CN104368367B - A kind of Graphene/hydroxyl cupric phosphate composite catalyst and preparation method thereof - Google Patents
A kind of Graphene/hydroxyl cupric phosphate composite catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the preparation field of composite catalyzing material, be specifically related to a kind of Graphene/hydroxyl cupric phosphate composite catalyst and preparation method thereof.Concretely comprise the following steps: 1) prepare the graphene oxide water solution of certain solubility；2) a certain amount of graphene oxide water solution is added in soluble copper salt and soluble phosphate reaction system；3) regulation pH value；4) above-mentioned suspension is placed 100 ~ 140 DEG C of reaction 6 12h in a kettle., cool down, be centrifuged, wash after dry to obtain Graphene/hydroxyl cupric phosphate composite catalyst.In composite catalyst, the mass ratio of graphene nanometer sheet and hydroxyl cupric phosphate is 0.2～6% 99.8～94%, and ratio of greater inequality is 2% 98%.This composite catalyst has good catalytic performance under simulated solar irradiation, can be applicable to the water treatment field of industrial wastewater.
Description
Technical field
The present invention relates to belong to the preparation field of composite catalyzing material, be specifically related to a kind of Graphene/hydroxyl cupric phosphate multiple
Close catalyst and preparation method thereof.
Technical background
Currently, the most serious problem of environmental pollution has obtained the great attention of people, and wherein water pollution problems is the most urgently
Prevention to be obtained and improvement.But along with water pollutant qualitative diversity and complexity, traditional method for treating water can not be expired
The requirement of foot people.The advantages such as photocatalysis is simple to operate by self, low energy consumption, reaction condition gentleness, non-secondary pollution, become
The new technique processed for waste water, has vast potential for future development.Hydroxyl cupric phosphate (Cu2(OH)PO4) it is a kind of novel photocatalysis
Agent, all has under ultraviolet-visible even region of ultra-red and is preferably catalyzed activity, is a kind of to have the novel of applications well prospect
Active photocatalyst.But, hydroxyl cupric phosphate prepared by existing method there is also of both problem: 1) di prepared
Shot copper footpath is bigger, mainly more than micron order；2) under the auxiliary not having electronics trapping agent hydrogen peroxide, hydroxyl cupric phosphate
Performance of catalyzing and degrading pollutant is the most weak.
Summary of the invention
It is an object of the invention to solve the problem that existing method exists, from reducing catalyst particle size, increasing its specific surface
Amass and a kind of Graphene/hydroxyl cupric phosphate composite catalyst of the aspects such as its electron-hole separates offer and preparation method thereof is provided.
We pass through one kettle way fabricated in situ Graphene/hydroxyl cupric phosphate composite catalyst, find hydroxyl cupric phosphate
Particle diameter reduction and the graphene nanometer sheet mixed can significantly improve the photocatalysis degradation organic contaminant of hydroxyl cupric phosphate
Energy.
The present invention is with graphene oxide, and soluble copper salt, soluble phosphate are that raw material is prepared for Graphene/di
Copper composite catalyst.
A kind of Graphene/hydroxyl cupric phosphate composite catalyst, it includes: graphene nanometer sheet and hydroxyl cupric phosphate；It is special
Levy and be: shared by each composition, mass ratio is: graphene nanometer sheet 0.2 ~ 6 %, hydroxyl cupric phosphate 99.8 ~ 94 %；Described Graphene/
In hydroxyl cupric phosphate composite catalyst, graphene nanometer sheet is attached to the surface of hydroxyl cupric phosphate or is connected between hydroxyl cupric phosphate；
The thickness of graphene nanometer sheet is 0.37 ~ 5nm, and structure is single or multiple lift；Hydroxyl cupric phosphate is bar-shaped, and a length of 200 ~ 500
nm。
A kind of preparation method of Graphene/hydroxyl cupric phosphate composite catalyst, its step is as follows:
(1) graphene oxide of measured amounts, puts in beaker, adds a certain amount of pure water, seals with preservative film, super
Sound dispersion processes 12 ~ 24 h, then carries out the stir process of 12 ~ 24 h on magnetic stirring apparatus；
(2) pending good after, be centrifuged separating treatment, take supernatant, stand-by after having demarcated graphene oxide concentration；
(3) weighing a certain amount of soluble copper salt, after being completely dissolved in water, stirring is lower adds a certain amount of titanium pigment
Hydrochlorate, adds a certain amount of graphene oxide water solution after stirring 30 ~ 60 min；
(4) regulating pH with sodium hydroxide after continuing stirring 10 ~ 30min is 7, subsequently above-mentioned suspension is loaded reactor
In, move in air dry oven, at 100 ~ 140 DEG C, react 6 ~ 24 h prepare precipitation, by centrifugation, washing, obtain stone after drying
Ink alkene/hydroxyl cupric phosphate composite catalyst powder.
In step (1), graphene oxide used uses Hummers method (J Am Chem Soc. 1958,80,1339.)
It is prepared from.
Graphene oxide water solution concentration prepared in step (2) is 0.2 ~ 6 mg/mL.
In step (3), copper ion and phosphate anion are according to stoichiometric proportion dispensing 2:1.
Graphene and the mass ratio of hydroxyl cupric phosphate in gained Graphene/hydroxyl cupric phosphate composite catalyst in step (4)
For graphite 0.2 ~ 6 % 99.8 ~ 94 %.
The Graphene of the present invention/hydroxyl cupric phosphate composite catalyst has good photocatalysis degradation organic contaminant
Can, can be used for the water treatment field of industrial wastewater.
The catalytic performance test method used is as follows:
Graphene/hydroxyl cupric phosphate the composite catalyst weighing 100 mg is inserted in photocatalytic system, the lower addition 150 of stirring
The methylene blue solution of mL 10.0 mg/L, be subsequently placed in dark after stirring and adsorbing half an hour xenon lamp (800 nm >=λ >=
Light-catalyzed reaction is carried out under 320nm).
In the case of not adding electronics trapping agent, Graphene/hydroxyl cupric phosphate composite catalyst can drop in 1 hour
Solve and remove the methylene blue of 80% in aqueous systems.The above results shows, prepared Graphene/hydroxyl cupric phosphate composite catalyst exists
There is under simulated solar irradiation the photocatalysis performance of excellence, be a kind of potential Industrial Wastewater Treatment material.
Advantages of the present invention is as follows:
Using the Graphene/hydroxyl cupric phosphate composite catalyzing material of one kettle way fabricated in situ, this method building-up process is simple, easily
Operation, is the synthetic method of a kind of effective graphene inorganic composite.
The hydroxyl cupric phosphate of synthesis is bar-shaped, a length of 200 ~ 500 nm, and its particle diameter is less than published patent
(CN201310531313.5), the thickness of graphene nanometer sheet is 0.37 ~ 5 nm, is attached to hydroxyl cupric phosphate surface or is connected to
Between hydroxyl cupric phosphate granule, the migration of electrons in photocatalytic process can be effectively improved, suppress the compound of electrons, from
And enhance the photocatalysis performance of this hydroxyl cupric phosphate, it is a kind of potential to can be applicable to the light of contaminant degradation in industrial wastewater
Catalysis material.
Accompanying drawing explanation
Fig. 1 is the XRD figure of Graphene in the present invention/hydroxyl cupric phosphate composite catalyst.
Fig. 2 is the SEM figure of Graphene in the present invention/hydroxyl cupric phosphate composite catalyst.
Fig. 3 is the catalytic degradation performance map of composite catalyst in embodiment 3 under room temperature.
Detailed description of the invention
As shown in Figure 1 and Figure 2, showing for Graphene/hydroxyl cupric phosphate composite catalyst of being prepared by the method for the present invention
It is intended to；The preparation method of the present invention is illustrated below in conjunction with example.
Embodiment 1: prepare Graphene/hydroxyl cupric phosphate composite catalyst that mass ratio is 0.2 99.8 and measure its light and urge
Change performance, specifically comprise the following steps that
(1): prepare the graphene oxide water solution of 0.2 mg/mL；
(2): weigh after the copper nitrate of 1.87 g is dissolved in water, the lower disodium hydrogen phosphate adding 0.7098 g of stirring, stirs
Add the above-mentioned graphene oxide water solution of 10 mL after mixing 30 ~ 60min, continue stirring 10 ~ 30min, subsequently mixed solution is filled
Enter in stainless steel cauldron, move in air dry oven, under the conditions of 120 DEG C, react 6 h prepare Graphene/hydroxyl cupric phosphate
Precipitation, by centrifugation, washs and obtains Graphene/hydroxyl cupric phosphate composite catalyst powder after drying
(3) use U.S. Quanta 200 type environmental scanning electron microscope (SEM) that sample is carried out morphology observation, adopt
With Germany D8X type X-ray diffractometer (XRD), sample is carried out thing to characterize mutually.Fig. 1 is the typical SEM figure of sample in embodiment 1,
It can clearly be seen that hydroxyl cupric phosphate pattern is bar-shaped, a length of 200 ~ 500 nm, at hydroxyl cupric phosphate plane of crystal and crystal
Between can substantially observe graphene nanometer sheet.Fig. 2 is the typical XRD figure of sample in embodiment 1, marks with the XRD of hydroxyl cupric phosphate
Quasi-trace analysis, shows that crystal contained in composite catalyst is pure hydroxyl cupric phosphate.
(4) Graphene/hydroxyl cupric phosphate composite catalyst weighing 100 mg is inserted in photocatalytic system, and stirring is lower to add
The methylene blue solution of 150 mL 10.0 mg/L, is subsequently placed in stirring and adsorbing in dark and makes catalyst reach absorption half an hour
Balance.Use 300 W xenon lamps, (under (800 nm >=λ >=320nm), carry out away from catalyst about 10 cm at ultraviolet-visible light
According to, sample every 30 min, through 5000 rpm, 10 minutes centrifugal after take the supernatant at 664 nm, measure residue Asia in clear liquid
The absorbance of methyl blue, thus obtain the degradation rate of a time period methylene blue.The light of sample during b curve is embodiment 1 in Fig. 3
Catalysis methylene blue degradation curve, it is seen that its photocatalysis performance is better than blank sample (pure hydroxyl cupric phosphate) (a curve in Fig. 3).
Embodiment 2: prepare Graphene/hydroxyl cupric phosphate composite catalyst that mass ratio is 0.5 99.5 and measure its light and urge
Change performance, specifically comprise the following steps that
(1): prepare the graphene oxide water solution of 0.5 mg/mL；
(2): weigh after the copper sulphate pentahydrate of 2.50 g is dissolved in water, the lower phosphoric acid hydrogen two adding 0.7098 g of stirring
Sodium, adds the above-mentioned graphene oxide water solution of 10 mL after stirring 30 ~ 60min, continues stirring 10 ~ 30min, subsequently will mixing
Solution loads in stainless steel cauldron, moves in air dry oven, reacts 12 h and prepare Graphene/hydroxyl under the conditions of 120 DEG C
Cupric phosphate precipitates, and by centrifugation, washs and obtains Graphene/hydroxyl cupric phosphate composite catalyst powder after drying.
(3) use U.S. Quanta 200 type environmental scanning electron microscope (SEM) that sample is carried out morphology observation, adopt
With Germany D8X type X-ray diffractometer (XRD), sample is carried out thing to characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst weighing 100 mg is inserted in photocatalytic system, and stirring is lower to add
The methylene blue solution of 150 mL 10.0 mg/L, is subsequently placed in stirring and adsorbing in dark and makes catalyst reach absorption half an hour
Balance.Use 300 W xenon lamps, (under (800 nm >=λ >=320nm), carry out away from catalyst about 10 cm at ultraviolet-visible light
According to, sample every 30 min, through 5000 rpm, 10 minutes centrifugal after take the supernatant at 664 nm, measure residue Asia in clear liquid
The absorbance of methyl blue, thus obtain the degradation rate of a time period methylene blue.The light of sample during c curve is embodiment 2 in Fig. 3
Catalysis methylene blue degradation curve, it is seen that its photocatalysis performance is better than blank sample and embodiment 1 sample.
Embodiment 3: prepare Graphene/hydroxyl cupric phosphate composite catalyst that mass ratio is 1 99 and measure its photocatalytic
Can, specifically comprise the following steps that
(1): prepare the graphene oxide water solution of 1 mg/mL；
(2): weigh after the copper chloride dihydrate of 2.06 g is dissolved in water, the lower phosphoric acid hydrogen two adding 0.7098 g of stirring
Sodium, adds the above-mentioned graphene oxide water solution of 10 mL after stirring 30 ~ 60min, continues stirring 10 ~ 30min, subsequently will mixing
Solution loads in stainless steel cauldron, moves in air dry oven, reacts 12 h and prepare Graphene/hydroxyl under the conditions of 120 DEG C
Cupric phosphate precipitates, and by centrifugation, washs and obtains Graphene/hydroxyl cupric phosphate composite catalyst powder after drying.
(3) use U.S. Quanta 200 type environmental scanning electron microscope (SEM) that sample is carried out morphology observation, adopt
With Germany D8X type X-ray diffractometer (XRD), sample is carried out thing to characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst weighing 100 mg is inserted in photocatalytic system, and stirring is lower to add
The methylene blue solution of 150 mL 10.0 mg/L, is subsequently placed in stirring and adsorbing in dark and makes catalyst reach absorption half an hour
Balance.Use 300 W xenon lamps, (under (800 nm >=λ >=320nm), carry out away from catalyst about 10 cm at ultraviolet-visible light
According to, sample every 30 min, through 5000 rpm, 10 minutes centrifugal after take the supernatant at 664 nm, measure residue Asia in clear liquid
The absorbance of methyl blue, thus obtain the degradation rate of a time period methylene blue.The light of sample during d curve is embodiment 3 in Fig. 3
Catalysis methylene blue degradation curve, it is seen that its photocatalysis performance is better than blank sample and embodiment 1 and example 2 sample, such as Fig. 3 institute
Show.
Embodiment 4: prepare Graphene/hydroxyl cupric phosphate composite catalyst that mass ratio is 2 98 and measure its photocatalytic
Can, specifically comprise the following steps that
(1): prepare the graphene oxide water solution of 2 mg/mL；
(2): weigh after the copper chloride dihydrate of 2.06 g is dissolved in water, the lower diammonium phosphate adding 0.575 g of stirring,
Add the above-mentioned graphene oxide water solution of 10 mL after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently by mixed solution
Load in stainless steel cauldron, move in air dry oven, under the conditions of 120 DEG C, react 8 h prepare Graphene/di
Copper precipitates, and by centrifugation, washs and obtains Graphene/hydroxyl cupric phosphate composite catalyst powder after drying.
(3) use U.S. Quanta 200 type environmental scanning electron microscope (SEM) that sample is carried out morphology observation, adopt
With Germany D8X type X-ray diffractometer (XRD), sample is carried out thing to characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst weighing 100 mg is inserted in photocatalytic system, and stirring is lower to add
The methylene blue solution of 150 mL 10.0 mg/L, is subsequently placed in stirring and adsorbing in dark and makes catalyst reach absorption half an hour
Balance.Use 300 W xenon lamps, (under (800 nm >=λ >=320nm), carry out away from catalyst about 10 cm at ultraviolet-visible light
According to, sample every 30 min, through 5000 rpm, 10 minutes centrifugal after take the supernatant at 664 nm, measure residue Asia in clear liquid
The absorbance of methyl blue, thus obtain the degradation rate of a time period methylene blue.The light of sample during e curve is embodiment 4 in Fig. 3
Catalysis methylene blue degradation curve, it is seen that its photocatalysis performance is optimum.
Embodiment 5: prepare Graphene/hydroxyl cupric phosphate composite catalyst that mass ratio is 4 96 and measure its photocatalysis
Performance, specifically comprises the following steps that
(1): prepare the graphene oxide water solution of 4 mg/mL；
(2): weigh after the copper chloride dihydrate of 2.06 g is dissolved in water, the lower diammonium phosphate adding 0.575 g of stirring,
Add the above-mentioned graphene oxide water solution of 10 mL after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently by mixed solution
Load in stainless steel cauldron, move in air dry oven, under the conditions of 120 DEG C, react 6 h prepare Graphene/di
Copper precipitates, and by centrifugation, washs and obtains Graphene/hydroxyl cupric phosphate composite catalyst powder after drying.
(3) use U.S. Quanta 200 type environmental scanning electron microscope (SEM) that sample is carried out morphology observation, adopt
With Germany D8X type X-ray diffractometer (XRD), sample is carried out thing to characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst weighing 100 mg is inserted in photocatalytic system, and stirring is lower to add
The methylene blue solution of 150 mL 10.0 mg/L, is subsequently placed in stirring and adsorbing in dark and makes catalyst reach absorption half an hour
Balance.Use 300 W xenon lamps, (under (800 nm >=λ >=320nm), carry out away from catalyst about 10 cm at ultraviolet-visible light
According to, sample every 30 min, through 5000 rpm, 10 minutes centrifugal after take the supernatant at 664 nm, measure residue Asia in clear liquid
The absorbance of methyl blue, thus obtain the degradation rate of a time period methylene blue.The light of sample during f curve is embodiment 5 in Fig. 3
Catalysis methylene blue degradation curve.
Embodiment 6: prepare Graphene/hydroxyl cupric phosphate composite catalyst that mass ratio is 6 94 and measure its photocatalysis
Performance, specifically comprises the following steps that
(1): prepare the graphene oxide water solution of 6 mg/mL；
(2): weigh after the copper chloride dihydrate of 2.06 g is dissolved in water, the lower diammonium phosphate adding 0.575 g of stirring,
Add the above-mentioned graphene oxide water solution of 10 mL after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently by mixed solution
Load in stainless steel cauldron, move in air dry oven, under the conditions of 120 DEG C, react 8 h prepare Graphene/di
Copper precipitates, and by centrifugation, washs and obtains Graphene/hydroxyl cupric phosphate composite catalyst powder after drying
(3) use U.S. Quanta 200 type environmental scanning electron microscope (SEM) that sample is carried out morphology observation, adopt
With Germany D8X type X-ray diffractometer (XRD), sample is carried out thing to characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst weighing 100 mg is inserted in photocatalytic system, and stirring is lower to add
The methylene blue solution of 150 mL 10.0 mg/L, is subsequently placed in stirring and adsorbing in dark and makes catalyst reach absorption half an hour
Balance.Use 300 W xenon lamps, (under (800 nm >=λ >=320nm), carry out away from catalyst about 10 cm at ultraviolet-visible light
According to, sample every 30 min, through 5000 rpm, 10 minutes centrifugal after take the supernatant at 664 nm, measure residue Asia in clear liquid
The absorbance of methyl blue, thus obtain the degradation rate of a time period methylene blue.The light of sample during g curve is embodiment 6 in Fig. 3
Catalysis methylene blue degradation curve.
Claims (8)
1. Graphene/hydroxyl cupric phosphate composite catalyst, it includes: graphene nanometer sheet and hydroxyl cupric phosphate；Its feature
It is: shared by each composition, mass ratio is: graphene nanometer sheet 0.2～6%, hydroxyl cupric phosphate 99.8～94%；
The preparation method of described composite catalyst is as follows: the graphene oxide of (1) measured amounts is put in beaker, adds certain
The pure water of amount, seals with preservative film, and ultrasonic disperse processes 12～24h, then carries out the stirring of 12～24h on magnetic stirring apparatus
Process；
(2) pending good after, be centrifuged separating treatment, take supernatant, stand-by after having demarcated graphene oxide concentration；
(3) weighing a certain amount of soluble copper salt, after being completely dissolved in water, stirring is lower adds a certain amount of soluble phosphoric acid
Salt, adds a certain amount of graphene oxide water solution after stirring 30～60min；
(4) regulating pH with sodium hydroxide after continuing stirring 10～30min is 7, loads in reactor by above-mentioned suspension subsequently, moves
Enter in air dry oven, prepare precipitation in 100～140 DEG C of reactions 6～24h, by centrifugation, washing, obtain Graphene/hydroxyl after drying
Base cupric phosphate composite catalyst powder.
A kind of Graphene/hydroxyl cupric phosphate composite catalyst the most according to claim 1, it is characterised in that: described graphite
In alkene/hydroxyl cupric phosphate composite catalyst, graphene nanometer sheet is attached to the surface of hydroxyl cupric phosphate or is connected to hydroxyl cupric phosphate
Between.
A kind of Graphene/hydroxyl cupric phosphate composite catalyst the most according to claim 1, it is characterised in that: Graphene is received
The thickness of rice sheet is 0.37～5nm, and structure is single or multiple lift.
A kind of Graphene/hydroxyl cupric phosphate composite catalyst the most according to claim 1, it is characterised in that: di
Copper is bar-shaped, a length of 200～500nm.
5. the preparation method of Graphene/hydroxyl cupric phosphate composite catalyst according to claim 1, it is characterised in that step
Rapid as follows:
(1) graphene oxide of measured amounts is put in beaker, adds a certain amount of pure water, seals with preservative film, ultrasonic point
Dissipate and process 12～24h, on magnetic stirring apparatus, then carry out the stir process of 12～24h；
(2) pending good after, be centrifuged separating treatment, take supernatant, stand-by after having demarcated graphene oxide concentration；
(3) weighing a certain amount of soluble copper salt, after being completely dissolved in water, stirring is lower adds a certain amount of soluble phosphoric acid
Salt, adds a certain amount of graphene oxide water solution after stirring 30～60min；
(4) regulating pH with sodium hydroxide after continuing stirring 10～30min is 7, loads in reactor by above-mentioned suspension subsequently, moves
Enter in air dry oven, prepare precipitation in 100～140 DEG C of reactions 6～24h, by centrifugation, washing, obtain Graphene/hydroxyl after drying
Base cupric phosphate composite catalyst powder.
The preparation method of a kind of Graphene/hydroxyl cupric phosphate composite catalyst the most according to claim 5, its feature exists
In: in described step (3), soluble copper salt can be the one in copper nitrate, copper chloride, copper sulfate, copper acetate.
The preparation method of a kind of Graphene/hydroxyl cupric phosphate composite catalyst the most according to claim 5, its feature exists
In: in described step (3), soluble phosphate is the one of dibastic sodium phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate.
The preparation method of a kind of Graphene/hydroxyl cupric phosphate composite catalyst the most according to claim 5, its feature exists
In: in step (3), copper ion and phosphate anion are according to stoichiometric proportion 2:1 dispensing.
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| CN101835609A (en) * | 2007-09-10 | 2010-09-15 | 三星电子株式会社 | Graphene sheet and process of preparing the same |
| CN103537308A (en) * | 2013-11-01 | 2014-01-29 | 长沙理工大学 | Preparation method of tetrahydroxy copper phosphate catalyst |
| CN103537309A (en) * | 2013-11-01 | 2014-01-29 | 长沙理工大学 | Application of tetrahydroxy copper phosphate as organic wastewater degradation catalyst |
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| CN101835609A (en) * | 2007-09-10 | 2010-09-15 | 三星电子株式会社 | Graphene sheet and process of preparing the same |
| CN103537308A (en) * | 2013-11-01 | 2014-01-29 | 长沙理工大学 | Preparation method of tetrahydroxy copper phosphate catalyst |
| CN103537309A (en) * | 2013-11-01 | 2014-01-29 | 长沙理工大学 | Application of tetrahydroxy copper phosphate as organic wastewater degradation catalyst |
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