级别，也就是的石墨烯量子点可表现出一些独特的性能，如：强量子局限效应、边缘效应、良好的电子传到能力及上转换发光特性等；同时，石墨烯量子点还具有无毒、价格低廉的良好特性，在步骤四中，石墨烯量子点与二维钨酸铋纳米片结合，石墨烯量子点可作为活性位点以提高二维钨酸铋的催化活性。In step three, the obtained graphene quantum dots are zero-dimensional few-layer graphene materials, which are at the nanometer level in three dimensions, that is, graphene quantum dots can exhibit some unique properties, such as strong quantum Confinement effect, edge effect, good electron transfer ability and up-conversion luminescence characteristics, etc.; at the same time, graphene quantum dots also have good characteristics of non-toxicity and low price. In step four, graphene quantum dots and two-dimensional tungstic acid Combined with bismuth nanosheets, graphene quantum dots can be used as active sites to improve the catalytic activity of two-dimensional bismuth tungstate.
步骤五中，将制成的钨酸铋-石墨烯进入聚丙烯酰胺的立体三维结构，在步骤六和步骤七中，进一步地将苯胺引入并聚合，导电水凝胶作为催化剂载体，不仅能够实现催化剂的均匀分散，增大催化剂的活性面积；同时，导电水凝胶还具有良好的电学性能，与催化剂结合形成力电结合催化体系，进一步综合提升了催化剂的催化性能。同时，凝胶状载体在使用后便于催化剂的回收，实现了催化剂的回收再利用。In step five, the prepared bismuth tungstate-graphene is incorporated into the three-dimensional structure of polyacrylamide. In steps six and seven, aniline is further introduced and polymerized, and the conductive hydrogel is used as a catalyst carrier, which can not only achieve The uniform dispersion of the catalyst increases the active area of the catalyst; at the same time, the conductive hydrogel also has good electrical properties, and it combines with the catalyst to form a force-electric combined catalytic system, which further comprehensively improves the catalytic performance of the catalyst. At the same time, the gel-like carrier facilitates the recovery of the catalyst after use, and realizes the recovery and reuse of the catalyst.
实施例4Example 4
本实施例为测定实施例1～3制得的石墨烯-钨酸铋-导电水凝胶催化性能的具体实施例，本实施例中，所使用的对照催化剂为钨酸铋粉末。This example is a specific example for measuring the catalytic performance of the graphene-bismuth tungstate-conductive hydrogel prepared in Examples 1 to 3. In this example, the control catalyst used is bismuth tungstate powder.
实验方法experimental method
石墨烯-钨酸铋-导电水凝胶电极制备Preparation of graphene-bismuth tungstate-conductive hydrogel electrode
在实施例1～3de步骤五溶液中放入合适大小的碳布，使得溶液与碳布接触并形成面积为1cm 2的薄凝胶层，不改变之后的步骤，得到石墨烯-钨酸铋-导电水凝胶电极。 Put a carbon cloth of a suitable size in the solution in step 5 of Examples 1 to 3de so that the solution contacts the carbon cloth and forms a thin gel layer with an area of 1 cm 2 without changing the subsequent steps to obtain graphene-bismuth tungstate- Conductive hydrogel electrode.
电化学测试Electrochemical test
在电化学工作站上采用传统三电极体系进行电化学测试，参比电极为饱和甘汞电极，对电极为石墨电极，石墨烯-钨酸铋-导电水凝胶电极为工作电极，0.5mol L -1H 2SO 4溶液为电解液。采用线性扫描伏安法(LSV)，设置扫描范围为-0.2V～-1.2V，扫描速率为5mV s -1，记录线性扫描伏安曲线。 In conventional three-electrode system electrochemical workstation electrochemical test, the reference electrode is a saturated calomel electrode, counter electrode is a graphite electrode, a graphene - bismuth tungstate - conductive hydrogel working electrode, 0.5mol L - 1 H 2 SO 4 solution is the electrolyte. Using linear sweep voltammetry (LSV), set the sweep range from -0.2V to -1.2V, and the sweep rate to 5mV s -1 , and record the linear sweep voltammetry curve.
实验结果Experimental results
从图2可以看出，石墨烯-钨酸铋-导电水凝胶的起始过电位相较于钨酸铋粉末提升14％，经超声后起始过电位相较于钨酸铋粉末可提升27％。It can be seen from Figure 2 that the initial overpotential of graphene-bismuth tungstate-conductive hydrogel is increased by 14% compared with that of bismuth tungstate powder, and the initial overpotential after ultrasound can be increased compared to that of bismuth tungstate powder. 27%.
实施例5Example 5
本实施例为测定实施例1～3制得的石墨烯-钨酸铋-水凝胶催化性能的具体实施例，本实施例中，所使用的对照为不添加石墨烯量子点的钨酸铋-水凝胶催化体系光降解罗丹明B。This example is a specific example for measuring the catalytic performance of the graphene-bismuth tungstate-hydrogel prepared in Examples 1 to 3. In this example, the control used is bismuth tungstate without graphene quantum dots -Hydrogel catalytic system for photodegradation of rhodamine B.
实验方法experimental method
光电催化降解罗丹明B测试Photoelectrocatalytic degradation of rhodamine B test
取含有一定量的石墨烯-钨酸铋光催化剂的水凝胶置于100mL浓度为5mg/L的有机染料Rh B溶液中，避光条件下搅拌120min至催化剂对有机染料RhB达到吸附-脱附平衡。然后在功率为300W的氙灯光源(放置滤光片λ≥420nm)照射下进行可见光催化降解反应，同时对反应容器进行超声(频率53KHz)力学作用。每隔30min取出3mL样品清液测定吸光度，计算得到有机染料RhB降解率。Take the hydrogel containing a certain amount of graphene-bismuth tungstate photocatalyst and place it in 100 mL of the organic dye Rh B solution with a concentration of 5 mg/L, and stir for 120 min under dark conditions until the catalyst reaches the adsorption-desorption of the organic dye RhB balance. Then, the visible light catalytic degradation reaction is carried out under the irradiation of a xenon lamp light source with a power of 300W (placement of the filter λ≥420nm), and the reaction vessel is subjected to ultrasonic (frequency 53KHz) mechanical action at the same time. Take out 3mL sample supernatant every 30min to measure the absorbance, and calculate the degradation rate of organic dye RhB.
实验结果Experimental results
从图3可以看出，经过120min后，石墨烯-钨酸铋-水凝胶降解体系经光照及超声作用其催化降解率达到90.1％。在相同的反应时间 下，相较于不添加石墨烯量子点的钨酸铋水凝胶降解体系，其降解率提高了26.7％，表现出极好的催化降解能力。It can be seen from Figure 3 that after 120 minutes, the degradation rate of the graphene-bismuth tungstate-hydrogel degradation system is 90.1% under the action of light and ultrasound. Under the same reaction time, compared with the bismuth tungstate hydrogel degradation system without graphene quantum dots, its degradation rate is increased by 26.7%, showing excellent catalytic degradation ability.
本发明实施例1～3中，所制得的产品为凝胶状结构，与现有技术中粉末或液体催化剂相比，本发明制得的凝胶在回收时方便快捷，可实现催化剂的快速简便回收。In Examples 1 to 3 of the present invention, the products prepared have a gel-like structure. Compared with powder or liquid catalysts in the prior art, the gel prepared by the present invention is convenient and quick to recover, and can achieve rapid catalyst recovery. Easy to recycle.
综上所述，本申请提供了一种钨酸铋-石墨烯-导电水凝胶的制备方法，为：水热反应制备钨酸铋、超声剥离、石墨烯量子点制备、激光溶蚀复合、交联聚合、苯胺浸及二次聚合。本申请还提供了一种上述制备方法得到的产品在电解催化剂中的应用。本申请提供的技术方案中，通过引入石墨烯量子点，增加钨酸铋的活性位点以提高电催化性能；进一步地，与导电凝胶结合，基于导电凝胶的电学性能及三维结构，使钨酸铋-石墨烯进一步均匀分散，防止催化剂团聚，增大催化剂的催化面积，并且凝胶在催化完成后，回收方便。本申请提供的一种钨酸铋-石墨烯-导电水凝胶的制备方法及其应用，解决了现有技术中，用于电解水阴极析氢反应的催化剂，存在着催化性能差及无法回收的的技术缺陷。In summary, this application provides a method for preparing bismuth tungstate-graphene-conductive hydrogel, which includes: preparing bismuth tungstate by hydrothermal reaction, ultrasonic stripping, preparing graphene quantum dots, laser ablation composite, cross-linking Union polymerization, aniline immersion and secondary polymerization. The application also provides an application of the product obtained by the above preparation method in an electrolysis catalyst. In the technical solution provided in this application, graphene quantum dots are introduced to increase active sites of bismuth tungstate to improve electrocatalytic performance; further, combined with conductive gel, based on the electrical properties and three-dimensional structure of conductive gel, The bismuth tungstate-graphene is further uniformly dispersed to prevent agglomeration of the catalyst, increase the catalytic area of the catalyst, and the gel is easy to recover after the catalysis is completed. The preparation method and application of bismuth tungstate-graphene-conductive hydrogel provided by the present application solve the problem of poor catalytic performance and unrecyclable catalysts used in the cathode hydrogen evolution reaction of electrolyzed water in the prior art. Technical defects.
以上所述仅是本申请的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。The above are only the preferred embodiments of this application. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of this application, several improvements and modifications can be made, and these improvements and modifications are also Should be regarded as the scope of protection of this application.

Claims (10)

  1. 一种钨酸铋-石墨烯-导电水凝胶的制备方法，其特征在于，所述制备方法为：A preparation method of bismuth tungstate-graphene-conductive hydrogel, characterized in that, the preparation method is:
    步骤一、水热反应制备钨酸铋：钨酸钠、硝酸铋与CTAB混和后溶于水中，搅拌后进行水热反应，所述水热反应结束后依次经洗涤和干燥，得片层钨酸铋；Step 1. Hydrothermal reaction to prepare bismuth tungstate: sodium tungstate, bismuth nitrate and CTAB are mixed and dissolved in water, stirred and then undergoes a hydrothermal reaction. After the hydrothermal reaction is completed, they are washed and dried sequentially to obtain lamellar tungstate bismuth;
    步骤二、超声剥离：所述片层钨酸铋溶解后超声剥离，得分散二维钨酸铋纳米片；Step 2. Ultrasonic peeling: the lamellae are dissolved and then ultrasonically peeled to obtain dispersed two-dimensional bismuth tungstate nanosheets;
    步骤三、石墨烯量子点制备：石墨烯溶解后，激光处理，得石墨烯量子点；Step 3. Preparation of graphene quantum dots: After the graphene is dissolved, laser processing is performed to obtain graphene quantum dots;
    步骤四、激光溶蚀复合：所述分散二维钨酸铋纳米片与所述石墨烯量子点混合，进行激光溶蚀复合，得石墨烯-钨酸铋；Step 4. Laser ablation composite: the dispersed two-dimensional bismuth tungstate nanosheets are mixed with the graphene quantum dots to perform laser ablation composite to obtain graphene-bismuth tungstate;
    步骤五、交联聚合：石墨烯-钨酸铋、丙烯酰胺溶液、交联剂与引发剂混合后，聚合得第五产物；Step 5. Cross-linking polymerization: graphene-bismuth tungstate, acrylamide solution, cross-linking agent and initiator are mixed to polymerize to obtain the fifth product;
    步骤六、苯胺浸入：所述第五产物与苯胺溶液混合，静置得第六产物；Step 6. Aniline immersion: the fifth product is mixed with the aniline solution, and the sixth product is obtained by standing still;
    步骤七、二次聚合：所述第六产物与引发剂溶液混合，聚合得钨酸铋-石墨烯-聚丙烯酰胺-聚苯胺导电水凝胶产品。Step 7. Secondary polymerization: The sixth product is mixed with the initiator solution and polymerized to obtain a conductive hydrogel product of bismuth tungstate-graphene-polyacrylamide-polyaniline.
  2. 根据权利要求1所述的制备方法，其特征在于，以摩尔份计，钨酸铋、石墨烯、丙烯酰胺及苯胺的投料比为(0.01～0.05):(0.003～0.015):(1～5):(0.1～0.5)。The preparation method according to claim 1, wherein the ratio of bismuth tungstate, graphene, acrylamide and aniline is (0.01～0.05): (0.003～0.015): (1～5 ): (0.1～0.5).
  3. 根据权利要求1所述的制备方法，其特征在于，所述制备方法还包括：除杂；The preparation method according to claim 1, wherein the preparation method further comprises: removing impurities;
    所述除杂的方法为：步骤七所得导电水凝胶粗品于水中静置得纯品。The method for removing impurities is as follows: the crude conductive hydrogel obtained in step 7 is left standing in water to obtain a pure product.
  4. 根据权利要求1所述的制备方法，其特征在于，步骤一中， 所述水热反应的温度为120～160℃，所述水热反应的时间为18～24h；The preparation method according to claim 1, wherein in step 1, the temperature of the hydrothermal reaction is 120-160°C, and the time of the hydrothermal reaction is 18-24h;
    步骤二中，所述超声分散的频率为20～25KHz，所述超声分散的时间为1～3h。In the second step, the frequency of the ultrasonic dispersion is 20-25 KHz, and the time of the ultrasonic dispersion is 1-3h.
  5. 根据权利要求1所述的制备方法，其特征在于，步骤三中，所述激光处理的处理时间为1～3h，所述激光处理的激光波长为10～760nm，所述激光处理的脉冲频率为10～100Hz，所述激光处理的单脉冲能量为200～500mJ。The preparation method according to claim 1, wherein in step 3, the processing time of the laser treatment is 1 to 3 hours, the laser wavelength of the laser treatment is 10 to 760 nm, and the pulse frequency of the laser treatment is 10-100 Hz, and the single pulse energy of the laser treatment is 200-500 mJ.
  6. 根据权利要求1所述的制备方法，其特征在于，步骤四中，所述激光溶蚀复合的作用时间为30～60min，所述激光溶蚀复合的激光波长为10～760nm，所述激光溶蚀复合的脉冲频率为10～100Hz，所述激光溶蚀复合的单脉冲能量为20～50mJ。The preparation method according to claim 1, characterized in that, in step 4, the action time of the laser ablation composite is 30-60 min, the laser wavelength of the laser ablation composite is 10 to 760 nm, and the laser ablation composite The pulse frequency is 10-100 Hz, and the single pulse energy of the laser ablation composite is 20-50 mJ.
  7. 根据权利要求1所述的制备方法，其特征在于，步骤五中，所述丙烯酰胺溶液的浓度为1～5mol/L，所述丙烯酰胺溶液的溶剂为去离子水；The preparation method according to claim 1, wherein in step 5, the concentration of the acrylamide solution is 1 to 5 mol/L, and the solvent of the acrylamide solution is deionized water;
    步骤六中，所述苯胺溶液的浓度为0.3～1.5mol/L，所述苯胺溶液的溶剂选自：盐酸、去离子水中任何一种或多种；In step 6, the concentration of the aniline solution is 0.3-1.5 mol/L, and the solvent of the aniline solution is selected from any one or more of hydrochloric acid and deionized water;
    步骤七中，所述引发剂与丙烯酰胺的摩尔比为1:(200～600)。In step 7, the molar ratio of the initiator to acrylamide is 1: (200-600).
  8. 根据权利要求1所述的制备方法，其特征在于，所述引发剂选自：过硫酸铵、过硫酸钾以及N,N,N′,N′-四甲基乙二胺中的任何一种或多种；The preparation method according to claim 1, wherein the initiator is selected from any one of ammonium persulfate, potassium persulfate and N,N,N',N'-tetramethylethylenediamine Or multiple
    所述交联剂选自：N，N-亚甲基双丙烯酰胺、偶氮二异丁氰以及N,N′-二异丙基双丙烯酰胺中的任何一种或多种。The crosslinking agent is selected from any one or more of N,N-methylenebisacrylamide, azobisisobutyronitrile and N,N'-diisopropylbisacrylamide.
  9. 根据权利要求1所述的制备方法，其特征在于，步骤一中，所述聚合的方法为：60～80℃条件下水浴/油浴加热聚合10～30min；The preparation method according to claim 1, characterized in that, in step 1, the polymerization method is: water bath/oil bath heating polymerization at 60-80°C for 10-30 minutes;
    步骤六中，所述静置的温度为室温，所述静置的时间为6～12h；In step 6, the standing temperature is room temperature, and the standing time is 6-12h;
    步骤七中，所述聚合的方法为：室温条件下静置聚合4～8h。In step 7, the polymerization method is: standing for polymerization at room temperature for 4 to 8 hours.
  10. 一种包括权利要求1至9任意一项所述的制备方法得到的产品在电解催化剂中的应用。An application of the product obtained by the preparation method according to any one of claims 1 to 9 in an electrolysis catalyst.
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