CN106391110B - The preparation method of hydroxide copper benzoate-SiO2 composite materials with photocatalytic - Google Patents
The preparation method of hydroxide copper benzoate-SiO2 composite materials with photocatalytic Download PDFInfo
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- CN106391110B CN106391110B CN201610788582.3A CN201610788582A CN106391110B CN 106391110 B CN106391110 B CN 106391110B CN 201610788582 A CN201610788582 A CN 201610788582A CN 106391110 B CN106391110 B CN 106391110B
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- copper benzoate
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 21
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 21
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 21
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 21
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 title claims description 22
- 230000001699 photocatalysis Effects 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- OVMZYIMAAFBAGQ-UHFFFAOYSA-L C(C1=CC=CC=C1)(=O)[O-].O[Cu+] Chemical compound C(C1=CC=CC=C1)(=O)[O-].O[Cu+] OVMZYIMAAFBAGQ-UHFFFAOYSA-L 0.000 claims abstract description 22
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 22
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 11
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- -1 hydroxide benzene Copper formate Chemical compound 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical compound CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 26
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 16
- 239000000975 dye Substances 0.000 abstract description 12
- 239000002351 wastewater Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000009881 electrostatic interaction Effects 0.000 abstract description 2
- 238000009434 installation Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000009885 systemic effect Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000012545 processing Methods 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
- 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 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 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 description 3
- 125000005909 ethyl alcohol group Chemical group 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
- 230000008569 process Effects 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 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
- 238000005297 material degradation process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000011160 research Methods 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
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011229 interlayer 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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 kind of hydroxide copper benzoate SiO with photocatalytic2The preparation method of composite material, first Kocide SD is prepared using the precipitation method, stratiform hydroxide copper benzoate is prepared as primary raw material using Kocide SD, benzoic acid, then it is made to carry out hydrothermal synthesis reaction with silicon dioxide microsphere to get assembling product hydroxide copper benzoate silica.The present invention is prepared for the LDH Cu@SiO2 composite materials of nucleocapsid by self-assembly method, and fibrous LDH Cu are equably wrapped in SiO2On microballoon, whole pattern is complete.Compared with conventional layered Nano compound, dispersibility is more preferable in the reaction system, and photocatalytic activity is more preferable；LDH‑Cu@SiO2LDH Cu in composite material can improve the degradation efficiency of waste water from dyestuff by organic substance in the various ways Synergistic degradation waste water from dyestuff such as ion exchange, electrostatic interaction.The preparation method is simple and effective, does not need special installation, and a kind of method of simple possible is provided for the compound of more different function materials.
Description
Technical field
The invention belongs to catalysis material preparing technical fields, and in particular to a kind of hydroxide benzene first with photocatalytic
Sour copper-SiO2The preparation method of composite material.
Background technology
China's rapid economic development in recent years, the industry developments impetus such as industry, building, weaving are swift and violent, a large amount of Industry Wastes
Gurry discharge causes problem of environmental pollution further serious.Therefore to all kinds of environmental contaminants be effectively treated have become one compel
In the task of the eyebrows and eyelashes.A large amount of colorful wastewaters that wherein industries such as papermaking, printing and dyeing are discharged have big toxicity, complicated component, difficult life
The features such as object is degraded, the extensive concern of researcher is constantly subjected to about the processing of this kind of waste water.Conventional processes master at present
Want active carbon adsorption, biological degradation method, dosing absorption method.But there are processing cost height, degradation be not thorough for above-mentioned several method
Bottom, there are secondary pollution etc. defects, it is difficult to which large-scale promotion or treatment effect are bad.
Photocatalysis technology has the characteristics that environmentally protective, clean energy saving, is very active one of the research field of academia,
It has broad application prospects in environmental protection, new function material exploitation, Solar use etc..But with TiO2To represent
Catalysis material be easy to happen photoetch phenomenon, stability is not high；And band gap is wide, internal carrier coincidence rate height etc. lacks
It falls into and makes photocatalysis performance bad, greatly limit further application and development.Therefore to have material modification, modification and
Developing novel photocatalysis material becomes the hot issue of current research.
Invention content
The object of the present invention is to provide a kind of hydroxide copper benzoate-SiO with photocatalytic2The preparation of composite material
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, is specifically implemented according to the following steps：
Step 1, stratiform hydroxide copper benzoate is prepared；
Step 2, silicon dioxide microsphere is prepared；
Step 3, the stratiform hydroxide copper benzoate obtained by step 1 is placed in water with the silicon dioxide microsphere obtained by step 2
In, after carrying out hydrothermal synthesis reaction 24~36h under the conditions of 120~160 DEG C, by products therefrom through filtering, with deionized water, nothing
Water-ethanol washing is dried in thermostatic drying chamber for 24 hours to get stratiform hydroxide copper benzoate-SiO2Composite material (LDH-Cu@
SiO2)。
It is of the invention to be further characterized in that,
In step 1, the preparation process of stratiform hydroxide copper benzoate is：
Step 1.1：Concentrated ammonia liquor is added dropwise into copper nitrate solution, is stirred continuously, after light blue precipitation to be generated, at normal temperatures
Continue 0.5~1h of stirring, be aged 6~8h after solution thoroughly precipitation, filtered, is used in combination deionized water to carry out sediment more
Secondary washing then dries 24~32h, obtains Kocide SD at normal temperatures；
Step 1.2：Kocide SD, benzoic acid are placed in deionized water, are sufficiently stirred under the conditions of 90~100 DEG C
Lower back flow reaction 18~for 24 hours, it waits for after reaction, product is by suction filtration, washing, 24~32h of air drying to get stratiform hydrogen-oxygen
Change copper benzoate (LDH-Cu).
In step 1.1, the amount ratio of a concentration of 0.32mol/L of copper nitrate solution, concentrated ammonia liquor and copper nitrate solution are 1:
18~25.
In step 1.2, the amount ratio of Kocide SD and benzoic acid is 1~1.5:1.
In step 2, the preparation process of silicon dioxide microsphere is：
Step 2.1：At normal temperatures, deionized water, ammonium hydroxide and absolute ethyl alcohol are mixed, with obtained solution A；By ethyl alcohol and just
Silester mixes, with obtained B solution；
Step 2.2：B solution is added drop-wise in solution A by stirring simultaneously, and sealing is reacted for 24 hours, through being centrifuged at a high speed, through washing
Wash, dry after to get silica.
Ammonium hydroxide and the amount ratio of deionized water are 1 in solution A:1~1.2, the amount ratio of absolute ethyl alcohol and deionized water is
1:1.5~2；The amount ratio of ethyl alcohol and ethyl orthosilicate is 4~5 in B solution:1.
In step 2.2, the amount ratio of solution A and B solution is 1~1.5:1.
In step 3, the amount ratio of stratiform hydroxide copper benzoate and silicon dioxide microsphere is 1~2:1.
The invention has the advantages that being prepared for the LDH-Cu@SiO of nucleocapsid structure by self-assembly method2Composite material,
The LDH-Cu of threadiness is equably wrapped in SiO2On microballoon, whole pattern is complete.Compared with conventional layered Nano compound,
Dispersibility is more preferable in reaction system, and photocatalytic activity is more preferable； LDH-Cu@SiO2LDH-Cu in composite material can by from
Organic substance in the various ways Synergistic degradation waste water from dyestuff such as sub- exchange, electrostatic interaction, improves the degradation efficiency of waste water from dyestuff.It should
Preparation method is simple and effective, does not need special installation, is that the compound of more different function materials provides a kind of simple possible
Method.
Description of the drawings
Fig. 1 is the SEM figures of stratiform hydroxide copper benzoate obtained by the embodiment of the present invention；
Fig. 2 is the SEM figures of stratiform hydroxide copper benzoate-silica obtained by the method for the present invention；
Fig. 3 is that the SEM of 3 gained stratiform hydroxide copper benzoate of the embodiment of the present invention-silica schemes；
Fig. 4 is the hydroxide copper benzoate-SiO that the present invention has photocatalytic2Layer obtained by the preparation method of composite material
Degradation effect figure of the shape hydroxide copper benzoate-silica to methyl orange；
Fig. 5 is the hydroxide copper benzoate-SiO that the present invention has photocatalytic2Layer obtained by the preparation method of composite material
Degradation effect figure of the shape hydroxide copper benzoate-silica to rhodamine；
Fig. 6 is the hydroxide copper benzoate-SiO that the present invention has photocatalytic2Layer obtained by the preparation method of composite material
The degradation principles figure of shape hydroxide copper benzoate-silica.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of hydroxide copper benzoate-SiO with photocatalytic of the present invention2The preparation method of composite material, first uses
The precipitation method prepare Kocide SD, using Kocide SD, benzoic acid as primary raw material prepare stratiform hydroxide copper benzoate, then make its with
Silicon dioxide microsphere carries out hydrothermal synthesis reaction to get assembling product-hydroxide copper benzoate-silica.Specifically according to
Lower step is implemented：
Step 1, concentrated ammonia liquor is added dropwise into copper nitrate solution, is stirred continuously, after light blue precipitation to be generated, at normal temperatures after
0.5~1h of continuous stirring is aged 6~8h after solution thoroughly precipitation, is filtered, and is used in combination deionized water to carry out sediment multiple
Washing then dries 24~32h, obtains Kocide SD at normal temperatures；Wherein, a concentration of 0.32mol/L of copper nitrate solution, dense ammonia
The amount ratio of water and copper nitrate solution is 1:18~25.
Step 2, Kocide SD, benzoic acid are placed in deionized water, under being sufficiently stirred under the conditions of 90~100 DEG C
Back flow reaction 18~for 24 hours, it waits for after reaction, product is by suction filtration, washing, 24~32h of air drying to get stratiform hydroxide
Copper benzoate (LDH-Cu).Wherein, the amount ratio of Kocide SD and benzoic acid is 1~1.5:1.
Step 3, at normal temperatures, deionized water, ammonium hydroxide and absolute ethyl alcohol are mixed, with obtained solution A；By ethyl alcohol and positive silicon
Acetoacetic ester mixes, with obtained 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 is reacted for 24 hours, through being centrifuged at a high speed, to get silica after washed, drying.Wherein, ammonium hydroxide in solution A
Amount ratio with deionized water is 1:1~1.2, the amount ratio of absolute ethyl alcohol and deionized water is 1:1.5~2.Second in B solution
The amount ratio of alcohol and ethyl orthosilicate is 4~5:1.
Step 4, the stratiform hydroxide copper benzoate obtained by step 2 is placed in water with the silicon dioxide microsphere obtained by step 3
In (amount ratio of stratiform hydroxide copper benzoate and silicon dioxide microsphere be 1~2:1) it, is subsequently placed at and is lined with polytetrafluoroethyl-ne
In the stainless steel cauldron of alkene, be put into homogeneous reactor under the conditions of 120~160 DEG C carry out hydrothermal synthesis reaction 24~
After 36h, products therefrom washed through filtering, with deionized water, absolute ethyl alcohol, dried for 24 hours to get stratiform hydrogen in thermostatic drying chamber
Aoxidize copper benzoate-silicon dioxide composite material (LDH-Cu SiO2)。
Embodiment 1
Step 1, the copper nitrate for weighing 3.0g is dissolved in 50mL water, is obtained copper nitrate solution, is added dropwise into copper nitrate solution
2.5mL concentrated ammonia liquors, are stirred continuously, and after light blue precipitation to be generated, continue to stir 0.5h at normal temperatures, wait for that solution thoroughly precipitates
After be aged 6h, filtered, deionized water be used in combination repeatedly to wash sediment, then it is dry at normal temperatures for 24 hours, obtain hydrogen-oxygen
Change copper；
Step 2,0.7140g Kocide SDs, 0.7170g benzoic acid are placed in 20mL deionized waters, under the conditions of 95 DEG C
It carries out being sufficiently stirred lower back flow reaction for 24 hours, wait for after reaction, product is by suction filtration, washing, air drying for 24 hours to get stratiform
Hydroxide copper benzoate (LDH-Cu).
Step 3, at normal temperatures, 31.5mL deionized waters, 30mL ammonium hydroxide and 20mL absolute ethyl alcohols are mixed, with being made, A is molten
Liquid；50mL ethyl alcohol is mixed with 11mL ethyl orthosilicates, with obtained B solution；B solution is added drop-wise in solution A by stirring simultaneously, close
Envelope is reacted for 24 hours, through being centrifuged at a high speed, to get silica after washed, drying.
Step 4,0.1g stratiform hydroxide copper benzoates are taken to be placed in 20mL water with 0.1g silicon dioxide microspheres, then by it
It is placed in the stainless steel cauldron for being lined with polytetrafluoroethylene (PTFE), is put into homogeneous reactor progress hydro-thermal conjunction under the conditions of 140 DEG C
At reaction 30h after, products therefrom wash through filtering, with deionized water, absolute ethyl alcohol, thermostatic drying chamber dry for 24 hours to get
Stratiform hydroxide copper benzoate-silicon dioxide composite material (LDH-Cu@SiO2)。
Embodiment 2
Step 1, the copper nitrate for weighing 3.0g is dissolved in 50mL water, obtains copper nitrate solution, 3mL is added dropwise into copper nitrate solution
Concentrated ammonia liquor is stirred continuously, and after light blue precipitation to be generated, is continued to stir 1h at normal temperatures, is aged after solution thoroughly precipitation
8h is filtered, and deionized water is used in combination repeatedly to wash sediment, is then dried 32h at normal temperatures, is obtained Kocide SD；
Step 2,1.5g Kocide SDs, 1g benzoic acid are placed in 45mL deionized waters, are carried out under the conditions of 90 DEG C abundant
The lower back flow reaction 18h of stirring waits for after reaction, product is by suction filtration, washing, air drying 32h to get stratiform hydroxide benzene
Copper formate (LDH-Cu).
Step 3, at normal temperatures, 30mL deionized waters, 30mL ammonium hydroxide and 20mL absolute ethyl alcohols are mixed, with obtained solution A；
50mL ethyl alcohol is mixed with 10mL ethyl orthosilicates, with obtained B solution；B solution is added drop-wise in solution A by stirring simultaneously, is sealed
It reacts for 24 hours, through being centrifuged at a high speed, to get silica after washed, drying.
Step 4,0.2g stratiform hydroxide copper benzoates are taken to be placed in 20mL water with 0.1g silicon dioxide microspheres, then by it
It is placed in the stainless steel cauldron for being lined with polytetrafluoroethylene (PTFE), is put into homogeneous reactor progress hydro-thermal conjunction under the conditions of 120 DEG C
At reaction for 24 hours after, products therefrom wash through filtering, with deionized water, absolute ethyl alcohol, thermostatic drying chamber dry for 24 hours to get
Stratiform hydroxide copper benzoate-silicon dioxide composite material (LDH-Cu@SiO2)。
Embodiment 3
Step 1, the copper nitrate for weighing 3.0g is dissolved in 50mL water, obtains copper nitrate solution, 2mL is added dropwise into copper nitrate solution
Concentrated ammonia liquor is stirred continuously, and after light blue precipitation to be generated, continues to stir 45min at normal temperatures, old after solution thoroughly precipitation
Change 7h, filtered, deionized water is used in combination repeatedly to wash sediment, then dries 28h at normal temperatures, obtain hydroxide
Copper；
Step 2,1.2g Kocide SDs, 1g benzoic acid are placed in 36mL deionized waters, are carried out under the conditions of 100 DEG C abundant
The lower back flow reaction 20h of stirring waits for after reaction, product is by suction filtration, washing, air drying 28h to get stratiform hydroxide benzene
Copper formate (LDH-Cu).
Step 3, at normal temperatures, 36mL deionized waters, 30mL ammonium hydroxide and 24mL absolute ethyl alcohols are mixed, with obtained solution A；
40mL ethyl alcohol is mixed with 10mL ethyl orthosilicates, with obtained B solution；B solution is added drop-wise in solution A by stirring simultaneously, is sealed
It reacts for 24 hours, through being centrifuged at a high speed, to get silica after washed, drying.
Step 4, it takes 0.15g stratiform hydroxide copper benzoates to be placed in 20mL water with 0.1g silicon dioxide microspheres, then will
It is placed in the stainless steel cauldron for being lined with polytetrafluoroethylene (PTFE), is put into homogeneous reactor and carries out hydro-thermal under the conditions of 160 DEG C
After synthetic reaction 32h, products therefrom washed through filtering, with deionized water, absolute ethyl alcohol, dried for 24 hours, i.e., in thermostatic drying chamber
Obtain stratiform hydroxide copper benzoate-silicon dioxide composite material (LDH-Cu@SiO2)。
The SEM that Fig. 1 is step 2 gained of embodiment of the present invention LDH-Cu schemes, as seen from the figure, the lamellar compound of synthesis
With threadiness shape characteristic, can with clear view to this since nano unit layer overlaps to form special construction.Fig. 2 and figure
3 for utilize the method for the present invention difference the hydro-thermal reaction time products therefrom SEM figure, wherein Fig. 2 be 160 DEG C for 24 hours the case where
What lower reaction generated, Fig. 3 is generated in the case of reacting 36h at 160 DEG C.Reaction for 24 hours when although most of stratiform hydroxides
Copper benzoate is all wrapped on silicon dioxide microsphere, but its basic pattern still present it is spherical, it is only a small amount of similar cellular
Structural generation.And the LDH-Cu@SiO that stratiform hydroxide copper benzoate is generated with silica assembling are found out when reacting 36h2
Uniform honeycomb structure is showed, there is large specific surface area, and package assembly is complete.Subsequent optical Catalysis experiments are chosen this
Structural composite material carries out.
By prepared LDH-Cu@SiO2Composite material carries out photocatalysis experiment, to test its photocatalytic activity：
a:To methyl orange catalytic degradation
It takes the methyl orange solution of a concentration of 10mg/L of 50mL to be put into 100mL beakers, 0.05g LDH-Cu@SiO is added2Material
Material (honeycomb structure with embodiment 3) opens magnetic agitation and ensures that material is uniformly dispersed in reaction process, is being protected from light dark
Under conditions of react 1h, it is intermediate that a small amount of solution is taken to measure suction 463nm at after high speed centrifugation, filtering per minor tick 20min
Shading value, the reaction was continued for later on ultra violet lamp, and absorbance value is measured according to the method described above per minor tick 20min samplings,
Stop when the absorbance value continuously measured tends towards stability.By the real time data measured according to formula η=﹝ (A1-A2)/A2﹞ *
100% calculates catalysis degradation modulus.
b:To rhodamine B catalytic degradation
Process is identical as a, and absorbance value is measured only at 554nm.
Test result is as shown in Figures 4 and 5, and wherein Fig. 4 is methyl orange degradation effect, and Fig. 5 is rhodamine B degradation effect.
In incipient 1h, system is under the conditions of dark reaction, control group (1) TiO2To organic dyestuff substantially without degradation, reason is
Photocatalytic reaction conditions do not have.But then under the conditions of ultraviolet light, the 1st group of degradation efficiency increases sharply, final to degrade
Rate is more than 95%.And control group (2) LDH-Cu then just shows certain processing capacity under the conditions of system is in dark reaction, this
It is related to have an ion-exchange capacity with lamellar compound, some dyes molecule is entered under specific system pH value in the form of anion
Between LDH-Cu compound layers, it is adsorbed on material by electrostatic force.So in incipient 1h, methyl orange solution is dense
Degree is gradually reduced, but photocatalytic activity is not high, and final degradation efficiency is 70% or so.(3) organize LDH-Cu@SiO2As a result table
It is bright, after forming core-shell structure copolymer composite construction, the material not only under the conditions of dark reaction can direct adsorpting dye molecule, and
Under ultraviolet light, photocatalytic activity is preferable, and final degradation efficiency is close to 100%.Under equal conditions, the catalyst is not only
It is applied widely, and the synergistic effect of suction-operated and photocatalytic degradation is but also the simple TiO of its degradation efficiency ratio2Photocatalysis
Agent will be got well.Fig. 4 is the experimental results showed that similar result is also presented in the processing to rhodamine B.
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, while under the conditions of ultraviolet light, with SiO2
The dye molecule bound directly is degraded by the form of photochemical catalytic oxidation.And form LDH-Cu@SiO2Afterwards material specific surface area,
Dispersion performance improves to some extent in solution, ultimately helps to promote photocatalytic degradation efficiency.
For photochemical reaction, reaction medium has a major impact reaction rate, product purity etc., mixes
Difference in liquid and heterogeneous medium is very big.Layered double-hydroxide material (Layered double hydroxide, LDH) can
As material of main part, will there is photoactive substance to fix, and provide orderly controllable two-dimensional layer space, to change master
The optics of object, electrical properties are simultaneously used for photocatalysis field.Nano-meter SiO_22Microballoon has smooth surface, grain size unification, dispersibility
Good advantage, and have both nano-particle large specific surface area, quantum size effect feature.By being self-assembly of LDH@SiO2
The nanocomposite 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 waits for that degradation product also can be by LDH class objects
It is upright to connect absorption, to improve the degradation efficiency of waste water from dyestuff jointly in a manner of synergistic effect, in practical novel photocatalysis
It is a breakthrough in terms of agent development.
Claims (7)
1. the hydroxide copper benzoate-SiO with photocatalytic2The preparation method of composite material, which is characterized in that specifically according to
Following steps are implemented：
Step 1, stratiform hydroxide copper benzoate is prepared；
Step 2, silicon dioxide microsphere is prepared；
Step 3, the stratiform hydroxide copper benzoate obtained by step 1 is placed in water with the silicon dioxide microsphere obtained by step 2,
After carrying out hydrothermal synthesis reaction 24~36h under the conditions of 120~160 DEG C, by products therefrom through filtering, with deionized water, anhydrous second
Alcohol washing is dried in thermostatic drying chamber for 24 hours to get stratiform hydroxide copper benzoate-SiO2Composite material；
In step 1, the preparation process of stratiform hydroxide copper benzoate is：
Step 1.1：Concentrated ammonia liquor is added dropwise into copper nitrate solution, is stirred continuously, after light blue precipitation to be generated, continues at normal temperatures
0.5~1h is stirred, 6~8h is aged after solution thoroughly precipitation, is filtered, deionized water is used in combination repeatedly to wash sediment
It washs, then dries 24~32h at normal temperatures, obtain Kocide SD；
Step 1.2：Kocide SD, benzoic acid are placed in deionized water, are sufficiently stirred next time under the conditions of 90~100 DEG C
Stream reaction 18~for 24 hours, it waits for after reaction, product is by suction filtration, washing, 24~32h of air drying to get stratiform hydroxide benzene
Copper formate.
2. the hydroxide copper benzoate-SiO according to claim 1 with photocatalytic2The preparation method of composite material,
It is characterized in that, in step 1.1, the amount ratio of a concentration of 0.32mol/L of copper nitrate solution, concentrated ammonia liquor and copper nitrate solution are
1:18~25.
3. the hydroxide copper benzoate-SiO according to claim 1 with photocatalytic2The preparation method of composite material,
It is characterized in that, in step 1.2, the amount ratio of Kocide SD and benzoic acid is 1~1.5:1.
4. the hydroxide copper benzoate-SiO according to claim 1 with photocatalytic2The preparation method of composite material,
It is characterized in that, in step 2, the preparation process of silicon dioxide microsphere is：
Step 2.1：At normal temperatures, deionized water, ammonium hydroxide and absolute ethyl alcohol are mixed, with obtained solution A；By ethyl alcohol and positive silicic acid
Ethyl ester mixes, with obtained B solution；
Step 2.2：B solution is added drop-wise in solution A by stirring simultaneously, and sealing reaction is for 24 hours, washed, dry through being centrifuged at a high speed
To get silica after dry.
5. the hydroxide copper benzoate-SiO according to claim 4 with photocatalytic2The preparation method of composite material,
It is characterized in that, ammonium hydroxide and the amount ratio of deionized water are 1 in solution A:1~1.2, the amount ratio of absolute ethyl alcohol and deionized water
It is 1:1.5~2；The amount ratio of ethyl alcohol and ethyl orthosilicate is 4~5 in B solution:1.
6. the hydroxide copper benzoate-SiO according to claim 4 with photocatalytic2The preparation method of composite material,
It is characterized in that, in step 2.2, the amount ratio of solution A and B solution is 1~1.5:1.
7. the hydroxide copper benzoate-SiO according to claim 1 with photocatalytic2The preparation method of composite material,
It is characterized in that, in step 3, the amount ratio of stratiform hydroxide copper benzoate and silicon dioxide microsphere is 1~2:1.
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