CN109046470B - Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst and preparation method and application thereof - Google Patents
Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- B01J35/39—
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- B01J35/50—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
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- 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
Abstract
The invention provides Linquist type K7HNb6O19The preparation method of the-polypyrrole-reduced graphene oxide composite photocatalyst comprises the following steps: mixing ethanol solution of pyrrole with dispersion liquid of graphene oxide, and adding K7HNb6O19Then carrying out one-step hydrothermal reaction on the mixed solution, and finally washing and drying a reaction product to obtain K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst. The preparation method disclosed by the invention is simple in principle, mild in condition and easy to operate, the prepared composite photocatalyst presents the appearance of peony, and has good catalytic activity and stability, the composite photocatalyst can still show good hydrogen production activity under the condition that no noble metal is used as a cocatalyst, the photocatalytic hydrogen production rate can reach 207.56 mu mol/g/h, and the preparation method has a good application prospect.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst and preparation method and application thereof.
Background
The hydrogen energy is an energy source with high heat value, cleanness, safety and environmental protection, and is an ideal secondary energy source. However, the main methods for producing hydrogen gas so far include production of hydrogen by fossil fuel, production of hydrogen by electrolysis of water, production of hydrogen by cracking of methanol, and the like. The traditional hydrogen production has the problems of laggard process, more energy consumption, high production cost, poor economic benefit and the like, and relatively speaking, the hydrogen prepared by photocatalytic water decomposition has excellent application prospect in the aspects of solving the environmental problem, the cost problem, the energy problem and the like. The hydrogen prepared by photocatalytic water decomposition has the advantages of no secondary pollution, no need of providing additional energy for absorbing sunlight and the like, so the hydrogen is concerned by researchers at home and abroad.
Graphene is a carbon atom through sp2The hybrid structure has a series of unique properties, and the graphene is compounded with the photocatalyst by utilizing the property of large specific surface area of the graphene, so that the activity of the photocatalyst can be improved, and the light can be increasedSelectivity of the catalyst. Meanwhile, the graphene has good conductivity, so that separation of photo-generated electrons and holes is facilitated, and the efficiency of photocatalytic hydrogen production is improved. Therefore, the graphene has good application prospect in the field of photocatalytic hydrogen production.
The polyoxometallate is applied to the field of photocatalysis due to the advantages of high catalytic activity, strong oxidizability, good selectivity, no toxicity, mild reaction conditions and the like. However, Linquist type K7HNb6O19The band gap is 4.12 eV, the band gap is wide, and visible light cannot be fully utilized.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a Linquist type K7HNb6O19The-polypyrrole-reduced graphene oxide composite photocatalyst is prepared through one-step hydrothermal reaction, is mild in condition and simple to operate, and can not fully utilize visible light due to wide band gap7HNb6O19The graphene is compounded with graphene, so that the recombination rate of photoproduction electrons and electron holes is effectively reduced, and the photocatalytic activity is improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
linquist type K7HNb6O19The preparation method of the-polypyrrole-reduced graphene oxide composite photocatalyst comprises the following steps:
Preferably, the concentration of the substance in the mixed solution A in the step 1 is 2mg/mL, and the ultrasonic time is 1-1.5 h.
Preferably, the volume ratio of the pyrrole to the ethanol in the step 2 is 9-15: 100.
Preferably, the dripping speed of the ethanol solution of the pyrrole in the step 3 is 1.1-3.3 mL/min, and the stirring speed is 800-1200 rpm.
Preferably, K in step 47HNb6O19The amount of the substance is 0.025 to 0.5 mmol.
Preferably, the heating rate and the cooling rate of the hydrothermal reaction in the step 5 are both 10 ℃/min, the temperature of the hydrothermal reaction is 160-190 ℃, and the reaction time is 11-13 h.
Preferably, the washing and drying process of the hydrothermal product in step 5 is as follows: firstly, centrifugally washing with deionized water for at least 3 times, then centrifugally washing with ethanol for 2 times, and finally, carrying out vacuum drying on the washed product, wherein the drying temperature is 60-65 ℃, and the drying time is 12-15 h.
The invention also protects the Linquist type K prepared by the preparation method7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst.
The invention also protects the Linquist type K prepared by the preparation method7HNb6O19Application of the polypyrrole-reduced graphene oxide composite photocatalyst in photocatalytic hydrogen production.
Preferably, photocatalytic hydrogen production is carried out in a vacuum environment under the condition of a 300W xenon lamp, the reaction temperature is 4-6 ℃, and the reaction time is 4-6 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the mixed Linquist type K7HNb6O19The raw materials of pyrrole and graphene oxide are prepared into Linquist type K by a one-step hydrothermal method7HNb6O19The preparation raw materials are easy to obtain, the process is simple, the conditions are mild, and the photocatalyst has good stability and recyclability;
2. according to the invention, the polyoxometallate is compounded with the graphene, so that the application range of the polyoxometallate is expanded, and the performance of the polyoxometallate is improved;
3. in the invention, K is7HNb6O19Is compounded with graphene, and K is improved7HNb6O19The light response range reduces the band gap, reduces the recombination rate of photo-generated electrons and electron holes, and improves the photocatalytic activity;
4. the invention changes K by adding pyrrole7HNb6O19The peony-shaped photocatalyst is prepared according to the shape of the photocatalyst, and the blooming degree of the peony of the photocatalyst is controlled by controlling the adding amount of pyrrole;
5. linquist type K prepared by the invention7HNb6O19The polypyrrole-reduced graphene oxide composite photocatalyst still has good hydrogen production activity under the condition that no noble metal is used as a cocatalyst, and the hydrogen production rate can reach 207.56 mu mol/g/h.
Drawings
FIG. 1 is a scanning electron micrograph of a composite photocatalyst prepared in examples 1, 2 and 3 according to the present invention;
FIG. 2 is a scanning electron micrograph of the composite photocatalyst prepared in examples 2, 4, 5 and 6 of the present invention;
FIG. 3 is a scanning electron micrograph of the composite photocatalyst prepared in example 2, example 7 and example 8 of the present invention;
FIG. 4 shows K in the present invention7HNb6O19A graph comparing the photocatalytic hydrogen production activity of the composite photocatalysts prepared in the examples 1, 2 and 3;
FIG. 5 is a graph comparing the photocatalytic hydrogen production activity of the composite photocatalysts prepared in examples 2, 4, 5 and 6 of the present invention;
FIG. 6 is a graph comparing the photocatalytic hydrogen production activity of the composite photocatalysts prepared in examples 2, 7 and 8 of the present invention;
FIG. 7 is a photocatalytic hydrogen production cycle diagram of the composite photocatalyst prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments. The scope of the invention is not limited to the specific embodiments. In the following examples, the modified Hummers method was used with reference to the following references: 1. preparing graphene oxide by improving a Hummers method and representing the graphene oxide; it was published in 2015 4 months on package journal, volume 7, phase 2; 2. the optimization and improvement of the preparation method of the graphene oxide are published in 2016 (10) at volume 44, 19 of Guangzhou chemical engineering; 3. research on graphene oxide prepared by improving the Hummers method and copper ion adsorption of graphene oxide is published in industrial water and wastewater in 2015 8 months.
Example 1
Example 2
The same synthesis method as that of example 1, except that K is used in step 4 of this example7HNb6O19The dosage of (b) is 0.25mmol, obtaining Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst, labeled # 2.
Example 3
The same synthesis method as that of example 1, except that K is used in step 4 of this example7HNb6O19The dosage of (b) is 0.375mmol, obtaining Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst, labeled # 3.
Example 4
The same synthetic method as in example 2, except that the amounts of pyrrole and ethanol added in step 2 of this example were 0. mu.L and 1mL, respectively, gave Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst, labeled # 4.
Example 5
The same synthetic method as in example 2, except that the amounts of pyrrole and ethanol added in step 2 of this example were 90. mu.L and 1mL, respectively, gave Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst, labeled # 5.
Example 6
The same synthetic method as in example 2, except that the amounts of pyrrole and ethanol added in step 2 of this example were 130. mu.L and 1mL, respectively, gave Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst, labeled 6 #.
Example 7
The same synthesis method as that of example 2, except for the difference of step 5 in this exampleThe hydrothermal reaction temperature is 160 ℃, and Linquist type K is obtained7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst, labeled 7 #.
Example 8
The same synthesis method as that of example 2, except that the hydrothermal reaction temperature in step 5 of this example was 190 ℃ to obtain Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst, labeled # 8.
Firstly, the 1# to 8# composite photocatalysts are subjected to morphological characterization by using a scanning electron microscope, fig. 1 is a scanning electron microscope image of the composite photocatalysts prepared in examples 1, 2 and 3 of the present invention, fig. 2 is a scanning electron microscope image of the composite photocatalysts prepared in examples 2, 4, 5 and 6 of the present invention, fig. 3 is a scanning electron microscope image of the composite photocatalysts prepared in examples 2, 7 and 8 of the present invention, and as can be seen from fig. 1 to 3, the composite material presents a peony flower shape. Temperature and K7HNb6O19The dosage of the compound mainly influences the particle size of the peony, and the dosage of the pyrrole mainly influences the blooming degree of the peony.
Then, the 1# to 8# composite photocatalyst is subjected to a photocatalytic hydrogen production experiment, a methanol solution with the volume fraction of 20% is prepared firstly, then 50mg of the 1# to 8# composite photocatalyst is mixed with 50mL of the methanol solution with the volume fraction of 20% respectively, the mixture is placed in a photocatalytic reactor, and the photocatalytic activity test is carried out by irradiating the mixture for 5 hours at the temperature of 5 ℃ under the vacuum condition by using visible light (a 300W xenon lamp).
FIG. 4 shows K in the present invention7HNb6O19Fig. 5 is a graph showing the photocatalytic hydrogen production activity of the composite photocatalysts prepared in examples 2, 4, 5 and 6, and fig. 6 is a graph showing the photocatalytic hydrogen production activity of the composite photocatalysts prepared in examples 2, 7 and 8. As can be seen from FIGS. 4-6, the morphology and hydrogen production activity of the composite material are influenced by temperature and hydrogenPyrrole amount and K7HNb6O19Influence of the amount. K7HNb6O19When the using amount of the catalyst is less than 0.25mmol, agglomeration can be caused due to too small particle size, and the hydrogen production rate is low; k7HNb6O19When the using amount is 0.25mmol, the peony shape with uniform appearance is presented, and the hydrogen production rate reaches 207.56 mu mol/h/g at most; k7HNb6O19When the using amount is more than 0.25mmol, the particle size is enlarged, the appearance is collapsed, and the hydrogen production rate is reduced. The consumption of pyrrole affects the blooming degree of peony, the material is in a shape of a bud without pyrrole, the hydrogen production rate is very low (26 mu mol/h/g), the peony gradually blooms along with the addition of the pyrrole, and the hydrogen production rate is also gradually increased; when the adding amount of the pyrrole is 110 mu L, the peony blooms completely, and the hydrogen production rate reaches the maximum value; when the pyrrole amount is more than 110 mu L, the buds reappear to cause uneven appearance and lower hydrogen production rate; the temperature mainly influences the particle size of the peony, the particle size is smaller when the temperature is 160 ℃, the agglomeration phenomenon exists, and the hydrogen production rate is only 26.16 mu mol/h/g; when the temperature is 180 ℃, the obtained composite photocatalyst is in a uniform peony shape, and the photocatalytic hydrogen production activity is high; the temperature is 190 ℃, the appearance is collapsed, and the hydrogen production rate is reduced to 49.8 mu mol/h/g.
Table 1 is a hydrogen generation rate table of 1# to 8# composite photocatalysts in a photocatalytic hydrogen production experiment, and Linquist type K prepared by the method can be seen from the table7HNb6O19The-polypyrrole-reduced graphene oxide composite photocatalyst has excellent photocatalytic activity.
Table 11 # to 8# composite photocatalyst hydrogen generation rate table
Finally, performing a photocatalytic hydrogen production cycle experiment on the 2# composite photocatalyst, firstly preparing a 20% methanol solution by volume fraction, then mixing 50mg of the 2# composite photocatalyst with 50mL of 20% methanol solution respectively, placing the mixture in a photocatalytic reactor, and irradiating the mixture for 5 hours by using visible light (300W xenon lamp) at 5 ℃ under a vacuum condition, wherein the first cycle experiment is performed; then vacuumizing, and irradiating for 5h under the same condition, wherein the second cycle experiment is carried out; vacuumizing again, and irradiating for 5h under the same condition, wherein the cycle experiment is carried out for the third time; finally, vacuumizing is carried out again, and the irradiation is carried out for 5 hours under the same conditions to form a fourth cycle experiment.
FIG. 7 is a photocatalytic hydrogen production cycle chart, and it can be seen from FIG. 7 that Linquist type K prepared by the invention7HNb6O19The polypyrrole-reduced graphene oxide composite photocatalyst has good stability, and still has good photocatalytic activity after four cycles.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
- Linquist type K7HNb6O19The preparation method of the polypyrrole-reduced graphene oxide composite photocatalyst is characterized by comprising the following steps:step 1, preparing graphene oxide by an improved Hummers method, mixing the obtained graphene oxide with water, and performing ultrasonic dispersion to obtain a mixed solution A;step 2, mixing pyrrole and ethanol to obtain an ethanol solution of pyrrole;step 3, dropwise adding the ethanol solution of pyrrole obtained in the step 2 into the mixed solution A obtained in the step 1, and stirring for 30-45 min to obtain a mixed solution B;step 4, adding K into the mixed solution B obtained in the step 37HNb6O19Obtaining a mixed solution C, wherein the graphene oxide, the pyrrole and the K used in the step 1, the step 2 and the step 47HNb6O19The dosage ratio is 4 mg: 110 μ L: 0.25 mmol;step 5, carrying out hydrothermal reaction on the mixed solution C obtained in the step 4, washing and drying a hydrothermal product to obtain a peony-shaped Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst;and 5, both the temperature rising rate and the temperature reduction rate of the hydrothermal reaction in the step 5 are 10 ℃/min, the temperature of the hydrothermal reaction is 160-180 ℃, and the reaction time is 6-12 h.
- 2. Linquist type K according to claim 17HNb6O19The preparation method of the-polypyrrole-reduced graphene oxide composite photocatalyst is characterized in that the concentration of the substance of the mixed solution A in the step 1 is 2mg/mL, and the ultrasonic time is 1-1.5 h.
- 3. Linquist type K according to claim 17HNb6O19The preparation method of the-polypyrrole-reduced graphene oxide composite photocatalyst is characterized in that the volume ratio of pyrrole to ethanol in the step 2 is 9-15: 100.
- 4. Linquist type K according to claim 17HNb6O19The preparation method of the-polypyrrole-reduced graphene oxide composite photocatalyst is characterized in that in the step 3, the dripping speed of an ethanol solution of pyrrole is 1.1-3.3 mL/min, and the stirring speed is 800-1200 rpm.
- 5. Linquist type K according to claim 17HNb6O19The preparation method of the polypyrrole-reduced graphene oxide composite photocatalyst is characterized in that the washing and drying processes of the hydrothermal product in the step 5 are as follows: firstly, centrifugally washing with deionized water for at least 3 times, then centrifugally washing with ethanol for 2 times, and finally, carrying out vacuum drying on the washed product, wherein the drying temperature is 60-65 ℃, and the drying time is 12-15 h.
- Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst, characterized in that it is prepared by the preparation method of any one of claims 1 to 5.
- 7. The Linquist type K of claim 67HNb6O19The application of the polypyrrole-reduced graphene oxide composite photocatalyst is characterized by being used for photocatalytic hydrogen production.
- 8. Linquist type K according to claim 77HNb6O19The application of the polypyrrole-reduced graphene oxide composite photocatalyst is characterized in that photocatalytic hydrogen production is carried out in a vacuum environment under the condition of a 300W xenon lamp, the reaction temperature is 4-6 ℃, and the reaction time is 4-6 hours.
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| CN103084211B (en) * | 2012-12-24 | 2014-10-22 | 东北师范大学 | Polyniobate-based photocatalyst and preparation method thereof |
| CN103913492B (en) * | 2014-03-26 | 2015-12-09 | 青岛大学 | A kind of Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode and its preparation method and application |
| CN108080032A (en) * | 2017-12-29 | 2018-05-29 | 济宁学院 | The preparation method of silver orthophosphate/polyacid@polypyrrole nucleocapsid photochemical catalysts |
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