CN104368367A - Graphene/copper hydroxyphosphate composite catalyst and preparation method thereof - Google Patents
Graphene/copper hydroxyphosphate composite catalyst and preparation method thereof Download PDFInfo
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- CN104368367A CN104368367A CN201410447867.1A CN201410447867A CN104368367A CN 104368367 A CN104368367 A CN 104368367A CN 201410447867 A CN201410447867 A CN 201410447867A CN 104368367 A CN104368367 A CN 104368367A
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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
Abstract
The invention belongs to the field of preparation of composite catalytic materials, in particular relates to a graphene / copper hydroxyphosphate composite catalyst and a preparation method thereof. The specific steps are as follows: 1) preparing a graphene oxide water solution with certain solubility; 2) adding a certain amount of graphene oxide water solution into a soluble copper salt and soluble phosphate reaction system; 3) adjusting the pH value; 4) putting the suspension into a reactor for reaction for 6-12h at 100-140 DEG C, cooling, centrifuging, washing and drying to obtain the graphene / copper hydroxyphosphate composite catalyst. The mass ratio of graphene nano sheet to copper hydroxyphosphate in the graphene / copper hydroxyphosphate composite catalyst is 0.2-6%: 99.8-94%, and optimally is 2%: 98%. The composite catalyst has good catalytic performance under simulated sunlight, and can be applied to the field of water treatment of industrial wastewater.
Description
Technical field
The present invention relates to the preparation field belonging to compound catalyze material, be specifically related to a kind of Graphene/hydroxyl cupric phosphate composite catalyst and preparation method thereof.
Technical background
Current, day by day serious problem of environmental pollution has obtained the great attention of people, and wherein water pollution problems is urgently prevented especially and administered.But along with water pollutant qualitative diversity and complexity, traditional method for treating water can not meet the requirement of people.Photocatalysis relies on the advantages such as self is simple to operate, low energy consumption, reaction condition gentleness, non-secondary pollution, has become the new technology of wastewater treatment, has had vast potential for future development.Hydroxyl cupric phosphate (Cu
2(OH) PO
4) be a kind of novel photocatalyst, under ultraviolet-visible even region of ultra-red, all have good catalytic activity, be a kind of novel active photochemical catalyst with applications well prospect.But hydroxyl cupric phosphate prepared by existing method also deposits problem both ways: the hydroxyl cupric phosphate particle diameter 1) prepared is larger, mainly more than micron order; 2) do not have electron capture agent hydrogen peroxide auxiliary under, the performance of catalyzing and degrading pollutant of hydroxyl cupric phosphate is also more weak.
Summary of the invention
The object of the invention is to solve existing method Problems existing, from reduction catalyst particle size, increase its specific area and accelerate the aspects such as its electron-hole is separated a kind of Graphene/hydroxyl cupric phosphate composite catalyst and preparation method thereof is provided.
We are by one kettle way fabricated in situ Graphene/hydroxyl cupric phosphate composite catalyst, find that the particle diameter of hydroxyl cupric phosphate reduces and the graphene nanometer sheet mixed can significantly improve the photocatalysis degradation organic contaminant performance of hydroxyl cupric phosphate.
The present invention is with graphene oxide, and soluble copper salt, soluble phosphate are that Graphene/hydroxyl cupric phosphate composite catalyst prepared by raw material.
A kind of Graphene/hydroxyl cupric phosphate composite catalyst, it comprises: graphene nanometer sheet and hydroxyl cupric phosphate; It is characterized in that: shared by each composition, mass ratio is: graphene nanometer sheet 0.2 ~ 6 %, hydroxyl cupric phosphate 99.8 ~ 94 %; In described Graphene/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 length is 200 ~ 500 nm.
A preparation method for Graphene/hydroxyl cupric phosphate composite catalyst, its step is as follows:
(1) graphene oxide of measured amounts, puts into beaker, adds a certain amount of pure water, and with preservative film sealing, ultrasonic disperse process 12 ~ 24 h, then carries out the stir process of 12 ~ 24 h on magnetic stirring apparatus;
(2) pending good after, carry out centrifuging treatment, get supernatant, stand-by after having demarcated graphene oxide concentration;
(3) take a certain amount of soluble copper salt, after dissolving completely in water, under stirring, add a certain amount of soluble phosphate, after stirring 30 ~ 60 min, add a certain amount of graphene oxide water solution;
(4) pH is regulated to be 7 with NaOH after continuing stirring 10 ~ 30min, subsequently above-mentioned suspension is loaded in reactor, move in air dry oven, at 100 ~ 140 DEG C, react the obtained precipitation of 6 ~ 24 h, after centrifugal, washing, drying, obtain Graphene/hydroxyl cupric phosphate composite catalyst powder.
In step (1), graphene oxide used adopts Hummers method (J Am Chem Soc. 1958,80,1339.) to be prepared from.
Graphene oxide water solution concentration prepared in step (2) is 0.2 ~ 6 mg/mL.
Copper ion and phosphate anion to be prepared burden 2:1 according to stoichiometric proportion in step (3).
In step (4), in gained Graphene/hydroxyl cupric phosphate composite catalyst, the mass ratio of Graphene and hydroxyl cupric phosphate is graphite 0.2 ~ 6 % ︰ 99.8 ~ 94 %.
Graphene of the present invention/hydroxyl cupric phosphate composite catalyst has good photocatalysis degradation organic contaminant performance, can be used for the water treatment field of industrial wastewater.
The catalytic performance test method adopted is as follows:
Graphene/hydroxyl cupric phosphate the composite catalyst taking 100 mg is inserted in photocatalytic system, add the methylene blue solution of 150 mL 10.0 mg/L under stirring, after being then placed in dark stirring and adsorbing half an hour, under xenon lamp (800 nm >=λ >=320nm), carry out light-catalyzed reaction.
When not adding electron capture agent, Graphene/hydroxyl cupric phosphate composite catalyst degradable in 1 hour removes the methylenum careuleum of in aqueous systems 80%.The above results shows, prepared Graphene/hydroxyl cupric phosphate composite catalyst has excellent photocatalysis performance under simulated solar irradiation, is a kind of potential Industrial Wastewater Treatment material.
Advantage of the present invention is as follows:
Adopt the Graphene/hydroxyl cupric phosphate compound catalyze material of one kettle way fabricated in situ, this method building-up process is simple, easy to operate, is a kind of synthetic method of effective graphene inorganic composite.
The hydroxyl cupric phosphate of synthesis is bar-shaped, length is 200 ~ 500 nm, its particle diameter is less than published patent (CN201310531313.5), the thickness of graphene nanometer sheet is 0.37 ~ 5 nm, be attached to hydroxyl cupric phosphate surface or be connected between hydroxyl cupric phosphate particle, effectively can improve the migration of electrons in photocatalytic process, suppress the compound of electrons, thus enhance the photocatalysis performance of this hydroxyl cupric phosphate, be a kind of potential catalysis material that can be applicable to contaminant degradation in industrial wastewater.
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, the schematic diagram of Graphene/hydroxyl cupric phosphate composite catalyst for being prepared by method of the present invention; Preparation method of the present invention is illustrated below in conjunction with example.
Embodiment 1: preparation quality is than the Graphene/hydroxyl cupric phosphate composite catalyst being 0.2 ︰ 99.8 and measure its photocatalysis performance, concrete steps are as follows:
(1): the graphene oxide water solution preparing 0.2 mg/mL;
(2): the copper nitrate weighing 1.87 g is dissolved into after in water, the sodium hydrogen phosphate of 0.7098 g is added under stirring, the above-mentioned graphene oxide water solution of 10 mL is added after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently mixed solution is loaded in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 6 h obtain Graphene/hydroxyl cupric phosphate precipitation, after centrifugal, washing and drying, obtain Graphene/hydroxyl cupric phosphate composite catalyst powder
(3) adopt U.S. Quanta 200 type environmental scanning electron microscope (SEM) to carry out morphology observation to sample, adopt German D8X type X-ray diffractometer (XRD) to carry out thing to sample and characterize mutually.Fig. 1 is the typical SEM figure of sample in embodiment 1, and obviously can see that hydroxyl cupric phosphate pattern is bar-shaped, length is 200 ~ 500 nm, obviously can observe graphene nanometer sheet between hydroxyl cupric phosphate plane of crystal and crystal.Fig. 2 is the typical XRD figure of sample in embodiment 1, compares, show that crystal contained in composite catalyst is pure hydroxyl cupric phosphate with the XRD standard diagram of hydroxyl cupric phosphate.
(4) Graphene/hydroxyl cupric phosphate composite catalyst taking 100 mg is inserted in photocatalytic system, adds the methylene blue solution of 150 mL 10.0 mg/L under stirring, is then placed in dark stirring and adsorbing and makes catalyst reach adsorption equilibrium half an hour.Adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, thus obtain the degradation rate of a time period methylene blue.In Fig. 3, b curve is the photocatalysis methylene blue degradation curve of sample in embodiment 1, and its photocatalysis performance is better than blank sample (pure hydroxyl cupric phosphate) (in Fig. 3 a curve) as seen.
Embodiment 2: preparation quality is than the Graphene/hydroxyl cupric phosphate composite catalyst being 0.5 ︰ 99.5 and measure its photocatalysis performance, concrete steps are as follows:
(1): the graphene oxide water solution preparing 0.5 mg/mL;
(2): the cupric sulfate pentahydrate weighing 2.50 g is dissolved into after in water, the sodium hydrogen phosphate of 0.7098 g is added under stirring, the above-mentioned graphene oxide water solution of 10 mL is added after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently mixed solution is loaded in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 12 h obtain Graphene/hydroxyl cupric phosphate precipitation, after centrifugal, washing and drying, obtain Graphene/hydroxyl cupric phosphate composite catalyst powder.
(3) adopt U.S. Quanta 200 type environmental scanning electron microscope (SEM) to carry out morphology observation to sample, adopt German D8X type X-ray diffractometer (XRD) to carry out thing to sample and characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst taking 100 mg is inserted in photocatalytic system, adds the methylene blue solution of 150 mL 10.0 mg/L under stirring, is then placed in dark stirring and adsorbing and makes catalyst reach adsorption equilibrium half an hour.Adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, thus obtain the degradation rate of a time period methylene blue.In Fig. 3, c curve is the photocatalysis methylene blue degradation curve of sample in embodiment 2, and its photocatalysis performance is better than blank sample and embodiment 1 sample as seen.
Embodiment 3: preparation quality is than the Graphene/hydroxyl cupric phosphate composite catalyst being 1 ︰ 99 and measure its photocatalysis performance, concrete steps are as follows:
(1): the graphene oxide water solution preparing 1 mg/mL;
(2): the copper chloride dihydrate weighing 2.06 g is dissolved into after in water, the sodium hydrogen phosphate of 0.7098 g is added under stirring, the above-mentioned graphene oxide water solution of 10 mL is added after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently mixed solution is loaded in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 12 h obtain Graphene/hydroxyl cupric phosphate precipitation, after centrifugal, washing and drying, obtain Graphene/hydroxyl cupric phosphate composite catalyst powder.
(3) adopt U.S. Quanta 200 type environmental scanning electron microscope (SEM) to carry out morphology observation to sample, adopt German D8X type X-ray diffractometer (XRD) to carry out thing to sample and characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst taking 100 mg is inserted in photocatalytic system, adds the methylene blue solution of 150 mL 10.0 mg/L under stirring, is then placed in dark stirring and adsorbing and makes catalyst reach adsorption equilibrium half an hour.Adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, thus obtain the degradation rate of a time period methylene blue.In Fig. 3, d curve is the photocatalysis methylene blue degradation curve of sample in embodiment 3, and its photocatalysis performance is better than blank sample and embodiment 1 and example 2 sample as seen, as shown in Figure 3.
Embodiment 4: preparation quality is than the Graphene/hydroxyl cupric phosphate composite catalyst being 2 ︰ 98 and measure its photocatalysis performance, concrete steps are as follows:
(1): the graphene oxide water solution preparing 2 mg/mL;
(2): the copper chloride dihydrate weighing 2.06 g is dissolved into after in water, the diammonium hydrogen phosphate of 0.575 g is added under stirring, the above-mentioned graphene oxide water solution of 10 mL is added after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently mixed solution is loaded in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 8 h obtain Graphene/hydroxyl cupric phosphate precipitation, after centrifugal, washing and drying, obtain Graphene/hydroxyl cupric phosphate composite catalyst powder.
(3) adopt U.S. Quanta 200 type environmental scanning electron microscope (SEM) to carry out morphology observation to sample, adopt German D8X type X-ray diffractometer (XRD) to carry out thing to sample and characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst taking 100 mg is inserted in photocatalytic system, adds the methylene blue solution of 150 mL 10.0 mg/L under stirring, is then placed in dark stirring and adsorbing and makes catalyst reach adsorption equilibrium half an hour.Adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, thus obtain the degradation rate of a time period methylene blue.In Fig. 3, e curve is the photocatalysis methylene blue degradation curve of sample in embodiment 4, and its photocatalysis performance is optimum as seen.
Embodiment 5: preparation quality is than the Graphene/hydroxyl cupric phosphate composite catalyst being 4 ︰ 96 and measure its photocatalysis performance, concrete steps are as follows:
(1): the graphene oxide water solution preparing 4 mg/mL;
(2): the copper chloride dihydrate weighing 2.06 g is dissolved into after in water, the diammonium hydrogen phosphate of 0.575 g is added under stirring, the above-mentioned graphene oxide water solution of 10 mL is added after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently mixed solution is loaded in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 6 h obtain Graphene/hydroxyl cupric phosphate precipitation, after centrifugal, washing and drying, obtain Graphene/hydroxyl cupric phosphate composite catalyst powder.
(3) adopt U.S. Quanta 200 type environmental scanning electron microscope (SEM) to carry out morphology observation to sample, adopt German D8X type X-ray diffractometer (XRD) to carry out thing to sample and characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst taking 100 mg is inserted in photocatalytic system, adds the methylene blue solution of 150 mL 10.0 mg/L under stirring, is then placed in dark stirring and adsorbing and makes catalyst reach adsorption equilibrium half an hour.Adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, thus obtain the degradation rate of a time period methylene blue.In Fig. 3, f curve is the photocatalysis methylene blue degradation curve of sample in embodiment 5.
Embodiment 6: preparation quality is than the Graphene/hydroxyl cupric phosphate composite catalyst being 6 ︰ 94 and measure its photocatalysis performance, concrete steps are as follows:
(1): the graphene oxide water solution preparing 6 mg/mL;
(2): the copper chloride dihydrate weighing 2.06 g is dissolved into after in water, the diammonium hydrogen phosphate of 0.575 g is added under stirring, the above-mentioned graphene oxide water solution of 10 mL is added after stirring 30 ~ 60min, continue stirring 10 ~ 30min, subsequently mixed solution is loaded in stainless steel cauldron, move in air dry oven, under 120 DEG C of conditions, react 8 h obtain Graphene/hydroxyl cupric phosphate precipitation, after centrifugal, washing and drying, obtain Graphene/hydroxyl cupric phosphate composite catalyst powder
(3) adopt U.S. Quanta 200 type environmental scanning electron microscope (SEM) to carry out morphology observation to sample, adopt German D8X type X-ray diffractometer (XRD) to carry out thing to sample and characterize mutually.
(4) Graphene/hydroxyl cupric phosphate composite catalyst taking 100 mg is inserted in photocatalytic system, adds the methylene blue solution of 150 mL 10.0 mg/L under stirring, is then placed in dark stirring and adsorbing and makes catalyst reach adsorption equilibrium half an hour.Adopt 300 W xenon lamps, at ultraviolet-visible light (under (800 nm >=λ >=320nm), from catalyst about 10, cm place is shone, every 30 min samplings, through 5000 rpm, 10 minutes centrifugal after get supernatant liquor and measure in clear liquid at 664 nm places the absorbance remaining methylene blue, thus obtain the degradation rate of a time period methylene blue.In Fig. 3, g curve is the photocatalysis methylene blue degradation curve of sample in embodiment 6.
Claims (8)
1. Graphene/hydroxyl cupric phosphate composite catalyst, it comprises: graphene nanometer sheet and hydroxyl cupric phosphate; It is characterized in that: shared by each composition, mass ratio is: graphene nanometer sheet 0.2 ~ 6 %, hydroxyl cupric phosphate 99.8 ~ 94 %.
2. a kind of Graphene/hydroxyl cupric phosphate composite catalyst according to claim 1, is characterized in that: in described Graphene/hydroxyl cupric phosphate composite catalyst, graphene nanometer sheet is attached to the surface of hydroxyl cupric phosphate or is connected between hydroxyl cupric phosphate.
3. a kind of Graphene/hydroxyl cupric phosphate composite catalyst according to claim 1, is characterized in that: the thickness of graphene nanometer sheet is 0.37 ~ 5nm, and structure is single or multiple lift.
4. a kind of Graphene/hydroxyl cupric phosphate composite catalyst according to claim 1, is characterized in that: hydroxyl cupric phosphate is bar-shaped, and length is 200 ~ 500 nm.
5. a preparation method for Graphene/hydroxyl cupric phosphate composite catalyst according to claim 1, is characterized in that step is as follows:
(1) graphene oxide of measured amounts puts into beaker, adds a certain amount of pure water, and with preservative film sealing, ultrasonic disperse process 12 ~ 24 h, then carries out the stir process of 12 ~ 24 h on magnetic stirring apparatus;
(2) pending good after, carry out centrifuging treatment, get supernatant, stand-by after having demarcated graphene oxide concentration;
(3) take a certain amount of soluble copper salt, after dissolving completely in water, under stirring, add a certain amount of soluble phosphate, after stirring 30 ~ 60 min, add a certain amount of graphene oxide water solution;
(4) pH is regulated to be 7 with NaOH after continuing stirring 10 ~ 30min, subsequently above-mentioned suspension is loaded in reactor, move in air dry oven, 100 ~ 140 DEG C of obtained precipitations of reaction 6 ~ 24 h, after centrifugal, washing, drying, obtain Graphene/hydroxyl cupric phosphate composite catalyst powder.
6. the preparation method of a kind of Graphene/hydroxyl cupric phosphate composite catalyst according to claim 5, is characterized in that: in described step (3), soluble copper salt can be the one in copper nitrate, copper chloride, copper sulphate, copper acetate.
7. the preparation method of a kind of Graphene/hydroxyl cupric phosphate composite catalyst according to claim 5, is characterized in that: in described step (3), soluble phosphate can be the one of dibastic sodium phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate etc.
8. the preparation method of a kind of Graphene/hydroxyl cupric phosphate composite catalyst according to claim 5, is characterized in that: in step (3), copper ion and phosphate anion are prepared burden according to stoichiometric proportion 2:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107570184A (en) * | 2017-09-04 | 2018-01-12 | 东华理工大学 | A kind of preparation method of water chestnut shape hydroxyl cupric phosphate catalysis material |
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| US20090068470A1 (en) * | 2007-09-12 | 2009-03-12 | Samsung Electronics Co., Ltd. | Graphene shell and process of preparing the same |
| CN101835609A (en) * | 2007-09-10 | 2010-09-15 | 三星电子株式会社 | Graphene sheet and process of preparing the same |
| US20120255899A1 (en) * | 2011-04-11 | 2012-10-11 | Industry-University Cooperation Foundation Hanyang University | Separation membrane including graphene |
| CN103537309A (en) * | 2013-11-01 | 2014-01-29 | 长沙理工大学 | Application of tetrahydroxy copper phosphate as organic wastewater degradation catalyst |
| CN103537308A (en) * | 2013-11-01 | 2014-01-29 | 长沙理工大学 | Preparation method of tetrahydroxy copper phosphate catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| US20090068470A1 (en) * | 2007-09-12 | 2009-03-12 | Samsung Electronics Co., Ltd. | Graphene shell and process of preparing the same |
| US20120255899A1 (en) * | 2011-04-11 | 2012-10-11 | Industry-University Cooperation Foundation Hanyang University | Separation membrane including graphene |
| CN103537309A (en) * | 2013-11-01 | 2014-01-29 | 长沙理工大学 | Application of tetrahydroxy copper phosphate as organic wastewater degradation catalyst |
| CN103537308A (en) * | 2013-11-01 | 2014-01-29 | 长沙理工大学 | Preparation method of tetrahydroxy copper phosphate catalyst |
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| CN107570184A (en) * | 2017-09-04 | 2018-01-12 | 东华理工大学 | A kind of preparation method of water chestnut shape hydroxyl cupric phosphate catalysis material |
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