CN109046470A - Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst and its preparation method and application - Google Patents

Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst and its preparation method and application Download PDF

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CN109046470A
CN109046470A CN201810939195.4A CN201810939195A CN109046470A CN 109046470 A CN109046470 A CN 109046470A CN 201810939195 A CN201810939195 A CN 201810939195A CN 109046470 A CN109046470 A CN 109046470A
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CN109046470B (en
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柏*
党东宾
李薇薇
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Henan University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/36Catalysts 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042Decomposition of water
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0266Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1088Non-supported catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The present invention provides Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst and its preparation method and application, the preparation of the composite photo-catalyst add K the following steps are included: the ethanol solution of pyrroles is mixed with the dispersion liquid of graphene oxide7HNb6O19, mixed solution is then subjected to a step hydro-thermal reaction, reaction product washing is finally dried to obtain K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst.Preparation method principle of the invention is simple, mild condition, it is easily operated, peony pattern is presented in composite photo-catalyst obtained, and the composite photo-catalyst has preferable catalytic activity and stability, it remains to show preferable production hydrogen activity in the case where no noble metal is as co-catalyst, Photocatalyzed Hydrogen Production rate has fine application prospect up to 207.56 μm of ol/g/h.

Description

Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst And its preparation method and application
Technical field
The present invention relates to catalysis material technical fields, specially Linquist type K7HNb6O19Polypyrrole-oxygen reduction Graphite alkene composite photo-catalyst and its preparation method and application.
Background technique
Hydrogen Energy is that a kind of calorific value is very high, cleaning, the energy of safety and environmental protection, is a kind of highly desirable secondary energy sources.But it arrives So far, preparing hydrogen main method has fossil fuel hydrogen manufacturing, water electrolysis hydrogen production, methanol decomposition legal system hydrogen etc..These tradition Hydrogen manufacturing there is a problem of that technique is backward, energy consumption is more, high production cost and deficiency in economic performance etc. are larger, comparatively, light Hydrogen made from water is catalytically decomposed and is solving environmental problem, cost problem, before energy problem etc. shows fabulous application Scape.Hydrogen made from photochemical catalyzing does not have secondary pollution, absorbs sunlight and does not need to provide the advantages such as additional energy, institute With the concern by domestic and international researcher.
Graphene is that carbon atom passes through sp2Hydridization is constituted, and has a series of unique properties, we are big using graphene This property of specific surface area, keeps it compound with photochemical catalyst, and the activity of photochemical catalyst can be improved, and increases the selection of photochemical catalyst Property.Graphene has good conductive property simultaneously, is conducive to the separation in light induced electron and hole, improves the effect of Photocatalyzed Hydrogen Production Rate.Therefore, graphene has fine application prospect in Photocatalyzed Hydrogen Production field.
And polyoxometallate is with its catalytic activity height, oxidisability is strong, and selectivity is good, nontoxic, and it is excellent that reaction condition is mild etc. Point is applied to photocatalysis field.But Linquist type K7HNb6O19Forbidden bandwidth is 4.12 eV, greater band gap, Bu Nengchong Divide and utilizes visible light.
Summary of the invention
The purpose of the present invention is to solve the deficiencies of above-mentioned technology, provide a kind of Linquist type K7HNb6O19Poly- pyrrole Cough up-redox graphene composite photo-catalyst and its preparation method and application, it is made by a step hydro-thermal reaction, condition temperature With, it is easy to operate, the Linquist type K of visible light will cannot be made full use of because of greater band gap7HNb6O19It is compound with graphene, The recombination rate of light induced electron and electron hole is effectively reduced, photocatalytic activity is improved.
To achieve the above object, the technical solution adopted by the present invention is that:
Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst preparation method, including with Lower step:
Graphene oxide is prepared by improved Hummers method in step 1, and obtained graphene oxide is mixed with water It closes, and ultrasonic disperse obtains mixed solution A;
Step 2 obtains the ethanol solution of pyrroles after mixing pyrroles and ethyl alcohol;
The ethanol solution for the pyrroles that step 2 obtains is added drop-wise in the mixed solution A that step 1 obtains, and stirs by step 3 30~45min obtains mixed solution B;
K is added into the mixed solution B that step 3 obtains in step 47HNb6O19Mixed solution C is obtained, wherein step 1, step Rapid 2 and step 4 in the graphene oxide, pyrroles and the K that use7HNb6O19Mass ratio be 4: 87~145: 34~685;
Step 5, the mixed solution C for obtaining step 4 carry out hydro-thermal reaction, and reaction product washing is dried to obtain Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst.
Preferably, the concentration of the substance of mixed solution A is 2mg/mL in step 1, and ultrasonic time is 1~1.5h.
Preferably, the volume ratio of pyrroles and ethyl alcohol is 9~15: 100 in step 2.
Preferably, the drop rate of the ethanol solution of pyrroles is 1.1~3.3mL/min, mixing speed 800 in step 3 ~1200rpm.
Preferably, the K in step 47HNb6O19The amount of substance is 0.025~0.5mmol.
Preferably, the heating rate of hydro-thermal reaction and rate of temperature fall are 10 DEG C/min, the temperature of hydro-thermal reaction in step 5 It is 160~190 DEG C, the reaction time is 11~13h.
Preferably, in step 5 hydrothermal product washing and drying process are as follows: first use deionized water centrifuge washing at least 3 It is secondary, it then uses ethyl alcohol centrifuge washing 2 times, is finally dried in vacuo the product of washing, drying temperature is 60~65 DEG C, dry Time is 12~15h.
The present invention also protects Linquist type K prepared by the preparation method7HNb6O19Polypyrrole-oxygen reduction Graphite alkene composite photo-catalyst.
The present invention also protects Linquist type K prepared by the preparation method7HNb6O19Polypyrrole-oxygen reduction Application of the graphite alkene composite photo-catalyst in terms of Photocatalyzed Hydrogen Production.
Preferably, Photocatalyzed Hydrogen Production carries out in 300W xenon lamp condition in vacuum environment, and reaction temperature is 4~6 DEG C, Reaction time is 4~6h.
Compared with prior art, beneficial effects of the present invention are as follows:
1, Linquist type K after the present invention will mix7HNb6O19, the raw material of pyrroles and graphene oxide passes through a step hydro-thermal Legal system obtains Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, prepares raw material and is easy to get, process Simply, mild condition, and the stability of photochemical catalyst is good, has Ke Xunhuanliyong property;
2, the present invention has expanded the application range of polyoxometallate by the way that polyoxometallate and graphene is compound, Improve the performance of polyoxometallate;
3, by K in the present invention7HNb6O19It is compound with graphene, improve K7HNb6O19Optical response range, reduce band Gap, reduces the recombination rate of light induced electron and electron hole, to improve photocatalytic activity;
4, the present invention changes K by the addition of pyrroles7HNb6O19" peony " shape is prepared in the pattern of itself Photochemical catalyst, and the additional amount by controlling pyrroles controls come the degree of bursting forth of " peony " to photochemical catalyst;
5, Linquist type K prepared by the present invention7HNb6O19Polypyrrole-redox graphene composite photo-catalyst exists Still there is preferable production hydrogen activity, hydrogen-producing speed is up to 207.56 μm of ol/g/ in the case where there is no noble metal to do co-catalyst h。
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of composite photo-catalyst prepared by embodiment 1 in the present invention, embodiment 2 and embodiment 3;
Fig. 2 is the scanning of composite photo-catalyst prepared by embodiment 2 in the present invention, embodiment 4, embodiment 5 and embodiment 6 Electron microscope;
Fig. 3 is the scanning electron microscope (SEM) photograph of composite photo-catalyst prepared by embodiment 2 in the present invention, embodiment 7 and embodiment 8;
Fig. 4 is K in the present invention7HNb6O19With the light of the composite photo-catalyst of embodiment 1, embodiment 2 and embodiment 3 preparation Catalysis produces hydrogen activity comparison diagram;
Fig. 5 is that the light of composite photo-catalyst prepared by embodiment 2 in the present invention, embodiment 4, embodiment 5 and embodiment 6 is urged Change and produces hydrogen activity comparison diagram;
Fig. 6 is that the Photocatalyzed Hydrogen Production of composite photo-catalyst prepared by embodiment 2 in the present invention, embodiment 7 and embodiment 8 is living Property comparison diagram;
Fig. 7 is the Photocatalyzed Hydrogen Production circulation figure for the composite photo-catalyst that in the present invention prepared by embodiment 2.
Specific embodiment
Below by specific embodiment example, the present invention will be described in detail.The scope of the present invention is not limited to the tool Body embodiment.In following embodiments, improved Hummers method used is referring to below with reference to document: 1, improving Hummers method Prepare graphene oxide and its characterization;It is delivered in April, 2015 in " packaging journal " the 2nd phase of volume 7;2, prepared by graphene oxide The Optimal improvements of method were delivered in 2016 10 in " Chemical Industry in Guangzhou " the 19th phase of volume 44;3, it improves Hummers method and prepares oxygen Graphite alkene and its absorption copper ion research, are delivered in August, 2015 at " industrial water and waste water ".
Embodiment 1
The graphene oxide as made from improved Hummers method of 4mg is added in the water of 2mL step 1, and ultrasound Disperse 2h, obtain uniform graphene oxide dispersion, substance withdrawl syndrome is 2 mg/mL;
Step 2, by the ethyl alcohol of 110 μ L pyrroles and 1mL be uniformly mixed obtain the ethanol solution of pyrroles;
The ethanol solution of pyrroles in step 2 is slowly dropped in the graphene oxide dispersion in step 1 by step 3, Mixed solution A is obtained using magnetic stirrer 30min, mixing speed 1000rpm;
Step 4, the K that 0.125mmol is added into the mixed solution A in step 37HNb6O19, obtain mixed solution B;
Mixed solution B in step 4 is placed in polytetrafluoroethyllining lining autoclave by step 5, is reacted in 180 DEG C 12h;By the compound obtained after reaction with deionized water centrifuge washing 3 times, then use ethyl alcohol centrifuge washing 2 times, after washing Product be dried in vacuo 12h at 60 DEG C, obtain Linquist type K7HNb6O19Polypyrrole-redox graphene complex light Catalyst is designated as 1#.
Embodiment 2
It is identical as the synthetic method of embodiment 1, the difference is that K in the step 4 of the present embodiment7HNb6O19Dosage For 0.25mmol, Linquist type K is obtained7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, is designated as 2#.
Embodiment 3
It is identical as the synthetic method of embodiment 1, the difference is that K in the step 4 of the present embodiment7HNb6O19Dosage For 0.375mmol, Linquist type K is obtained7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, is designated as 3#.
Embodiment 4
It is identical as the synthetic method of embodiment 2, the difference is that in the step 2 of the present embodiment pyrroles and ethyl alcohol addition Amount is respectively 0 μ L and 1mL, obtains Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, mark For 4#.
Embodiment 5
It is identical as the synthetic method of embodiment 2, the difference is that in the step 2 of the present embodiment pyrroles and ethyl alcohol addition Amount is respectively 90 μ L and 1mL, obtains Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, mark For 5#.
Embodiment 6
It is identical as the synthetic method of embodiment 2, the difference is that in the step 2 of the present embodiment pyrroles and ethyl alcohol addition Amount is respectively 130 μ L and 1mL, obtains Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, It is designated as 6#.
Embodiment 7
It is identical as the synthetic method of embodiment 2, the difference is that step 5 hydrothermal temperature of the present embodiment is 160 DEG C, obtain Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, is designated as 7#.
Embodiment 8
It is identical as the synthetic method of embodiment 2, the difference is that step 5 hydrothermal temperature of the present embodiment is 190 DEG C, obtain Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, is designated as 8#.
Firstly, 1#~8# composite photo-catalyst is carried out morphology characterization using scanning electron microscope by us, Fig. 1 is this The scanning electron microscope (SEM) photograph for the composite photo-catalyst that in invention prepared by embodiment 1, embodiment 2 and embodiment 3, Fig. 2 are real in the present invention The scanning electron microscope (SEM) photograph of composite photo-catalyst prepared by example 2, embodiment 4, embodiment 5 and embodiment 6 is applied, Fig. 3 is in the present invention The scanning electron microscope (SEM) photograph of composite photo-catalyst prepared by embodiment 2, embodiment 7 and embodiment 8, can be seen that compound from Fig. 1-Fig. 3 Peony pattern is presented in material.Temperature and K7HNb6O19Dosage mainly influence the partial size of peony, and the dosage of pyrroles is main Influence the degree of bursting forth of peony.
Then, 1#~8# composite photo-catalyst is carried out Photocatalyzed Hydrogen Production experiment by us, and dose volume score first is 20% methanol solution, the methanol for being respectively then 20% with the volume fraction of 50mL by 1#~8# composite photo-catalyst of 50mg Solution mixing, is placed in photo catalysis reactor, at 5 DEG C, in vacuum condition, irradiates 5h using visible light (300W xenon lamp), Carry out photocatalytic activity test.
Fig. 4 is K in the present invention7HNb6O19With the light of the composite photo-catalyst of embodiment 1, embodiment 2 and embodiment 3 preparation Catalysis produces hydrogen activity comparison diagram, and Fig. 5 is complex light prepared by embodiment 2 in the present invention, embodiment 4, embodiment 5 and embodiment 6 The Photocatalyzed Hydrogen Production activity comparison diagram of catalyst, Fig. 6 are the compound of embodiment 2 in the present invention, embodiment 7 and the preparation of embodiment 8 The Photocatalyzed Hydrogen Production activity comparison diagram of photochemical catalyst.It can be seen that the pattern of composite material from Fig. 4-Fig. 6 and produce hydrogen activity by temperature Degree, pyrroles's dosage and K7HNb6O19The influence of dosage.K7HNb6O19Dosage be less than 0.25mmol when, the too small group of will lead to of partial size Poly-, hydrogen-producing speed is lower;K7HNb6O19When dosage is 0.25mmol, show that the uniform tree peony of pattern is flower-shaped, and hydrogen-producing speed reaches To 207.56 μm of ol/h/g of highest;K7HNb6O19When dosage is greater than 0.25mmol, partial size becomes larger, and causes collapsing on pattern, makes Obtaining hydrogen-producing speed reduces.Pyrroles's dosage influences the degree of bursting forth of peony, and petal shape, hydrogen-producing speed is presented in material when without pyrroles Very low (26 μm of ol/h/g), with the addition of pyrroles, peony is gradually bursted forth, and hydrogen-producing speed also gradually increases;When pyrroles is added When amount is 110 μ L, peony is bursted forth completely, and hydrogen-producing speed reaches maximum value;When pyrroles's amount is greater than 110 μ L, petal goes out again Now cause pattern inhomogenous, hydrogen-producing speed is lower;Temperature mainly influences the partial size of peony, when temperature is 160 DEG C, partial size compared with Small, there are agglomeration, hydrogen-producing speed is only 26.16 μm of ol/h/g;When temperature is 180 DEG C, obtained composite photo-catalyst is in Existing uniform tree peony is flower-shaped, and Photocatalyzed Hydrogen Production activity is higher;Temperature is 190 DEG C, and pattern collapses, and hydrogen-producing speed is reduced to 49.8 μ mol/h/g。
Table 1 is 1#~8# composite photo-catalyst hydrogen generation rate table in carrying out Photocatalyzed Hydrogen Production experiment, can from table To find out Linquist type K prepared by the present invention7HNb6O19Polypyrrole-redox graphene composite photo-catalyst has excellent Good photocatalytic activity.
1 1# of table~8# composite photo-catalyst hydrogen generation rate table
Finally, 2# composite photo-catalyst is carried out Photocatalyzed Hydrogen Production circulation experiment by us, dose volume score first is 20% methanol solution, the methanol solution for being respectively then 20% with the volume fraction of 50mL by the 2# composite photo-catalyst of 50mg Mixing, is placed in photo catalysis reactor, at 5 DEG C, in vacuum condition, irradiates 5h using visible light (300W xenon lamp), is the One cycle experiment;Then it vacuumizes again, irradiates 5h under the same terms, be second of circulation experiment;Then it vacuumizes again, in 5h is irradiated under the same terms, is third time circulation experiment;It finally vacuumizes again, it is the 4th circulation that 5h is irradiated under the same terms Experiment.
Fig. 7 is Photocatalyzed Hydrogen Production circulation figure, from figure 7 it can be seen that Linquist type K prepared by the present invention7HNb6O19- Polypyrrole-redox graphene composite photo-catalyst stability is preferable, after four circulations, still has preferable photocatalysis Activity.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, without departing from the principle of the present invention, it can also make several improvements and retouch, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1.Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst preparation method, feature exist In, comprising the following steps:
Graphene oxide is prepared by improved Hummers method in step 1, and obtained graphene oxide is mixed with water, and Ultrasonic disperse obtains mixed solution A;
Step 2 obtains the ethanol solution of pyrroles after mixing pyrroles and ethyl alcohol;
The ethanol solution for the pyrroles that step 2 obtains is added drop-wise in the mixed solution A that step 1 obtains by step 3, and stirring 30~ 45min obtains mixed solution B;
K is added into the mixed solution B that step 3 obtains in step 47HNb6O19Obtain mixed solution C, wherein step 1, step 2 and Graphene oxide, pyrroles and the K used in step 47HNb6O19Mass ratio be 4: 87~145: 34~685;
Step 5, the mixed solution C for obtaining step 4 carry out hydro-thermal reaction, and reaction product washing is dried to obtain Linquist Type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst.
2. Linquist type K according to claim 17HNb6O19Polypyrrole-redox graphene composite photo-catalyst Preparation method, which is characterized in that in step 1 concentration of the substance of mixed solution A be 2mg/mL, ultrasonic time be 1~1.5h.
3. Linquist type K according to claim 17HNb6O19Polypyrrole-redox graphene composite photo-catalyst Preparation method, which is characterized in that in step 2 volume ratio of pyrroles and ethyl alcohol be 9~15: 100.
4. Linquist type K according to claim 17HNb6O19Polypyrrole-redox graphene composite photo-catalyst Preparation method, which is characterized in that in step 3 drop rate of the ethanol solution of pyrroles be 1.1~3.3mL/min, stirring speed Degree is 800~1200rpm.
5. Linquist type K according to claim 17HNb6O19Polypyrrole-redox graphene composite photo-catalyst Preparation method, which is characterized in that the K in step 47HNb6O19The amount of substance is 0.025~0.5mmol.
6. Linquist type K according to claim 17HNb6O19Polypyrrole-redox graphene composite photo-catalyst Preparation method, which is characterized in that the heating rate of hydro-thermal reaction and rate of temperature fall are 10 DEG C/min in step 5, and hydro-thermal is anti- The temperature answered is 160~190 DEG C, and the reaction time is 6~12h.
7. Linquist type K according to claim 17HNb6O19Polypyrrole-redox graphene composite photo-catalyst Preparation method, which is characterized in that the washing and drying process of hydrothermal product in step 5 are as follows: first with deionized water centrifugation wash It washs at least 3 times, then uses ethyl alcohol centrifuge washing 2 times, be finally dried in vacuo the product of washing, drying temperature is 60~65 DEG C, drying time is 12~15h.
8.Linquist type K7HNb6O19Polypyrrole-redox graphene composite photo-catalyst, which is characterized in that use right It is required that 1~7 described in any item preparation methods are prepared.
9. Linquist type K according to claim 87HNb6O19Polypyrrole-redox graphene composite photo-catalyst Application, which is characterized in that be used for Photocatalyzed Hydrogen Production.
10. Linquist type K according to claim 97HNb6O19Polypyrrole-redox graphene composite photo-catalyst Application, which is characterized in that Photocatalyzed Hydrogen Production carries out in 300W xenon lamp condition in vacuum environment, reaction temperature be 4~6 DEG C, the reaction time is 4~6h.
CN201810939195.4A 2018-08-12 2018-08-12 Linquist type K7HNb6O19-polypyrrole-reduced graphene oxide composite photocatalyst and preparation method and application thereof Active CN109046470B (en)

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CN111468100A (en) * 2020-04-18 2020-07-31 河南大学 Preparation method of in-situ grown niobium polyacid/graphite photocatalyst and application of photocatalyst in tetracycline degradation
CN111468100B (en) * 2020-04-18 2023-05-30 河南大学 Preparation method of in-situ grown polyacid niobium/graphene photocatalyst and application of in-situ grown polyacid niobium/graphene photocatalyst in tetracycline degradation
CN113477241A (en) * 2021-09-07 2021-10-08 华南理工大学 Ternary composite photocatalyst and preparation method and application thereof
CN113477241B (en) * 2021-09-07 2021-12-17 华南理工大学 Ternary composite photocatalyst and preparation method and application thereof
CN115400794A (en) * 2022-05-05 2022-11-29 河南大学 Preparation method and application of cobaltosic oxide/niobate composite material with p-n junction
CN115400794B (en) * 2022-05-05 2023-09-15 河南大学 Preparation method and application of cobaltosic oxide/niobate composite material with p-n junction

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