CN106391110A - Preparation method of copper benzoate hydroxide-SiO2 composite material with photocatalysis - Google Patents
Preparation method of copper benzoate hydroxide-SiO2 composite material with photocatalysis Download PDFInfo
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- CN106391110A CN106391110A CN201610788582.3A CN201610788582A CN106391110A CN 106391110 A CN106391110 A CN 106391110A CN 201610788582 A CN201610788582 A CN 201610788582A CN 106391110 A CN106391110 A CN 106391110A
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- hydroxide
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- preparation
- copper benzoate
- copper
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 26
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 25
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 25
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 25
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 title abstract description 10
- 238000007146 photocatalysis Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- OVMZYIMAAFBAGQ-UHFFFAOYSA-L C(C1=CC=CC=C1)(=O)[O-].O[Cu+] Chemical class C(C1=CC=CC=C1)(=O)[O-].O[Cu+] OVMZYIMAAFBAGQ-UHFFFAOYSA-L 0.000 claims abstract description 20
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 20
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004005 microsphere Substances 0.000 claims abstract description 19
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 8
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000012467 final product Substances 0.000 claims description 18
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 4
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical compound CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 19
- 238000006731 degradation reaction Methods 0.000 abstract description 18
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 230000009881 electrostatic interaction Effects 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000005750 Copper hydroxide Substances 0.000 abstract 2
- 229910001956 copper hydroxide Inorganic materials 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000010919 dye waste Substances 0.000 abstract 1
- 239000000835 fiber Substances 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 239000000975 dye Substances 0.000 description 10
- UUHPOCBHCIUKQE-UHFFFAOYSA-L [Si](=O)=O.C(C1=CC=CC=C1)(=O)[O-].[Cu+2].[OH-] Chemical compound [Si](=O)=O.C(C1=CC=CC=C1)(=O)[O-].[Cu+2].[OH-] UUHPOCBHCIUKQE-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229950000845 politef Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 241001466460 Alveolata Species 0.000 description 2
- FZOYSVJVTIXYIW-UHFFFAOYSA-L [Si](=O)=O.C(C1=CC=CC=C1)(=O)[O-].[Cu+2].C(C1=CC=CC=C1)(=O)[O-] Chemical compound [Si](=O)=O.C(C1=CC=CC=C1)(=O)[O-].[Cu+2].C(C1=CC=CC=C1)(=O)[O-] FZOYSVJVTIXYIW-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a copper benzoate hydroxide-SiO2 composite material with photocatalysis. The preparation method comprises preparing copper hydroxide by a precipitation method, preparing laminated copper benzoate hydroxide from the copper hydroxide and benzoic acid as main raw materials, and carrying out a hydro-thermal synthesis reaction process on the laminated copper benzoate hydroxide and SiO2 microspheres to obtain a copper benzoate hydroxide-SiO2 compound. Through a self-assembly method, an LDH-Cu@SiO2 composite material with a core-shell structure is obtained and LDH-Cu fibers uniformly coat the silicon dioxide microspheres so that the whole morphology is complete. Compared with the conventional layered nano-compounds, the copper benzoate hydroxide-SiO2 composite material has better dispersibility and better photocatalytic activity in the reaction system. LDH-Cu in the LDH-Cu@SiO2 composite material can synergistically degrade organic matters in dye waste water through ion exchange and electrostatic interaction and improve the degradation efficiency of dye wastewater. The preparation method is simple and effective, does not need special equipment, and provides a simple and feasible method for compounding different functional materials.
Description
Technical field
The invention belongs to catalysis material preparing technical field is and in particular to a kind of hydroxide benzene first with photocatalytic
Sour copper-SiO2The preparation method of composite.
Background technology
China's rapid economic development in the last few years, the industry development impetus such as industry, building, weaving is swift and violent, a large amount of Industry Wastes
Gurry discharge leads to problem of environmental pollution further serious.Therefore the effective process of all kinds of environmental contaminants is had become as with one compel
Task in the eyebrows and eyelashes.A large amount of colorful wastewaters that wherein industry such as papermaking, printing and dyeing is discharged have that toxicity is big, complicated component, difficult raw
The features such as thing is degraded, the process with regard to this kind of waste water is constantly subjected to the extensive concern of research worker.Conventional processes master at present
Will active carbon adsorption, biological degradation method, dosing absorption method.But above-mentioned several method exists, and processing cost is high, it is not thorough to degrade
Bottom, there is the aspect defect such as secondary pollution it is difficult to large-scale promotion or treatment effect be not good.
Photocatalysis technology has the features such as environmental protection, clean energy-conservation, is one of very active research field of academia,
Have broad application prospects at aspects such as environmental conservation, new function material exploitation, Solar use.But with TiO2For representing
Catalysis material be susceptible to photoetch phenomenon, stability is not high；And band gap width, internal carrier coincidence rate height etc. lack
Falling into makes photocatalysis performance not good, greatly limit further application and development.Therefore to the modification of existing material, modification and
Exploitation novel photocatalysis material becomes the hot issue of current research.
Content of the invention
It is an object of the invention to provide a kind of hydroxide copper benzoate-SiO with photocatalytic2The preparation of composite
Method, solves the problems, such as that existing catalysis material capacity usage ratio is low and poor to waste water from dyestuff photocatalytic degradation effect.
The technical solution adopted in the present invention is, a kind of hydroxide copper benzoate-SiO with photocatalytic2Composite wood
The preparation method of material, specifically implements according to following steps：
Step 1, prepares stratiform hydroxide copper benzoate；
Step 2, prepares silicon dioxide microsphere；
Step 3, the silicon dioxide microsphere of the stratiform hydroxide copper benzoate of step 1 gained and step 2 gained is placed in water
In, after carrying out hydrothermal synthesis reaction 24～36h under the conditions of 120～160 DEG C, by products therefrom through sucking filtration, deionized water, no
Water-ethanol washs, 24h is dried in thermostatic drying chamber, obtains final product stratiform hydroxide copper benzoate-SiO2Composite (LDH-Cu@
SiO2).
The present invention is further characterized in that,
In step 1, the preparation process of stratiform hydroxide copper benzoate is：
Step 1.1：To in copper nitrate solution, Deca strong aqua ammonia, is stirred continuously, after light blue precipitation to be generated, at normal temperatures
Continue stirring 0.5～1h, be aged 6～8h after solution thoroughly precipitates, carry out sucking filtration, and deionized water precipitate is carried out many
Secondary washing, is subsequently dried 24～32h at normal temperatures, obtains Copper hydrate；
Step 1.2：Copper hydrate, benzoic acid are placed in deionized water, are sufficiently stirred under the conditions of 90～100 DEG C
Lower back flow reaction 18～24h, after question response terminates, product, through sucking filtration, washing, normal temperature drying 24～32h, obtains final product stratiform hydrogen-oxygen
Change copper benzoate (LDH-Cu).
In step 1.1, the concentration of copper nitrate solution is 0.32mol/L, and strong aqua ammonia is 1 with the amount ratio of copper nitrate solution:
18～25.
In step 1.2, Copper hydrate and benzoic amount ratio are 1～1.5:1.
In step 2, the preparation process of silicon dioxide microsphere is：
Step 2.1：At normal temperatures, deionized water, ammonia and dehydrated alcohol are mixed, prepare to obtain solution A；By ethanol and just
Silester mixes, and prepares to obtain B solution；
Step 2.2：Stirring B solution is added drop-wise in solution A simultaneously, and sealing reaction 24h, through being centrifuged at a high speed, through washing
Wash, be dried after, obtain final product silicon dioxide.
In solution A, ammonia and the amount ratio of deionized water are 1:1～1.2, dehydrated alcohol with the amount ratio of deionized water is
1:1.5～2；In B solution, ethanol and the amount ratio of tetraethyl orthosilicate are 4～5:1.
In step 2.2, solution A is 1～1.5 with the amount ratio of B solution:1.
In step 3, stratiform hydroxide copper benzoate is 1～2 with the amount ratio of silicon dioxide microsphere:1.
The invention has the beneficial effects as follows, it is prepared for the LDH-Cu@SiO of nucleocapsid structure by self-assembly method2Composite,
Fibrous LDH-Cu is equably wrapped in SiO2On microsphere, overall pattern is complete.Compared with conventional layered Nano compound,
In reaction system, more preferably, photocatalytic activity is more preferable for dispersibility；LDH-Cu@SiO2LDH-Cu in composite can be by ion
Organic substance in the various ways Synergistic degradation waste water from dyestuff such as exchange, electrostatic interaction, improves the degradation efficiency of waste water from dyestuff.This system
Preparation Method effectively it is not necessary to special installation, is simply that the compound of more difference in functionality materials provides a kind of side of simple possible
Method.
Brief description
Fig. 1 is the SEM figure of embodiment of the present invention gained stratiform hydroxide copper benzoate；
Fig. 2 is the SEM figure of the inventive method gained stratiform hydroxide copper benzoate-silicon dioxide；
Fig. 3 is the SEM figure of the embodiment of the present invention 3 gained stratiform hydroxide copper benzoate-silicon dioxide；
Fig. 4 has the hydroxide copper benzoate-SiO of photocatalytic for the present invention2The preparation method resultant layer of composite
The degradation effect figure to methyl orange for the shape hydroxide copper benzoate-silicon dioxide；
Fig. 5 has the hydroxide copper benzoate-SiO of photocatalytic for the present invention2The preparation method resultant layer of composite
The degradation effect figure to rhodamine for the shape hydroxide copper benzoate-silicon dioxide；
Fig. 6 has the hydroxide copper benzoate-SiO of photocatalytic for the present invention2The preparation method resultant layer of composite
The degradation principles figure of shape hydroxide copper benzoate-silicon dioxide.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of hydroxide copper benzoate-SiO with photocatalytic of the present invention2The preparation method of composite, first adopts
The sedimentation method prepare Copper hydrate, with Copper hydrate, benzoic acid for primary raw material prepare stratiform hydroxide copper benzoate, then make its with
Silicon dioxide microsphere carries out hydrothermal synthesis reaction, obtains final product assembling product-hydroxide copper benzoate-silicon dioxide.Specifically according to
Lower step is implemented：
Step 1, in copper nitrate solution, Deca strong aqua ammonia, is stirred continuously, and after light blue precipitation to be generated, continues at normal temperatures
Continuous stirring 0.5～1h, is aged 6～8h after solution thoroughly precipitates, carries out sucking filtration, and deionized water is carried out repeatedly to precipitate
Washing, is subsequently dried 24～32h at normal temperatures, obtains Copper hydrate；Wherein, the concentration of copper nitrate solution is 0.32mol/L, dense ammonia
Water is 1 with the amount ratio of copper nitrate solution:18～25.
Step 2, Copper hydrate, benzoic acid are placed in deionized water, under being sufficiently stirred under the conditions of 90～100 DEG C
Back flow reaction 18～24h, after question response terminates, product, through sucking filtration, washing, normal temperature drying 24～32h, obtains final product stratiform hydroxide
Copper benzoate (LDH-Cu).Wherein, Copper hydrate and benzoic amount ratio are 1～1.5:1.
Step 3, at normal temperatures, deionized water, ammonia and dehydrated alcohol is mixed, prepares to obtain solution A；By ethanol and positive silicon
Acetoacetic ester mixes, and prepares to obtain B solution；Stirring B solution is added drop-wise in solution A simultaneously (amount ratio of solution A and B solution is 1～
1.5:1), sealing reaction 24h, through being centrifuged at a high speed, scrubbed, be dried after, obtain final product silicon dioxide.Wherein, ammonia in solution A
Amount ratio with deionized water is 1:1～1.2, dehydrated alcohol is 1 with the amount ratio of deionized water:1.5～2.Ethanol in B solution
Amount ratio with tetraethyl orthosilicate is 4～5:1.
Step 4, the silicon dioxide microsphere of the stratiform hydroxide copper benzoate of step 2 gained and step 3 gained is placed in water
In (amount ratio of stratiform hydroxide copper benzoate and silicon dioxide microsphere is 1～2:1), it is subsequently placed at and be lined with polytetrafluoroethyl-ne
In the stainless steel cauldron of alkene, put into carry out under the conditions of 120～160 DEG C in homogeneous reactor hydrothermal synthesis reaction 24～
After 36h, by products therefrom through sucking filtration, deionized water, absolute ethanol washing, 24h is dried in thermostatic drying chamber, obtain final product stratiform hydrogen
Oxidation copper benzoate-silicon dioxide composite material (LDH-Cu SiO2).
Embodiment 1
Step 1, the copper nitrate weighing 3.0g is dissolved in 50mL water, obtains copper nitrate solution, the Deca in copper nitrate solution
2.5mL strong aqua ammonia, is stirred continuously, and after light blue precipitation to be generated, continues stirring 0.5h at normal temperatures, after solution thoroughly precipitates
Ageing 6h, carries out sucking filtration, and deionized water is repeatedly washed to precipitate, subsequently 24h is dried at normal temperatures, obtains hydroxide
Copper；
Step 2,0.7140g Copper hydrate, 0.7170g benzoic acid is placed in 20mL deionized water, under the conditions of 95 DEG C
Carry out being sufficiently stirred for lower back flow reaction 24h, after question response terminates, product, through sucking filtration, washing, normal temperature drying 24h, obtains final product stratiform
Hydroxide copper benzoate (LDH-Cu).
Step 3, at normal temperatures, by 31.5mL deionized water, 30mL ammonia and 20mL dehydrated alcohol mix, prepare A is molten
Liquid；50mL ethanol is mixed with 11mL tetraethyl orthosilicate, prepares to obtain B solution；Stirring B solution is added drop-wise in solution A simultaneously, close
Envelope reaction 24h, through being centrifuged at a high speed, scrubbed, be dried after, obtain final product silicon dioxide.
Step 4, takes 0.1g stratiform hydroxide copper benzoate and 0.1g silicon dioxide microsphere to be placed in 20mL water, subsequently by it
It is placed in the stainless steel cauldron being lined with politef, put under the conditions of 140 DEG C, in homogeneous reactor, carry out hydro-thermal conjunction
After becoming reaction 30h, by products therefrom through sucking filtration, deionized water, absolute ethanol washing, 24h is dried in thermostatic drying chamber, obtain final product
Stratiform hydroxide copper benzoate-silicon dioxide composite material (LDH-Cu@SiO2).
Embodiment 2
Step 1, the copper nitrate weighing 3.0g is dissolved in 50mL water, obtains copper nitrate solution, Deca 3mL in copper nitrate solution
Strong aqua ammonia, is stirred continuously, and after light blue precipitation to be generated, continues stirring 1h at normal temperatures, is aged 8h after solution thoroughly precipitates,
Carry out sucking filtration, and deionized water is repeatedly washed to precipitate, subsequently 32h is dried at normal temperatures, obtains Copper hydrate；
Step 2,1.5g Copper hydrate, 1g benzoic acid are placed in 45mL deionized water, carry out fully under the conditions of 90 DEG C
Lower back flow reaction 18h of stirring, after question response terminates, product, through sucking filtration, washing, normal temperature drying 32h, obtains final product stratiform hydroxide benzene
Tubercuprose. (LDH-Cu).
Step 3, at normal temperatures, 30mL deionized water, 30mL ammonia and 20mL dehydrated alcohol is mixed, prepares to obtain solution A；
50mL ethanol is mixed with 10mL tetraethyl orthosilicate, prepares to obtain B solution；Stirring B solution is added drop-wise in solution A simultaneously, sealing
Reaction 24h, through being centrifuged at a high speed, scrubbed, be dried after, obtain final product silicon dioxide.
Step 4, takes 0.2g stratiform hydroxide copper benzoate and 0.1g silicon dioxide microsphere to be placed in 20mL water, subsequently by it
It is placed in the stainless steel cauldron being lined with politef, put under the conditions of 120 DEG C, in homogeneous reactor, carry out hydro-thermal conjunction
After becoming reaction 24h, by products therefrom through sucking filtration, deionized water, absolute ethanol washing, 24h is dried in thermostatic drying chamber, obtain final product
Stratiform hydroxide copper benzoate-silicon dioxide composite material (LDH-Cu@SiO2).
Embodiment 3
Step 1, the copper nitrate weighing 3.0g is dissolved in 50mL water, obtains copper nitrate solution, Deca 2mL in copper nitrate solution
Strong aqua ammonia, is stirred continuously, and after light blue precipitation to be generated, continues stirring 45min at normal temperatures, is aged after solution thoroughly precipitates
7h, carries out sucking filtration, and deionized water is repeatedly washed to precipitate, subsequently 28h is dried at normal temperatures, obtains Copper hydrate；
Step 2,1.2g Copper hydrate, 1g benzoic acid are placed in 36mL deionized water, carry out fully under the conditions of 100 DEG C
Lower back flow reaction 20h of stirring, after question response terminates, product, through sucking filtration, washing, normal temperature drying 28h, obtains final product stratiform hydroxide benzene
Tubercuprose. (LDH-Cu).
Step 3, at normal temperatures, 36mL deionized water, 30mL ammonia and 24mL dehydrated alcohol is mixed, prepares to obtain solution A；
40mL ethanol is mixed with 10mL tetraethyl orthosilicate, prepares to obtain B solution；Stirring B solution is added drop-wise in solution A simultaneously, sealing
Reaction 24h, through being centrifuged at a high speed, scrubbed, be dried after, obtain final product silicon dioxide.
Step 4, takes 0.15g stratiform hydroxide copper benzoate and 0.1g silicon dioxide microsphere to be placed in 20mL water, subsequently will
It is placed in the stainless steel cauldron being lined with politef, puts into and carries out hydro-thermal in homogeneous reactor under the conditions of 160 DEG C
After synthetic reaction 32h, by products therefrom through sucking filtration, deionized water, absolute ethanol washing, 24h is dried in thermostatic drying chamber, that is,
Obtain stratiform hydroxide copper benzoate-silicon dioxide composite material (LDH-Cu@SiO2).
Fig. 1 is the SEM figure of embodiment of the present invention step 2 gained LDH-Cu, as seen from the figure, the lamellar compound of synthesis
There is fibrous shape characteristic, special construction can be overlapped to form to this due to nano unit layer with clear view.Fig. 2 and Tu
3 is the SEM figure using the inventive method difference the hydro-thermal reaction time products therefrom, and wherein, Fig. 2 is in the case of 160 DEG C of 24h
Reaction generates, and Fig. 3 is to generate in the case of 160 DEG C of reaction 36h.Although most of stratiform hydroxide benzene during reaction 24h
Tubercuprose. is all wrapped on silicon dioxide microsphere, but its basic pattern still presents spherical, and only a small amount of is similar cellular
Structural generation.And react the LDH-Cu@SiO finding out during 36h that stratiform hydroxide copper benzoate is generated with silicon dioxide assembling2Present
Go out uniform alveolate texture, there is large specific surface area, and package assembly is complete.Subsequent optical Catalysis experiments choose this structure
Composite is carried out.
By prepared LDH-Cu@SiO2Composite carries out photocatalysis experiment, to test its photocatalytic activity：
a:To methyl orange catalytic degradation
Take the methyl orange solution that 50mL concentration is 10mg/L to put in 100mL beaker, add 0.05g LDH-Cu@SiO2Material
Material (having the alveolate texture of embodiment 3), opens magnetic agitation and ensures that in course of reaction, material is uniformly dispersed, dark in lucifuge
Under conditions of react 1h, middle every minor tick 20min takes a small amount of solution through high speed centrifugation, filter after measure suction 463nm at
Shading value, later on ultra violet lamp continues reaction, and every minor tick 20min samples mensuration absorbance value according to the method described above,
Stop when absorbance until continuously measuring tends towards stability.By the real time data recording according to formula η=(A1-A2)/A2*
100% calculating catalysis degradation modulus.
b:To rhodamine B catalytic degradation
Process is identical with a, mensuration absorbance value only at 554nm.
As shown in Figures 4 and 5, wherein Fig. 4 is methyl orange degradation effect to test result, and Fig. 5 is rhodamine B degradation effect.?
In incipient 1h, under the conditions of system is in dark reaction, matched group (1) TiO2Organic dyestuff is no degraded substantially, reason is
Photocatalytic reaction conditions do not possess.But subsequently under the conditions of ultraviolet light, the 1st group of degradation efficiency increases sharply, final degraded
Rate is more than 95%.And matched group (2) LDH-Cu then just shows certain disposal ability under the conditions of system is in dark reaction, this with
It is relevant that lamellar compound possesses ion-exchange capacity, and some dyes molecule is entered with anion form under specific system pH value
Between LDH-Cu compound layer, adsorb on material by electrostatic force.So in incipient 1h, methyl orange solution concentration
It is gradually reduced, but photocatalytic activity is not high, final degradation efficiency is 70% about.(3rd) group LDH-Cu@SiO2Result shows,
After forming core-shell structure copolymer composite construction, this material not only under the conditions of dark reaction can direct adsorpting dye molecule, and in purple
Under outer light irradiation, preferably, final degradation efficiency is close to 100% for photocatalytic activity.Under equal conditions, this catalyst is not only suitable for
Scope is wide, and the synergism of adsorption and photocatalytic degradation also makes its degradation efficiency than simple TiO2Photocatalyst will
Good.Fig. 4 is test result indicate that the process to rhodamine B also assumes similar result.
Fig. 6 is LDH-Cu@SiO2Degradation of dye principle process schematic, after forming composite construction, on the one hand with hydrogen bond shape
Formula and SiO2Dye molecule can be adsorbed to interlayer by the LDH-Cu being directly connected to, simultaneously under the conditions of ultraviolet light, with SiO2
Directly in conjunction with dye molecule be degraded by the form of photochemical catalytic oxidation.And form LDH-Cu@SiO2Afterwards material specific surface area,
In solution, dispersive property all improves to some extent, and ultimately helps to lift photocatalytic degradation efficiency.
For photochemical reaction, reaction medium has a major impact to aspects such as reaction rate, product purity, all mixes
Difference in liquid and heterogeneous medium is very big.Layered double-hydroxide material (Layered double hydroxide, LDH) can
Fixed using as material of main part, having photoactive material, and provide two-dimensional layer space controlled in order, thus changing master
The optics of object, electrical properties are simultaneously used for photocatalysis field.Nano-meter SiO_22Microsphere has smooth surface, particle diameter unification, dispersibility
Good advantage, and have that nanoparticle specific surface area is big, quantum size effect feature concurrently.By being self-assembly of LDH@SiO2
The nano composite material of nucleocapsid structure, is not only advantageous to increase the dispersibility of catalyst, changes reaction medium to improve photocatalysis
Activity；And special nucleocapsid structure reduces the loss of material in separation process, partly treat that degradation product also can be by LDH class thing
Upright connect absorption, thus jointly improving the degradation efficiency of waste water from dyestuff in synergistic mode, in practical novel photocatalysis
Agent development aspect is a breakthrough.
Claims (8)
1. there is the hydroxide copper benzoate-SiO of photocatalytic2The preparation method of composite it is characterised in that specifically according to
Following steps are implemented：
Step 1, prepares stratiform hydroxide copper benzoate；
Step 2, prepares silicon dioxide microsphere；
Step 3, the stratiform hydroxide copper benzoate of step 1 gained and the silicon dioxide microsphere of step 2 gained are placed in water,
After carrying out hydrothermal synthesis reaction 24～36h under the conditions of 120～160 DEG C, by products therefrom through sucking filtration, deionized water, anhydrous second
Alcohol washs, 24h is dried in thermostatic drying chamber, obtains final product stratiform hydroxide copper benzoate-SiO2Composite.
2. the hydroxide copper benzoate-SiO with photocatalytic according to claim 12The preparation method of composite,
It is characterized in that, in step 1, the preparation process of stratiform hydroxide copper benzoate is：
Step 1.1：To in copper nitrate solution, Deca strong aqua ammonia, is stirred continuously, and after light blue precipitation to be generated, continues at normal temperatures
Stirring 0.5～1h, is aged 6～8h after solution thoroughly precipitates, carries out sucking filtration, and deionized water is repeatedly washed to precipitate
Wash, subsequently 24～32h is dried at normal temperatures, obtains Copper hydrate；
Step 1.2：Copper hydrate, benzoic acid are placed in deionized water, carry out being sufficiently stirred for next time under the conditions of 90～100 DEG C
Stream reaction 18～24h, after question response terminates, product, through sucking filtration, washing, normal temperature drying 24～32h, obtains final product stratiform hydroxide benzene
Tubercuprose..
3. the hydroxide copper benzoate-SiO with photocatalytic according to claim 22The preparation method of composite,
It is characterized in that, in step 1.1, the concentration of copper nitrate solution is 0.32mol/L, and strong aqua ammonia with the amount ratio of copper nitrate solution is
1:18～25.
4. the hydroxide copper benzoate-SiO with photocatalytic according to claim 22The preparation method of composite,
It is characterized in that, in step 1.2, Copper hydrate and benzoic amount ratio are 1～1.5:1.
5. the hydroxide copper benzoate-SiO with photocatalytic according to claim 12The preparation method of composite,
It is characterized in that, in step 2, the preparation process of silicon dioxide microsphere is：
Step 2.1：At normal temperatures, deionized water, ammonia and dehydrated alcohol are mixed, prepare to obtain solution A；By ethanol and positive silicic acid
Ethyl ester mixes, and prepares to obtain B solution；
Step 2.2：Stirring B solution is added drop-wise in solution A simultaneously, sealing reaction 24h, through being centrifuged at a high speed, scrubbed, dry
After dry, obtain final product silicon dioxide.
6. the hydroxide copper benzoate-SiO with photocatalytic according to claim 52The preparation method of composite,
It is characterized in that, in solution A, ammonia and the amount ratio of deionized water are 1:1～1.2, the amount ratio of dehydrated alcohol and deionized water
For 1:1.5～2；In B solution, ethanol and the amount ratio of tetraethyl orthosilicate are 4～5:1.
7. the hydroxide copper benzoate-SiO with photocatalytic according to claim 52The preparation method of composite,
It is characterized in that, in step 2.2, solution A is 1～1.5 with the amount ratio of B solution:1.
8. the hydroxide copper benzoate-SiO with photocatalytic according to claim 12The preparation method of composite,
It is characterized in that, in step 3, stratiform hydroxide copper benzoate is 1～2 with the amount ratio of silicon dioxide microsphere:1.
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