CN106807381A - A kind of composite photo-catalyst and preparation method thereof - Google Patents
A kind of composite photo-catalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 119
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 118
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- 238000010438 heat treatment Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910001000 nickel titanium Inorganic materials 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 16
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 4
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- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 15
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 14
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 10
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
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- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
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- 239000010842 industrial wastewater Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
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- 239000010439 graphite Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
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- 238000000862 absorption spectrum Methods 0.000 description 1
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- 238000002306 biochemical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
A kind of composite photo-catalyst and preparation method thereof, it relates generally to photocatalysis technology field.Wherein, the method can be by being combined together that Graphene and NiTi layered dihydroxyl compound are stablized, make full use of the huge specific surface area of Graphene to improve the Dye Adsorption capacity of composite photo-catalyst, the separative efficiency of its carrier is improved using the excellent conductivity of Graphene two-dimensional structure；By being introduced into Graphene so that producing impurity energy level in composite photo-catalyst, the energy gap of composite photo-catalyst is reduced, enhance light abstraction width.Therefore, above-mentioned composite photo-catalyst preparation method, not only preparation process is simple is practical, and the composite photo-catalyst for preparing has, and light absorpting ability is strong, photocatalysis efficiency is high and steady performance, its treatment that can be applied to Industry Waste organic pollutants.
Description
Technical field
The present invention relates to photocatalysis technology field, in particular to a kind of composite photo-catalyst and preparation method thereof.
Background technology
As the fast development of China's industry, the discharge capacity of industrial wastewater increase year by year, cause the severe contamination of environment.Mesh
Before, traditional organic contamination substance treating method has physical method, chemical method and biochemical method etc., but have or it is many or
Few defect can not meet the requirement of sustainable development, be primarily present low catalytic efficiency, high cost, secondary pollution problems.Light
Catalysis technique be applied to environmental Kuznets Curves field have the advantages that efficiently, green, it is economical, effectively utilize solar energy.
At present, photochemical catalyst is to study a most commonly used branch in photocatalysis technology, however, all the time, light is urged
The problems such as agent is faced with complicated synthesis technique, low catalytic efficiency and high energy consumption, this causes it to be received in industrialized production and application
Limitation is arrived.
The content of the invention
It is an object of the invention to provide a kind of composite photo-catalyst, it has stronger light absorpting ability and higher urges
Change efficiency, can be used for the treatment of Industry Waste organic pollutants.
Another mesh of the invention is to provide a kind of preparation method of composite photo-catalyst, and it can be by Graphene (GNS)
With being combined together for Ni-Ti layered dihydroxyl compound (Ni-Ti LDH) stabilization, and its preparation process is simple, practicality, tool
There is industrial production prospect higher.
The present invention solves its technical problem to be realized using following technical scheme.
The present invention proposes a kind of preparation method of composite photo-catalyst, and it is comprised the following steps：
Deionized water and graphene oxide carried out into first time to mix, the solution of Graphene first is obtained；By Graphene first
Solution with glucose mix for second, obtains the solution of Graphene second, and it is molten to add the ammoniacal liquor that mass fraction is 24-26%
Liquid obtains the solution of Graphene the 3rd to third time mixing is carried out in the solution of Graphene second；Is carried out to the solution of Graphene the 3rd
After once heating, first time centrifuge washing is carried out；Enter to by adding deionized water in the Graphene after first time centrifuge washing
The 4th mixing of row, obtains graphene suspension, addition titanium tetrachloride solution, six water nickel nitrates and urea to graphene suspension
In carry out the 5th time mixing, obtain composite photo-catalyst mixed solution；Second is carried out to composite photo-catalyst mixed solution to add
After heat, second centrifuge washing is carried out.
The present invention proposes a kind of composite photo-catalyst, and it is obtained by the preparation method of above-mentioned composite photo-catalyst.
The beneficial effect of the composite photo-catalyst of the embodiment of the present invention and preparation method thereof is：Using simple and practical side
Method, by being combined together for GNS and Ni-Ti LDH stabilizations；Substantially increased by using the huge specific surface area of Graphene multiple
The Dye Adsorption capacity of closing light catalyst；Photoproduction electricity is greatly enhanced by using the excellent conductivity of Graphene two-dimensional structure
The transmission in son and hole, transfer, improve its separative efficiency；In addition, being introduced into for Graphene can be produced in composite photo-catalyst
Impurity energy level, the energy gap of reduction composite photo-catalyst, enhancing light abstraction width, therefore above-mentioned composite photo-catalyst preparation side
Method, not only preparation process is simple is practical, and the composite photo-catalyst for preparing has, and light absorpting ability is strong, high catalytic efficiency, property
Can stablize and wait excellent photocatalysis performance.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be attached to what is used needed for embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, thus be not construed as it is right
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is graphite oxide, the XRD of GNS, Ni-Ti LDH and GNS/LDH composites in the embodiment of the present invention 1；
Fig. 2 is the efficiency of different sample visible light photocatalytic degradation MB in test example of the present invention；
Fig. 3 be the embodiment of the present invention 1 in GNS/LDH composite photo-catalyst visible light photocatalytic degradation MB different times it is corresponding
The UV-vis spectroscopy curve of spectrum；
Fig. 4 is the photocatalysis stabilization of GNS/LDH composite photo-catalyst visible light photocatalytic degradations MB in the embodiment of the present invention 1
Property.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional product that can be obtained by commercially available purchase
Product.
Composite photo-catalyst of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of composite photo-catalyst provided in an embodiment of the present invention, comprises the following steps：
S1, deionized water and graphene oxide carry out first time mix, obtain the solution of Graphene first.
It should be noted that step S1 is mainly the process of the configuration solution of Graphene first.The solution of Graphene first is multiple
Important Matrix Solution in closing light catalyst preparation process, wherein the graphene oxide for containing is the final gained complex light for preparing urging
The important component of agent.Therefore, process and concentration are mixed with for it has certain technological requirement, specifically, on
State first time mixed process is carried out by carrying out to deionized water and graphene oxide ultrasonically treated 2 hours, is configured
The solution of Graphene first concentration be 0.45-0.55mg/mL, it is preferable that the concentration of the solution of Graphene first be 0.5mg/mL.
S2, the solution of Graphene first with glucose mix for second, obtain the solution of Graphene second, and add matter
Amount fraction is the ammonia spirit of 24-26% to third time mixing is carried out in the solution of Graphene second, obtains the solution of Graphene the 3rd.
It should be noted that in second mixing and third time mixed process, the glucose and ammoniacal liquor for being added are to make
For reducing agent is reduced to the graphene oxide in the solution of former Graphene first, it is set to be reduced to form graphene nanometer sheet,
So as to show surface-active state higher, be conducive to follow-up Ti4+And Ni2+And the combination of its stabilization.Requiring emphasis is, this
The reducing agent that embodiment is provided is by glucose and ammoniacal liquor while using, to enable that graphene oxide is quickly reduced to
Graphene nanometer sheet.
Further, in order to sufficiently mix and carrying out redox reaction reducing agent and the solution of Graphene first, this
Embodiment is to be realized within 1 hour by magnetic agitation respectively when second mixing is carried out and third time mixes.
Further, because the graphene oxide concentration in the solution of Graphene first is 0.45-0.55mg/mL, therefore must
Matched reducing agent must be added to reduce it, therefore, when glucose is added to the solution of Graphene first, added
Plus mass concentration of the glucose in the solution of Graphene first be 7-9mg/mL, it is therefore preferable to 8mg/mL；In addition, for ammoniacal liquor
Addition should also control in 1.5-5.5mL, be preferably controlled within 5mL, and be emphasized that the mass concentration of ammoniacal liquor
Why control in 24-26%, be not only due to it carries out reduction reaction as reducing agent and graphene oxide, it is often more important that
The aobvious alkalescence of the aqueous solution of itself, its concentration it is excessive or it is too small can influence the pH of whole solution, so as to influence redox reaction
Generation.
S3, first time heating is carried out to the solution of Graphene the 3rd after, carry out first time centrifuge washing.
It should be noted that first time heating and first time centrifuge washing are carried out to the solution of Graphene the 3rd, its main mesh
Be to be extracted and collected in order to the graphene nanometer sheet that obtains will be reduced.Wherein, first, by graphite by way of heating
The solution of alkene the 3rd is evaporated extraction；Secondly, the product after being extracted to evaporation carries out centrifuge washing, contains in removal product
Impurity；Finally, the solid resultant product collection for obtaining will be centrifuged, you can obtain the basic raw material of graphene nanometer sheet.
Further, effectively carried out in order that obtaining the extraction of graphene nanometer sheet in step 3 and collection process, this implementation
Example is heated when the first heating is carried out by the way of oil bath, and controls heat time first time at 1-4 hours, plus
Hot temperature control is at 94-96 DEG C, it is preferable that it is 95 DEG C to control heating-up temperature；When centrifuge washing is carried out, carried out with deionized water
3-5 washing, in 6000-7000rpm, centrifugation time is 1-1.5 hours for the rotating speed control of centrifuge.
S4, in step 3 by the Graphene after first time centrifuge washing add deionized water carry out the 4th time mixing,
Graphene suspension is obtained, is carried out the 5th time in addition titanium tetrachloride solution, six water nickel nitrates and urea to graphene suspension
Mixing, obtains composite photo-catalyst mixed solution.
Further, the process of step 4 is to prepare the most important step of composite photo-catalyst.First, received by by step 3
The graphene nanometer sheet and deionized water that collection is obtained carry out the 4th mixing, and it is 0.8-1.2mg/L's that configuration obtains mass concentration
Graphene suspension；Secondly, the 5th is carried out by adding titanium tetrachloride solution, six water nickel nitrates and urea and graphene suspension
Secondary mixing so that the graphene nanometer sheet being suspended in graphene suspension can be with Ti4+And Ni2+Stable is combined together.
It should be noted that before the 5th mixing is carried out, the urea for being added is as pH adjusting agent, to prepare Ni-Ti stratiform pair
Oxyhydroxide provides an environment for alkalescence.
Further, in order that the 5th time is more fully mixed, the present embodiment when mixing for the 5th time is stirred by magnetic force
Mix what is realized within 1 hour；In order that obtaining the graphene nanometer sheet and Ni-Ti stratiform oxyhydroxide in composite photo-catalyst mixed solution
Thing can preferably occur suction-operated, the present embodiment control Ti4+And Ni2+Molar concentration rate be 1：5, titanium tetrachloride solution
It is 1.1-1.0, the graphene nanometer sheet in graphene suspension with the total quality of six water nickel nitrates and the mass values of urea
The Ni-Ti layered dihydroxyl compound mass ratio formed in mixing with the 5th time is 1：26-30, therefore entered using aforementioned proportion relation
The mixing of row the 5th time can enable being combined together for Graphene and Ni-Ti LDH stabilizations, and it is high to form photocatalysis efficiency, property
The composite photo-catalyst mixed solution of energy stabilization.
It should be noted that after the 5th mixing is carried out, the light contained in the composite photo-catalyst mixed solution for obtaining
Catalyst is in particular, graphene/nickel-titanium layer shape oxyhydroxide composite visible light catalyst.
After S5, the composite photo-catalyst mixed solution to being obtained in step 4 carry out second heating, second centrifugation is carried out
Washing.
Further, second heating and second centrifuge washing, its purpose are carried out to composite photo-catalyst mixed solution
It is to extract and collect the graphene/nickel-titanium layer shape oxyhydroxide composite visible light catalyst prepared by the present embodiment.Therefore,
First, using the mode of heating of oil bath, it is 40-50 hours to control second heat time of heating, and heating-up temperature is 100-120
DEG C, solute extraction is carried out to composite photo-catalyst mixed solution；Secondly, to the solute for extracting, that is, it is exactly graphene/nickel-titanium layer
Shape oxyhydroxide composite visible light catalyst carries out centrifuge washing, it is necessary to illustrate, in order that the process effect of centrifuge washing
More preferably, washing process carries out repeatedly alternately washing fruit using deionized water and absolute ethyl alcohol, and in final centrifugation, centrifuge
Rotating speed control in 6000-7000rpm, centrifugation time is 1.5-2 hours.
Present invention also offers a kind of composite photo-catalyst, it is using the preparation method system of above-mentioned composite photo-catalyst
, the composite photo-catalyst is specifically graphene/nickel-titanium layer shape oxyhydroxide composite visible light catalyst, and it has light
The excellent photocatalysis performances such as absorbability is strong, high catalytic efficiency, stable performance, can be applied to field of industrial waste water treatment.
Feature of the invention and performance are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation method of composite photo-catalyst, and its preparation process is as follows：
First, the graphene oxide of 0.25g is weighed, is added in the beaker equipped with 500ml deionized waters, then beaker is put
Ultrasound 2 hours in Ultrasound Instrument, obtain the solution of Graphene first that mass concentration is 0.5mg/mL.
Secondly, the above-mentioned solution of 500mL Graphenes first is mixed with the glucose of 4g, and stirred with magnetic stirrer
Mix 1 hour, obtain the solution of Graphene second；It is molten to the ammoniacal liquor that 2mL mass fractions are 25% is added in the solution of Graphene second again
Liquid is stirred mixing, obtains the solution of Graphene the 3rd；95 DEG C of oil bath heatings 1 are carried out as the solution of Graphene the 3rd to obtained by small
When, obtain black sample, using deionized water this black sample is carried out 3 times washing after, with centrifuge 6000rpm rotating speed
Lower centrifugation, obtains graphene nanometer sheet.
Finally, it is stirred to by adding 100mL deionized waters in the graphene nanometer sheet after centrifuge washing, is configured to
1mg/mL graphene suspension, then by TiCl4With HCl volume ratios 1:1 0.1mL titanium tetrachloride solutions, the water nitre of 1.32g six
Sour nickel and 1.3g urea are dispersed in above-mentioned graphene suspension and carry out magnetic agitation 20 minutes, 100 DEG C of gained mixed solution
After oil bath heating 40 hours, using alternately washing 5 times of deionized water and absolute ethyl alcohol, it is in rotating speed with centrifuge finally
In the case of 6000rpm, centrifugation 1.8 hours is carried out to it.
The present embodiment additionally provides a kind of composite photo-catalyst, and it is the composite photo-catalyst system provided by the present embodiment
Preparation Method is obtained, and it is specifically a kind of graphene/nickel-titanium layer shape oxyhydroxide composite visible light catalyst.
Embodiment 2
The present embodiment provides a kind of preparation method of composite photo-catalyst, and its preparation process is as follows：
First, the graphene oxide of 0.25g is weighed, is added in the beaker equipped with 500ml deionized waters, then beaker is put
Ultrasound 2 hours in Ultrasound Instrument, obtain the solution of Graphene first that mass concentration is 0.5mg/mL.
Secondly, the above-mentioned solution of 500mL Graphenes first is mixed with the glucose of 4g, and stirred with magnetic stirrer
Mix 1 hour, obtain the solution of Graphene second；It is molten to the ammoniacal liquor that 5mL mass fractions are 25% is added in the solution of Graphene second again
Liquid is stirred mixing, obtains the solution of Graphene the 3rd；95 DEG C of oil bath heatings 4 are carried out as the solution of Graphene the 3rd to obtained by small
When, obtain black sample, using deionized water this black sample is carried out 4 times washing after, with centrifuge 7000rpm rotating speed
Lower centrifugation, obtains graphene nanometer sheet.
Finally, it is stirred to by adding 100mL deionized waters in the graphene nanometer sheet after centrifuge washing, is configured to
1mg/mL graphene suspension, then by TiCl4With HCl volume ratios 1:1 0.1mL titanium tetrachloride solutions, the water nitre of 1.32g six
Sour nickel and 1.3g urea are dispersed in above-mentioned graphene suspension and carry out magnetic agitation 40 minutes, 120 DEG C of gained mixed solution
After oil bath heating 50 hours, using alternately washing 6 times of deionized water and absolute ethyl alcohol, it is in rotating speed with centrifuge finally
In the case of 7000rpm, centrifugation 2 hours is carried out to it.
The present embodiment additionally provides a kind of composite photo-catalyst, and it is the composite photo-catalyst system provided by the present embodiment
Preparation Method is obtained, and it is specifically a kind of graphene/nickel-titanium layer shape oxyhydroxide composite visible light catalyst.
Embodiment 3
The present embodiment provides a kind of preparation method of composite photo-catalyst, and its preparation process is as follows：
First, the graphene oxide of 0.25g is weighed, is added in the beaker equipped with 500ml deionized waters, then beaker is put
Ultrasound 2 hours in Ultrasound Instrument, obtain the solution of Graphene first that mass concentration is 0.5mg/mL.
Secondly, the above-mentioned solution of 500mL Graphenes first is mixed with the glucose of 4g, and stirred with magnetic stirrer
Mix 1 hour, obtain the solution of Graphene second；Again to the ammoniacal liquor that addition 3.5mL mass fractions in the solution of Graphene second are 25%
Solution is stirred mixing, obtains the solution of Graphene the 3rd；95 DEG C of oil bath heatings 4 are carried out as the solution of Graphene the 3rd to obtained by
Hour, black sample is obtained, after 4 washings are carried out to this black sample using deionized water, with centrifuge turning in 6500rpm
The lower centrifugation of speed, obtains graphene nanometer sheet.
Finally, it is stirred to by adding 100mL deionized waters in the graphene nanometer sheet after centrifuge washing, is configured to
1mg/mL graphene suspension, then by TiCl4With HCl volume ratios 1:1 0.1mL titanium tetrachloride solutions, the water nitre of 1.32g six
Sour nickel and 1.3g urea are dispersed in above-mentioned graphene suspension and carry out magnetic agitation 40 minutes, 110 DEG C of gained mixed solution
After oil bath heating 45 hours, using alternately washing 6 times of deionized water and absolute ethyl alcohol, it is in rotating speed with centrifuge finally
In the case of 6500rpm, centrifugation 2 hours is carried out to it.
The present embodiment additionally provides a kind of composite photo-catalyst, and it is the composite photo-catalyst system provided by the present embodiment
Preparation Method is obtained, and it is specifically a kind of graphene/nickel-titanium layer shape oxyhydroxide composite visible light catalyst.
Test example
In order to carry out identification to the composite photo-catalyst obtained in the embodiment of the present invention, the present invention is respectively to embodiment
1 graphene oxide, graphene nanometer sheet (GNS), Ni-Ti stratiform oxyhydroxide (Ni-Ti LDH) and graphene/nickel-titanium
Stratiform oxyhydroxide composite visible light catalyst (GNS/LDH) carries out XRD tests, and its result is as shown in Figure 1.Need explanation
It is that the preparation of Ni-Ti LDH samples can individually be produced with urea method.
Reference picture 1 can be seen that graphene oxide after being reduced by reducing agent, lose original crystal structure, and
And entirely reduction process is very abundant；After GNS and Ni-Ti LDH generation absorption forms GNS/LDH, GNS/LDH still shows
The crystal structure characteristic of Ni-Ti LDH.Therefore, reference picture 1 can show prepared by the composite photo-catalyst in above-described embodiment
The various reactions of journey are very abundant, and the final product of gained is target product GNS/LDH.
Further, in order to evaluate the photocatalysis performance that embodiment prepares sample, this test example is to enter in accordance with the following methods
Row ground：First, it is 1 × 10 the catalyst sample of 50mg to be dispersed in into 100mL initial concentrations-5The methylene blue (MB) of mol/L is molten
In liquid, magnetic agitation 30 minutes under dark condition must reach the catalyst sample of adsorption saturation.Secondly, by visible ray
Lower photocatalytic degradation MB solution, evaluates the photocatalytic activity of prepared sample, specifically, with 300W xenon lamps as light source, passes through
Wave chopping glass filters off wavelength and is less than 420nm ultraviolet lights, and removing light by the beaker applied cyclic water system of light-catalyzed reaction illuminates the way
The fuel factor for rising, every certain reaction time, takes 4mL reaction solutions, and is separated by supercentrifuge, removes supernatant liquid.
Wherein, the absorption spectra of filtered fluid is detected by ultraviolet-visible spectrophotometer, and is absorbed at 663.5nm positions by observing
The change of peak intensity detects the change of its concentration.It should be noted that it can be seen from Lambert-Beer laws, during degraded t
Between efficiency can be by concentration ratio Ct/C0Value represents, wherein, C0It is initial concentration, CtIt is the methylene blue of light degradation t times
Concentration.The result of final test, refer to Fig. 2, Fig. 3 and Fig. 4.
Reference picture 2 is as can be seen that in same time, GNS/LDH degradeds MB's is fastest；Can be with bright with reference to Fig. 2 and Fig. 3
Aobvious to find out, over time, MB is degraded by GNS/LDH, and MB contents in filtered fluid are fewer and feweri, reach up to
During 90min, the MB in filtered fluid is almost all degraded.In addition, it is necessary to explanation, Fig. 4 is that the initial 50mg of test example is urged
Agent sample carries out data result successively obtained by the degradation experiment of five times to 5 parts of identical MB solution, from fig. 4, it can be seen that
In the degradation experiment of 5 times, with the increase of degraded number of times, degradation capabilities of the GNS/LDH for MB more slightly weakens, but
Degradation capability on the whole is still very strong, therefore can reflect from Fig. 4, the GNS/LDH composites tool prepared by the present embodiment
There is very strong photocatalysis stability.
In sum, the composite photo-catalyst preparation method of the embodiment of the present invention, it can be by Graphene and Ni-Ti LDH
Stable is combined together, and the Dye Adsorption that the specific surface area for making full use of Graphene huge improves composite photo-catalyst holds
Amount, the separative efficiency of its carrier is improve using the excellent conductivity of Graphene two-dimensional structure；In addition, the introducing of Graphene
So that generating impurity energy level in composite photo-catalyst, so as to reduce the energy gap of composite photo-catalyst, light suction is enhanced
Receive scope.Therefore, above-mentioned composite photo-catalyst preparation method, not only preparation process is simple is practical, and the complex light for preparing
Catalyst visible absorption ability is strong, photocatalysis efficiency is high, stable performance, and it can be applied to organic contamination in industrial wastewater
The treatment of thing.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of composite photo-catalyst, it is characterised in that it is comprised the following steps：
Deionized water and graphene oxide carried out into first time to mix, the solution of Graphene first is obtained；
The solution of the Graphene first with glucose mix for second, the solution of Graphene second is obtained, and add quality
Fraction is the ammonia spirit of 24-26% to third time mixing is carried out in the solution of the Graphene second, obtains Graphene the 3rd molten
Liquid；
After carrying out first time heating to the solution of the Graphene the 3rd, first time centrifuge washing is carried out；
The 4th mixing is carried out to by adding deionized water in the Graphene after the first time centrifuge washing, Graphene is obtained
Suspension, carries out the 5th mixing in addition titanium tetrachloride solution, six water nickel nitrates and urea to the graphene suspension, obtain
To composite photo-catalyst mixed solution；
After carrying out second heating to the composite photo-catalyst mixed solution, second centrifuge washing is carried out.
2. the preparation method of composite photo-catalyst according to claim 1, it is characterised in that the first time mixing be into
Row is ultrasonically treated 2 hours, and the concentration of the solution of the Graphene first is 0.45-0.55mg/mL.
3. the preparation method of composite photo-catalyst according to claim 1, it is characterised in that second mixing be into
Row magnetic agitation 1 hour, the concentration of glucose described in the solution of the Graphene second be 0.7-0.9mg/mL, addition it is described
The volume of ammonia spirit is 1.5-5.5mL.
4. the preparation method of composite photo-catalyst according to claim 1, it is characterised in that the first time heating plus
The hot time is 1-4 hours, and heating-up temperature is 94-96 DEG C.
5. the preparation method of composite photo-catalyst according to claim 1, it is characterised in that the graphene suspension
Concentration is 0.8-1.2mg/L；Before carrying out the 5th mixing, the Ti in the titanium tetrachloride solution of addition4+With it is described
The Ni of six water nickel nitrates2+Mol ratio is 1:5.
6. the preparation method of composite photo-catalyst according to claim 5, it is characterised in that the 5th mixing be into
Row magnetic agitation 20-40 minutes.
7. the preparation method of composite photo-catalyst according to claim 6, it is characterised in that second heating plus
The hot time is 40-50 hours, and heating-up temperature is 100-120 DEG C.
8. the preparation method of composite photo-catalyst according to claim 1, it is characterised in that the first time heating and institute
Stating second heating is heated by way of oil bath.
9. the preparation method of composite photo-catalyst according to claim 1, it is characterised in that second centrifuge washing
Carried out by the way that deionized water and absolute ethyl alcohol is used alternatingly.
10. a kind of composite photo-catalyst, it is characterised in that the composite photo-catalyst is according to claim 1-9 any one institute
The preparation method of the composite photo-catalyst stated is obtained.
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| CN115369439A (en) * | 2022-04-11 | 2022-11-22 | 天津工业大学 | Self-supporting oxygen evolution electrocatalyst coupling solar photo-thermal and preparation method and application thereof |
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| Title |
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| BEI LIET.AL: ""Visible-Light-Responsive Photocatalysts toward Water Oxidation Based on NiTi-Layered Double Hydroxide/Reduced Graphene Oxide Composite Materials"", 《ACS APPL. MATER. INTERFACES》 * |
| CHENGZHOU ZHUET.AL: ""Reducing Sugar: New Functional Molecules for the Green Synthesis of Graphene Nanosheets"", 《ACSNANO》 * |
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| CN115369439A (en) * | 2022-04-11 | 2022-11-22 | 天津工业大学 | Self-supporting oxygen evolution electrocatalyst coupling solar photo-thermal and preparation method and application thereof |
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Application publication date: 20170609 |