CN111471192A - Preparation method and application of bismuth tungstate-graphene-conductive hydrogel - Google Patents
Preparation method and application of bismuth tungstate-graphene-conductive hydrogel Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 99
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- 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
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- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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Abstract
The invention belongs to the technical field of electrolytic catalyst research and development, and particularly relates to a preparation method and application of bismuth tungstate-graphene-conductive hydrogel. The invention provides a preparation method of bismuth tungstate-graphene-conductive hydrogel, which comprises the following steps: preparing bismuth tungstate through hydrothermal reaction, carrying out ultrasonic stripping, preparing graphene quantum dots, carrying out laser corrosion compounding, carrying out cross-linking polymerization, carrying out aniline dipping and carrying out secondary polymerization. The invention also provides application of the product obtained by the preparation method in an electrolytic catalyst. By introducing graphene quantum dots, active sites of bismuth tungstate are increased to improve electrocatalytic performance; furthermore, the bismuth tungstate-graphene is further uniformly dispersed by combining with the conductive gel, so that the catalyst is prevented from agglomerating, the catalytic area of the catalyst is increased, and the gel is convenient to recover after the catalysis is finished; solves the technical defects that the catalyst used for photoelectric degradation or the cathode hydrogen evolution reaction of electrolyzed water in the prior art has poor catalytic performance and can not be recycled.
Description
Technical Field
The invention belongs to the technical field of electrolytic catalyst research and development, and particularly relates to a preparation method and application of bismuth tungstate-graphene-conductive hydrogel.
Background
The environmental and energy problems are a major problem facing human beings, and in order to realize sustainable development of human resources, people need to develop a clean energy system to reduce pollutant emission so as to protect the ecological environment. Renewable energy sources include solar energy, wind energy, hydrogen energy, biological energy and the like.
The hydrogen energy is a clean renewable dye, the combustion of the hydrogen gas can provide three times of energy compared with the common fossil fuel, and meanwhile, the product is pollution-free, and has the advantages of zero pollutant emission, recycling and the like. Since the first time self-electrolyzed water was reported, the method has since received extensive attention and research. The hydrogen generated by decomposing water by the supplied and requested electric energy can be directly supplied as energy, and the hydrogen can be stored for fuel cells and the like.
However, the cathodic Hydrogen Evolution Reaction (HER) of the electrolyzed water has a high kinetic potential ridge, which causes HER to be performed under a high overpotential and consumes excessively high electric energy, so that a suitable catalyst needs to be searched for reducing the potential and improving the hydrogen evolution efficiency. Platinum-based noble metals are the most ideal electrocatalyst for HER, but platinum-based materials are limited by problems of high price, low reserves and the like, and have great limitations in application.
In the prior art, bismuth tungstate (Bi)2WO6) The layered structure can promote the separation of photogenerated electrons and holes, is favorable for the transmission of ions between layers, and has better physical and chemical properties, such as ferroelectric, pyroelectric, photodegradation, piezoelectric, nonlinear dielectric polarization, luminescence property and the like. However, Bi alone2WO6The method has the defects in photodegradation, the visible light response range of the method is limited, and the recombination rate of photo-generated electrons and holes is high. Meanwhile, after the electrolysis reaction is finished, the catalyst cannot be recovered, so that the waste of the catalyst is caused, and the environmental pollution is brought.
Therefore, a preparation method and application of the bismuth tungstate-graphene-conductive hydrogel are developed to solve the technical defects that a catalyst for the cathodic hydrogen evolution reaction of electrolyzed water in the prior art has poor catalytic performance and cannot be recycled, and the problem to be solved by technical personnel in the field is urgently needed.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of bismuth tungstate-graphene-conductive hydrogel, which are used for solving the technical defects that a catalyst for an electrolytic water cathode hydrogen evolution reaction in the prior art has poor catalytic performance and cannot be recycled.
The invention provides a preparation method of bismuth tungstate-graphene-conductive hydrogel, which comprises the following steps:
step one, preparing bismuth tungstate through hydrothermal reaction: mixing sodium tungstate, bismuth nitrate and CTAB, dissolving in water, stirring, performing hydrothermal reaction, and washing and drying sequentially after the hydrothermal reaction is finished to obtain lamellar bismuth tungstate;
step two, ultrasonic stripping: ultrasonically stripping the dissolved lamellar bismuth tungstate to obtain dispersed two-dimensional bismuth tungstate nano-sheets;
step three, preparing the graphene quantum dots: after the graphene is dissolved, carrying out laser treatment to obtain graphene quantum dots;
step four, laser corrosion compounding: mixing the dispersed two-dimensional bismuth tungstate nano sheets with the graphene quantum dots, and performing laser corrosion compounding to obtain graphene-bismuth tungstate;
step five, cross-linking polymerization: mixing the graphene-bismuth tungstate, the acrylamide solution, the cross-linking agent and the initiator, and polymerizing to obtain a fifth product;
step six, aniline immersion: mixing the fifth product with an aniline solution, and standing to obtain a sixth product;
step seven, secondary polymerization: and mixing the sixth product with an initiator solution, and polymerizing to obtain a bismuth tungstate-graphene-polyacrylamide-polyaniline conductive hydrogel product.
Preferably, the feeding ratio of bismuth tungstate, graphene, acrylamide and aniline is (0.01-0.05): (0.003-0.015): 1-5): 0.1-0.5 in molar parts.
Preferably, the preparation method further comprises: removing impurities;
the impurity removal method comprises the following steps: and standing the crude product of the conductive hydrogel obtained in the step seven in water to obtain a pure product.
Preferably, in the first step, the temperature of the hydrothermal reaction is 120-160 ℃, and the time of the hydrothermal reaction is 18-24 h;
in the second step, the frequency of ultrasonic dispersion is 20-25 KHz, and the time of ultrasonic dispersion is 1-3 h.
Preferably, in the third step, the processing time of the laser processing is 1-3 h, the laser wavelength of the laser processing is 10-760 nm, the pulse frequency of the laser processing is 10-100 Hz, and the single pulse energy of the laser processing is 200-500 mJ.
Preferably, in the fourth step, the action time of the laser corrosion recombination is 30-60 min, the laser wavelength of the laser corrosion recombination is 10-760 nm, the pulse frequency of the laser corrosion recombination is 10-100 Hz, and the single pulse energy of the laser corrosion recombination is 20-50 mJ.
Preferably, in the fifth step, the concentration of the acrylamide solution is 1-5 mol/L, and the solvent of the acrylamide solution is deionized water;
in the sixth step, 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;
in the seventh step, the molar ratio of the initiator to the acrylamide is 1 (200-600).
Preferably, the initiator is selected from: any one or more of ammonium persulfate, potassium persulfate and N, N, N ', N' -tetramethylethylenediamine;
the cross-linking agent is selected from: any one or more of N, N-methylene bisacrylamide, azobisisobutyronitrile, and N, N' -diisopropylbisacrylamide.
Preferably, in the first step, the polymerization method is: heating and polymerizing for 10-30 min in a water bath/oil bath at the temperature of 60-80 ℃;
in the sixth step, the standing temperature is room temperature, and the standing time is 6-12 hours;
in the seventh step, the polymerization method comprises: standing and polymerizing for 4-8 h at room temperature.
The invention also provides application of a product obtained by the preparation method in an electrolytic catalyst.
In summary, the invention provides a preparation method of bismuth tungstate-graphene-conductive hydrogel, which comprises the following steps: preparing bismuth tungstate through hydrothermal reaction, carrying out ultrasonic stripping, preparing graphene quantum dots, carrying out laser corrosion compounding, carrying out cross-linking polymerization, carrying out aniline dipping and carrying out secondary polymerization. The invention also provides application of the product obtained by the preparation method in an electrolytic catalyst. In the technical scheme provided by the invention, the graphene quantum dots are introduced, so that the active sites of bismuth tungstate are increased to improve the electrocatalytic performance; furthermore, the bismuth tungstate-graphene is further uniformly dispersed based on the electrical property and the three-dimensional structure of the conductive gel in combination with the conductive gel, the catalyst agglomeration is prevented, the catalytic area of the catalyst is increased, and the gel is convenient to recover after the catalysis is finished. The invention provides a preparation method and application of bismuth tungstate-graphene-conductive hydrogel, which solve the technical defects that a catalyst for electrolytic water cathode hydrogen evolution reaction in the prior art has poor catalytic performance and cannot be recycled.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a preparation method of a bismuth tungstate-graphene-conductive hydrogel provided by the invention;
FIG. 2 is a graph showing the results of linear sweep voltammograms in example 4.
Detailed Description
The invention provides a preparation method and application of bismuth tungstate-graphene-conductive hydrogel, which are used for solving the technical defects that a catalyst for electrolytic water cathode hydrogen evolution reaction in the prior art has poor catalytic performance and cannot be recycled.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to illustrate the present invention in more detail, the following will specifically describe a preparation method and an application of the bismuth tungstate-graphene-conductive hydrogel provided by the present invention with reference to examples.
Example 1
Step one, weighing1mmol sodium tungstate (Na2 WO)4·2H2O), 2mmol of bismuth nitrate (Bi (NO)3)3·5H2O) and 0.05g CTAB are mixed and dissolved in 80ml of deionized water, the mixture is stirred at 60 ℃ and the rotating speed of 500r/min for 30min until the mixture is uniform, and the mixture is transferred to a hydrothermal kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 120 ℃, and the time of the hydrothermal reaction is 20 h. After the hydrothermal reaction is finished, sequentially washing and drying to obtain lamellar bismuth tungstate; wherein, the washing method comprises washing with water and ethanol for 3 times, and the drying method comprises: drying at 60 deg.C for 10 h.
Step two, taking 400mg of the lamellar bismuth tungstate obtained in the step one, dissolving the lamellar bismuth tungstate in 200ml of deionized water, and ultrasonically stripping the lamellar bismuth tungstate after the lamellar bismuth tungstate is dissolved to obtain dispersed two-dimensional bismuth tungstate nano-sheets; wherein the frequency of ultrasonic dispersion is 20KHz, and the time of ultrasonic dispersion is 1 h.
Weighing 5mg of graphene, dissolving the graphene in 10ml of deionized water, and carrying out ultrasonic dispersion at the frequency of 53KHz for 10min to fully dissolve the graphene; and after dissolution, carrying out laser treatment for 3h by using a wavelength of 532nm, a pulse frequency of 10Hz and a single pulse energy of 200mJ to obtain the graphene quantum dots.
And step four, mixing 5ml of the dispersed two-dimensional bismuth tungstate nano sheets obtained in the step two with the graphene quantum dot solution obtained in the step three, and in actual preparation, fully mixing the two by using an ultrasonic dispersion method. And after uniform mixing, carrying out laser corrosion compounding, wherein the action time of the laser corrosion compounding is 60min, the laser wavelength of the laser corrosion compounding is 10nm, the pulse frequency of the laser corrosion compounding is 100Hz, and the single pulse energy of the laser corrosion compounding is 10mJ, so as to obtain the graphene-bismuth tungstate. In the step, the mass ratio of the dispersed two-dimensional bismuth tungstate nano sheets to the graphene quantum dots is 2: 1.
Step five, preparing 1 mol/L Acrylamide (AM) solution, then adding graphene-bismuth tungstate, a cross-linking agent and an initiator (0.05 mol/L), uniformly mixing, and polymerizing for 30min at the water bath temperature of 60 ℃ to obtain transparent jelly-like hydrogel, namely a fifth product.
And step six, immersing the fifth product into a hydrochloric acid (aniline concentration is 1.5 mol/L) solution containing Aniline (ANI), and standing for 6 hours at room temperature to enable aniline monomer to enter the fifth product, namely the sixth product.
And step seven, immersing the sixth product into an aqueous solution of an initiator, initiating aniline monomer polymerization for 4 hours at room temperature to form a crude product of the bismuth tungstate-graphene-PAM-PANI conductive hydrogel, placing the crude product of the conductive hydrogel in a large amount of deionized water, and removing oligomers and unreacted aniline monomer to obtain a pure polyacrylamide-polyaniline composite hydrogel product. In the step, the initiator is ammonium persulfate; the molar charge ratio of the initiator to the aniline in the second step is 1: 1.
In the embodiment, the feeding ratio of the bismuth tungstate, the graphene, the acrylamide and the aniline is 0.03:0.003:5:0.1 in molar parts.
Example 2
Step one, weighing 1mmol of sodium tungstate (Na2 WO)4·2H2O), 2mmol of bismuth nitrate (Bi (NO)3)3·5H2O) and 0.05g CTAB are mixed and dissolved in 80ml of deionized water, the mixture is stirred at 70 ℃ and the rotating speed of 800r/min for 10min until the mixture is uniform, and the mixture is transferred to a hydrothermal kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 130 ℃, and the time of the hydrothermal reaction is 24 h. After the hydrothermal reaction is finished, sequentially washing and drying to obtain lamellar bismuth tungstate; wherein, the washing method comprises washing with water and ethanol for 3 times, and the drying method comprises: drying at 60 deg.C for 10 h.
Step two, taking 400mg of the lamellar bismuth tungstate obtained in the step one, dissolving the lamellar bismuth tungstate in 200ml of deionized water, and ultrasonically stripping the lamellar bismuth tungstate after the lamellar bismuth tungstate is dissolved to obtain dispersed two-dimensional bismuth tungstate nano-sheets; wherein the frequency of ultrasonic dispersion is 25KHz, and the time of ultrasonic dispersion is 2 h.
Weighing 10mg of graphene, dissolving the graphene in 10ml of deionized water, and performing ultrasonic dispersion at the frequency of 53KHz for 10min to fully dissolve the graphene; and after dissolution, performing laser treatment for 2h by using the wavelength of 10nm, the pulse frequency of 100Hz and the single pulse energy of 300mJ to obtain the graphene quantum dots.
And step four, mixing 5ml of the dispersed two-dimensional bismuth tungstate nano sheets obtained in the step two with the graphene quantum dot solution obtained in the step three, and in actual preparation, fully mixing the two by using an ultrasonic dispersion method. And after uniform mixing, carrying out laser corrosion compounding, wherein the action time of the laser corrosion compounding is 45min, the laser wavelength of the laser corrosion compounding is 532nm, the pulse frequency of the laser corrosion compounding is 10Hz, and the single pulse energy of the laser corrosion compounding is 50mJ, so as to obtain the graphene-bismuth tungstate. In the step, the mass ratio of the dispersed two-dimensional bismuth tungstate nano sheets to the graphene quantum dots is 1: 1.
Step five, preparing 3 mol/L Acrylamide (AM) solution, then adding graphene-bismuth tungstate, a cross-linking agent and an initiator (0.05 mol/L), uniformly mixing, and polymerizing for 30min at the water bath temperature of 60 ℃ to obtain transparent jelly-like hydrogel, namely a fifth product.
And step six, immersing the fifth product into a hydrochloric acid (aniline concentration is 0.3 mol/L) solution containing Aniline (ANI), and standing for 10 hours at room temperature to enable aniline monomer to enter the fifth product, namely the sixth product.
And step seven, immersing the sixth product into an aqueous solution of an initiator, initiating aniline monomer polymerization for 6 hours at room temperature to form a crude product of the bismuth tungstate-graphene-PAM-PANI conductive hydrogel, placing the crude product of the conductive hydrogel in a large amount of deionized water, and removing oligomers and unreacted aniline monomer to obtain a pure bismuth tungstate-graphene-conductive hydrogel product. In the step, the initiator is potassium persulfate; the molar charge ratio of the initiator to the aniline in the sixth step is 1: 1.
In the embodiment, the feeding ratio of the bismuth tungstate, the graphene, the acrylamide and the aniline is 0.055:0.015:1:0.2 in molar parts.
Example 3
Step one, weighing 1mmol of sodium tungstate (Na2 WO)4·2H2O), 2mmol of bismuth nitrate (Bi (NO)3)3·5H2O) and 0.05g CTAB, dissolved in 80ml of deionized water at 80 ℃ and 1000r/minStirring for 20min to be uniform, transferring to a hydrothermal kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 160 ℃, and the time of the hydrothermal reaction is 18 h. After the hydrothermal reaction is finished, sequentially washing and drying to obtain lamellar bismuth tungstate; wherein, the washing method comprises washing with water and ethanol for 3 times, and the drying method comprises: drying at 60 deg.C for 10 h.
Step two, taking 400mg of the lamellar bismuth tungstate obtained in the step one, dissolving the lamellar bismuth tungstate in 200ml of deionized water, and ultrasonically stripping the lamellar bismuth tungstate after the lamellar bismuth tungstate is dissolved to obtain dispersed two-dimensional bismuth tungstate nano-sheets; wherein the frequency of ultrasonic dispersion is 22KHz, and the time of ultrasonic dispersion is 3 h.
Weighing 20mg of graphene, dissolving the graphene in 10ml of deionized water, and carrying out ultrasonic dispersion at the frequency of 53KHz for 10min to fully dissolve the graphene; and after dissolution, performing laser treatment for 1h by using a wavelength of 760nm, a pulse frequency of 30Hz and a single pulse energy of 500mJ to obtain the graphene quantum dots.
And step four, mixing 5ml of the dispersed two-dimensional bismuth tungstate nano sheets obtained in the step two with the graphene quantum dot solution obtained in the step three, and in actual preparation, fully mixing the two by using an ultrasonic dispersion method. And after uniform mixing, carrying out laser corrosion compounding, wherein the action time of the laser corrosion compounding is 30min, the laser wavelength of the laser corrosion compounding is 532nm, the pulse frequency of the laser corrosion compounding is 50Hz, and the single pulse energy of the laser corrosion compounding is 40mJ, so as to obtain the graphene-bismuth tungstate. In the step, the mass ratio of the dispersed two-dimensional bismuth tungstate nano sheets to the graphene quantum dots is 2: 1.
Step five, preparing 5 mol/L Acrylamide (AM) solution, then adding graphene-bismuth tungstate, a cross-linking agent and an initiator (0.05 mol/L), uniformly mixing, and polymerizing for 30min at the water bath temperature of 80 ℃ to obtain transparent jelly-like hydrogel, namely a fifth product.
And step six, immersing the first product into a hydrochloric acid (aniline concentration is 1 mol/L) solution containing Aniline (ANI), standing for 12 hours at room temperature, and allowing aniline monomer to enter a fifth product, namely a sixth product.
And step seven, immersing the sixth product into an aqueous solution of an initiator, initiating aniline monomer polymerization for 8 hours at room temperature to form a crude product of the bismuth tungstate-graphene-PAM-PANI conductive hydrogel, placing the crude product of the conductive hydrogel in a large amount of deionized water, and removing oligomers and unreacted aniline monomer to obtain a pure bismuth tungstate-graphene-conductive hydrogel product. In the step, the initiator is N, N, N ', N' -tetramethylethylenediamine; the molar charge ratio of the initiator to the aniline in the step six is 1: 1.
in the embodiment, the feeding ratio of the bismuth tungstate, the graphene, the acrylamide and the aniline is 0.01:0.01:3:0.5 in molar parts.
In the preparation methods provided in embodiments 1 to 3, high-purity and high-efficiency synthesis of bismuth tungstate is performed first, but at this time, the prepared bismuth tungstate has a lamellar structure, and stacking thereof is severe, and effective catalysis cannot be performed. In the second step, the aggregation bismuth tungstate is subjected to ultrasonic treatment by means of ultrasonic action, so that the aggregation bismuth tungstate is effectively dispersed, a dispersed two-dimensional bismuth tungstate nano-sheet is obtained, the exposure area of the bismuth tungstate is increased, and more active areas are provided.
In the third step, the prepared graphene quantum dots are zero-dimensional few-layer graphene materials, and are in the nanometer level in three dimensions, that is, the graphene quantum dots can show some unique performances, such as: strong quantum confinement effect, edge effect, good electron transfer capability, up-conversion luminescence property and the like; meanwhile, the graphene quantum dots also have the good characteristics of no toxicity and low price, in the fourth step, the graphene quantum dots are combined with the two-dimensional bismuth tungstate nano-sheets, and the graphene quantum dots can be used as active sites to improve the catalytic activity of the two-dimensional bismuth tungstate.
Step five, the prepared bismuth tungstate-graphene enters a three-dimensional structure of polyacrylamide, aniline is further introduced and polymerized in step six and step seven, and the conductive hydrogel is used as a catalyst carrier, so that the uniform dispersion of the catalyst can be realized, and the active area of the catalyst is increased; meanwhile, the conductive hydrogel also has good electrical properties, and is combined with a catalyst to form a force-electricity combined catalytic system, so that the catalytic performance of the catalyst is further comprehensively improved. Meanwhile, the gel-like carrier is convenient for the recovery of the catalyst after use, and the recovery and the reutilization of the catalyst are realized.
Example 4
This example is a specific example for measuring the catalytic performance of the graphene-bismuth tungstate-conductive hydrogel prepared in examples 1 to 3, and in this example, the reference catalyst used is bismuth tungstate powder.
Experimental methods
Preparation of graphene-bismuth tungstate-conductive hydrogel electrode
Putting carbon cloth with proper size into the solution obtained in the step five of the embodiment 1 to 3de, so that the solution is in contact with the carbon cloth and the area of the carbon cloth is 1cm2The thin gel layer of (2) is not changed, and the graphene-bismuth tungstate-conductive hydrogel electrode is obtained.
Electrochemical testing
Performing electrochemical test on an electrochemical workstation by adopting a traditional three-electrode system, wherein a reference electrode is a saturated calomel electrode, a counter electrode is a graphite electrode, a graphene-bismuth tungstate-conductive hydrogel electrode is a working electrode, and 0.5mol L of the electrode is used as the working electrode-1H2SO4The solution is electrolyte, linear sweep voltammetry (L SV) is adopted, the sweep range is set to be-0.2V to-1.2V, and the sweep rate is 5mV s-1And recording a linear sweep voltammetry curve.
Results of the experiment
As can be seen from fig. 2, the initial overpotential of the graphene-bismuth tungstate-conductive hydrogel is improved by 14% compared with that of bismuth tungstate powder, and the initial overpotential after ultrasonic treatment can be improved by 27% compared with that of bismuth tungstate powder.
In summary, the invention provides a preparation method of bismuth tungstate-graphene-conductive hydrogel, which comprises the following steps: preparing bismuth tungstate through hydrothermal reaction, carrying out ultrasonic stripping, preparing graphene quantum dots, carrying out laser corrosion compounding, carrying out cross-linking polymerization, carrying out aniline dipping and carrying out secondary polymerization. The invention also provides application of the product obtained by the preparation method in an electrolytic catalyst. In the technical scheme provided by the invention, the graphene quantum dots are introduced, so that the active sites of bismuth tungstate are increased to improve the electrocatalytic performance; furthermore, the bismuth tungstate-graphene is further uniformly dispersed based on the electrical property and the three-dimensional structure of the conductive gel in combination with the conductive gel, the catalyst agglomeration is prevented, the catalytic area of the catalyst is increased, and the gel is convenient to recover after the catalysis is finished. The invention provides a preparation method and application of bismuth tungstate-graphene-conductive hydrogel, which solve the technical defects that a catalyst for electrolytic water cathode hydrogen evolution reaction in the prior art has poor catalytic performance and cannot be recycled.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of bismuth tungstate-graphene-conductive hydrogel is characterized by comprising the following steps:
step one, preparing bismuth tungstate through hydrothermal reaction: mixing sodium tungstate, bismuth nitrate and CTAB, dissolving in water, stirring, performing hydrothermal reaction, and washing and drying sequentially after the hydrothermal reaction is finished to obtain lamellar bismuth tungstate;
step two, ultrasonic stripping: ultrasonically stripping the dissolved lamellar bismuth tungstate to obtain dispersed two-dimensional bismuth tungstate nano-sheets;
step three, preparing the graphene quantum dots: after the graphene is dissolved, carrying out laser treatment to obtain graphene quantum dots;
step four, laser corrosion compounding: mixing the dispersed two-dimensional bismuth tungstate nano sheets with the graphene quantum dots, and performing laser corrosion compounding to obtain graphene-bismuth tungstate;
step five, cross-linking polymerization: mixing the graphene-bismuth tungstate, the acrylamide solution, the cross-linking agent and the initiator, and polymerizing to obtain a fifth product;
step six, aniline immersion: mixing the fifth product with an aniline solution, and standing to obtain a sixth product;
step seven, secondary polymerization: and mixing the sixth product with an initiator solution, and polymerizing to obtain a bismuth tungstate-graphene-polyacrylamide-polyaniline conductive hydrogel product.
2. The method according to claim 1, wherein the ratio of bismuth tungstate to graphene to acrylamide to aniline is (0.01-0.05), (0.003-0.015), (1-5) and (0.1-0.5).
3. The method of manufacturing according to claim 1, further comprising: removing impurities;
the impurity removal method comprises the following steps: and standing the crude product of the conductive hydrogel obtained in the step seven in water to obtain a pure product.
4. The preparation method according to claim 1, wherein in the first step, the temperature of the hydrothermal reaction is 120-160 ℃, and the time of the hydrothermal reaction is 18-24 h;
in the second step, the frequency of ultrasonic dispersion is 20-25 KHz, and the time of ultrasonic dispersion is 1-3 h.
5. The preparation method according to claim 1, wherein in the third step, the treatment time of the laser treatment is 1-3 h, the laser wavelength of the laser treatment is 10-760 nm, 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. The preparation method according to claim 1, wherein in the fourth step, the action time of the laser ablation recombination is 30-60 min, the laser wavelength of the laser ablation recombination is 10-760 nm, the pulse frequency of the laser ablation recombination is 10-100 Hz, and the single pulse energy of the laser ablation recombination is 20-50 mJ.
7. The preparation method according to claim 1, wherein in the fifth step, the concentration of the acrylamide solution is 1-5 mol/L, and the solvent of the acrylamide solution is deionized water;
in the sixth step, 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;
in the seventh step, the molar ratio of the initiator to the acrylamide is 1 (200-600).
8. The method according to claim 1, wherein the initiator is selected from the group consisting of: any one or more of ammonium persulfate, potassium persulfate and N, N, N ', N' -tetramethylethylenediamine;
the cross-linking agent is selected from: any one or more of N, N-methylene bisacrylamide, azobisisobutyronitrile, and N, N' -diisopropylbisacrylamide.
9. The method of claim 1, wherein in step one, the polymerization process comprises: heating and polymerizing for 10-30 min in a water bath/oil bath at the temperature of 60-80 ℃;
in the sixth step, the standing temperature is room temperature, and the standing time is 6-12 hours;
in the seventh step, the polymerization method comprises: standing and polymerizing for 4-8 h at room temperature.
10. Use of a product obtained by the method according to any one of claims 1 to 9 in an electrolytic catalyst.
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