CN109985645A - A kind of hollow Porous HAP microballoon composite material of CdS/ and its preparation and application - Google Patents
A kind of hollow Porous HAP microballoon composite material of CdS/ and its preparation and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 16
- 239000004098 Tetracycline Substances 0.000 claims abstract description 15
- 229960002180 tetracycline Drugs 0.000 claims abstract description 15
- 229930101283 tetracycline Natural products 0.000 claims abstract description 15
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 15
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 229940059939 kayexalate Drugs 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000001110 calcium chloride Substances 0.000 claims abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910000397 disodium phosphate Inorganic materials 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 description 10
- 230000003115 biocidal effect Effects 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
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- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
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- Catalysts (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention provides a kind of preparation methods of the hollow Porous HAP microballoon composite material of CdS/ characterized by comprising by CaCl2Solution is added in kayexalate solution, and Na is added dropwise in stirring2CO3Solution stirs to get white suspension, is centrifuged, and cleans, dry, obtains CaCO3Microballoon presoma；By CaCO3Microballoon forerunner dispersion liquid and Na2HPO4Solution mixing, adjusting pH are 10.5-11.5, are reacted, are cooled to room temperature at 110-130 DEG C, are centrifuged, and are cleaned, dry, obtain hollow Porous HAP microballoon；It is mixed after taking CdS and hollow Porous HAP microballoon to be dissolved in deionized water respectively, carries out hydro-thermal reaction, obtain the hollow Porous HAP microballoon composite material of CdS/.The present invention has the degradation property simple, quickly and efficiently for removing tetracycline wastewater.
Description
Technical field
The invention belongs to materialogy fields, are related to a kind of composite material, specifically a kind of high efficiency photocatalysis degradation four
The preparation method of the hollow Porous HAP microballoon composite material of the CdS/ of ring element waste water.
Background technique
As the further understanding and concern, the demand to environment remediation technology of people's environmental pollution also increasingly increase.
More especially be similar to the broad-spectrum antibiotics of quadracycline (TC) etc., due to being widely used caused by environmental pollution ask
Topic.These antibiotic, which are not only polluted caused by lake, river and ocean, to be got worse, but also is also resulted in the ecosystem various
Adverse effect, makes the healthy living of the mankind face grave danger.Therefore, the task of top priority be find it is a kind of green, it is sustainable
Method solve the problems, such as that antibiotic pollutes in water environment.Photocatalysis technology have the characteristics that efficiently, environmental protection, it is cheap, be
It is a kind of not only to have economized on resources but also environmental-friendly " green " method, thus people is more and more obtained in terms of antibiotic waste water processing
Favor.It is well known that the carrier of photocatalysis technology functionization is photochemical catalyst, so design and research and development high-performance optical catalysis
Agent is the core missions of photocatalytic degradation antibiotic waste water.But the photochemical catalyst currently used for photocatalytic degradation antibiotic waste water is general
Store-through is the removal rate of antibiotic is undesirable, mineralization rate is relatively low, photocatalyst activity and stability is poor and photochemical catalyst
Research and develop the defects of on the high side.In addition, compared with other water pollutants such as dyestuff, the more difficult light degradation of antibiotic.Therefore, it actively seeks
Summation exploitation has efficiently and the photocatalysis new material and its new preparation process and new technology of high stability are always researchers
It is insistent to pursue a goal.
In recent years, hydroxyapatite (Ca10(PO4)6(OH)2, HAP) and it is used as a kind of inorganic functional material, because it has well
Biocompatibility, bioactivity, nontoxicity, the environmental-friendly and characteristics such as cheap and be widely used in biomaterial
In.In addition, HAP has caused researchers' simultaneously also with excellent organic matter absorption and photocatalytic degradation capability
Great interest becomes one of the research hotspot of novel photocatalysis material.
Summary of the invention
It is an object of the present invention to provide materials and its system that a kind of pair of tetracycline wastewater has preferable Photocatalytic Degradation Property
Standby and application.
In order to achieve the above object, the present invention provides a kind of preparation sides of the hollow Porous HAP microballoon composite material of CdS/
Method characterized by comprising
Step 1: by CaCl2Solution is added in kayexalate (PSS) solution, and Na is added dropwise in stirring2CO3It is molten
Liquid stirs to get white suspension, and obtained solid is used deionized water and washes of absolute alcohol by centrifugation respectively, dry, obtains
CaCO3Microballoon presoma；
Step 2: preparing CaCO3Microballoon forerunner's dispersion liquid, by CaCO3Microballoon forerunner dispersion liquid and Na2HPO4Solution is mixed
It closes, adjusting pH with NaOH is 10.5-11.5, is reacted, is cooled to room temperature at 110-130 DEG C, is centrifuged, with deionized water and nothing
Water-ethanol cleaning, it is dry, obtain hollow Porous HAP microballoon；
Step 3: it is mixed after taking CdS and hollow Porous HAP microballoon to be dissolved in deionized water respectively, carries out hydro-thermal reaction, it is cooling
To room temperature, centrifugation is dry by obtained solid, obtains the hollow Porous HAP microballoon composite material of CdS/.
Preferably, the CaCl2The concentration of solution is 0.15M-0.25M.
Preferably, the concentration of the kayexalate (PSS) solution is 5mg/mL-15mg/mL.
Preferably, the Na2CO3The concentration of solution is 0.15M-0.25M.
Preferably, the CaCO3The solid content of microballoon forerunner's dispersion liquid is 5g/L-10g/L.
Preferably, the Na2HPO4The concentration of solution is 0.02M-0.06M.
Preferably, the CaCl2Solution, kayexalate solution and Na2CO3The volume ratio of solution is 1:9-11:
0.9-1.1。
Preferably, the CaCO3And Na2HPO4Molar ratio be 1:0.55-0.65.
Preferably, the weight ratio of the CdS and hollow Porous HAP microballoon is 1:9.5-10.5.
Preferably, the temperature of the hydro-thermal reaction in the step 3 is 75-85 DEG C.
The present invention also provides the hollow Porous HAP microballoon composite materials of CdS/ prepared by above-mentioned preparation method.
The present invention also provides the application methods of the hollow Porous HAP microballoon composite material of above-mentioned CdS/, which is characterized in that
It include: that the above-mentioned hollow Porous HAP microballoon composite material of CdS/ is placed in tetracycline, dark reaction reaches absorption-
Desorption equilibrium, illumination degrade to tetracycline.
The present invention uses hollow calcium carbonate (CaCO3) microballoon is template and prepares object in conjunction with hydro-thermal method.Using low
Warm water thermal method synthesizes CdS/ hollow porous micro sphere HAP composite material.The system of photochemical catalyst with specific composition and appearance structure
It is standby to play a key effect to raising photocatalysis performance.Hollow Porous HAP microballoon both can be used as a kind of good adsorbent, can also
Using the photochemical catalyst excellent as one kind.Porous characteristic means that light-catalyzed reaction can occur on bigger surface, and
The band structure of hollow Porous HAP microballoon can by it is subsequent it is CdS-loaded composite photo-catalyst obtained with this realize adjustment, into
And reach higher photocatalysis efficiency.So far, there is not yet the CdS/ for photocatalytic degradation tetracycline wastewater is hollow more
Hole HAP microballoon composite material and preparation method thereof patent of invention report.
Compared with prior art, the beneficial effects of the present invention are:
Preparation method of the present invention is scientific, rationally easy, low in cost, repeated height, the resulting hollow Porous HAP of CdS/ are micro-
Ball composite material has simple, removal tetracycline wastewater quickly and efficiently degradation property, thus before there is potential application
Scape.
Detailed description of the invention
Hollow Porous HAP microballoon scanning electron microscope (SEM) photo of Fig. 1
Fig. 2 CdS (10wt.%)/hollow Porous HAP microballoon composite material X-ray powder diffraction (XRD) diagram
Fig. 3 CdS (10wt.%)/hollow Porous HAP microballoon composite material scanning electron microscope (SEM) diagram
Fig. 4 CdS (10wt.%)/hollow Porous HAP microballoon composite material UV-Vis DRS map (UV-vis) figure
Show
Fig. 5 CdS (10wt.%)/hollow Porous HAP microballoon composite material is bent to absorption-photocatalysis performance of tetracycline
Line.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Used each raw material is commercial product in following embodiment.Polystyrolsulfon acid used in following embodiment
Sodium is bought in Guangdong Weng Jiang chemical reagent Co., Ltd (CAS NO.:25704-18-1)
The preparation of the hollow Porous HAP microballoon of embodiment 1:
Configure 50mL0.2M CaCl2Solution and 500mL10mg/mL PSS (kayexalate) solution, then by chlorine
Change calcium solution to be added in kayexalate solution, magnetic agitation sufficiently dissolves, then by 50mL 0.2M Na2CO3It is added dropwise
Above-mentioned solution, stirs 1h at room temperature, obtains white suspension, and obtained solid is used deionized water and dehydrated alcohol by centrifugation respectively
Three times, finally drying for 24 hours, obtains CaCO at 60 DEG C for cleaning3Microballoon presoma.
By the resulting CaCO of 0.2g3Microballoon presoma is scattered in 30mL deionized water, obtains CaCO3Microballoon presoma point
Dispersion liquid, by CaCO3The Na that microballoon forerunner dispersion liquid and concentration are 0.04M2HPO4Solution mixes (Ca:P=according to a certain percentage
1.67) it mixes, then with NaOH adjusting pH to 11, in the reaction kettle for stirring evenly and being transferred to polytetrafluoroethyllining lining, 120 DEG C
React 1h, be cooled to room temperature, be centrifuged, three times by obtained solid deionized water and washes of absolute alcohol, at 60 DEG C it is dry for 24 hours
To hollow Porous HAP microballoon.
Fig. 1 is the hollow Porous HAP microballoon scanning electron microscope (SEM) photograph (SEM) that present example 1 is prepared.It can be seen that made
Standby obtained HAP has hollow porous micro sphere structure, and Microsphere Size is about at 1.5 μm or so.
The preparation of 2 CdS of embodiment (10wt.%)/hollow Porous HAP microballoon composite material:
The hollow Porous HAP microballoon and 0.02g CdS that take 0.2g embodiment 1 to prepare are dissolved in the deionized water of 15mL respectively
In, ultrasound is uniformly mixed after 1 hour, is transferred in the reaction kettle of polytetrafluoroethyllining lining, 80 DEG C of progress hydro-thermal reaction 4h, cooling
To room temperature, centrifugation, by obtained solid deionized water and washes of absolute alcohol, at 60 DEG C it is dry for 24 hours, obtain CdS
(10wt.%)/hollow Porous HAP microballoon composite material.
Fig. 2 is that 2 preparation-obtained CdS (10wt.%) of present example/hollow Porous HAP microballoon composite material X is penetrated
Line powder diffraction (XRD) spectrogram.As seen from the figure, CdS (10wt.%)/hollow Porous HAP microballoon composite material XRD spectra is
The superposition of CdS characteristic absorption peak and HAP characteristic absorption peak, and there is no the appearance of other impurity peaks in composite material, show to close
At CdS (10wt.%)/hollow Porous HAP microballoon composite material purity it is higher.
Fig. 3 is that 2 preparation-obtained CdS (10wt.%) of present example/hollow Porous HAP microballoon composite material is swept
Retouch Electronic Speculum (SEM) diagram, it can be seen that little particle CdS is carried on the surface of hollow Porous HAP microballoon.
Fig. 4 is 2 preparation-obtained CdS (10wt.%) of present example/hollow Porous HAP microballoon composite material purple
Outside-visible diffusing reflection spectrum (UV-Vis DRS) figure, it can be seen that the composite material has superior Uv and visible light to absorb
Performance, can be used as photochemical catalyst come using.
3 absorption of embodiment-photocatalysis performance experiment:
Weigh the Fourth Ring that 0.05g CdS (10wt.%)/hollow Porous HAP microballoon composite material is placed in 100mL, 50mg/L
In plain (TC) solution, dark reaction 40min is to reach adsorption-desorption balance；Use the luxuriant and rich with fragrance Lay 300WXe xenon lamp of pool for light source, simulation is too
Sunlight irradiation, illumination at interval of 5min take the sample of 4mL to be centrifuged, supernatant are placed in cuvette after starting, and utilize
Shimadzu UV-2550 ultraviolet specrophotometer measures the absorption value of tetracycline, using C/C0Evaluate degradation rate, wherein C is illumination
The concentration of the tetracycline of sample after a certain period of time, C0For the concentration of the initial tetracycline of sample.
Fig. 5 is 3 preparation-obtained CdS (10wt.%) of present example/hollow Porous HAP microballoon composite material to four
Absorption-photocatalysis performance curve of ring element, the experimental results showed that it has photocatalytic degradation tetracycline very quickly and efficiently
Performance, the tetracycline removal rate for being 50mg/L to initial concentration in 30min is 90.2%, reaches simple, effective, economical, fast
The effect of the removal tetracycline wastewater of speed, can be applied to environment protection field.
Claims (10)
1. a kind of preparation method of the hollow Porous HAP microballoon composite material of CdS/ characterized by comprising
Step 1: by CaCl2Solution is added in kayexalate solution, and Na is added dropwise in stirring2CO3Solution stirs to get
White suspension, centrifugation, uses deionized water and washes of absolute alcohol for obtained solid respectively, dry, obtains CaCO3Microballoon forerunner
Body；
Step 2: preparing CaCO3Microballoon forerunner's dispersion liquid, by CaCO3Microballoon forerunner dispersion liquid and Na2HPO4Solution mixing, is used
It is 10.5-11.5 that NaOH, which adjusts pH, is reacted, is cooled to room temperature at 110-130 DEG C, is centrifuged, with deionized water and anhydrous second
Alcohol cleaning, it is dry, obtain hollow Porous HAP microballoon；
Step 3: being mixed after taking CdS and hollow Porous HAP microballoon to be dissolved in deionized water respectively, carry out hydro-thermal reaction, be cooled to room
Temperature, centrifugation is dry by obtained solid, obtains the hollow Porous HAP microballoon composite material of CdS/.
2. the preparation method of the hollow Porous HAP microballoon composite material of CdS/ as described in claim 1, which is characterized in that described
CaCl2The concentration of solution is 0.15M-0.25M.
3. the preparation method of the hollow Porous HAP microballoon composite material of CdS/ as described in claim 1, which is characterized in that described
Kayexalate solution concentration be 5mg/mL-15mg/mL.
4. the preparation method of the hollow Porous HAP microballoon composite material of CdS/ as described in claim 1, which is characterized in that described
Na2CO3The concentration of solution is 0.15M-0.25M.
5. the preparation method of the hollow Porous HAP microballoon composite material of CdS/ as described in claim 1, which is characterized in that described
CaCO3The solid content of microballoon forerunner's dispersion liquid is 5g/L-10g/L.
6. the preparation method of the hollow Porous HAP microballoon composite material of CdS/ as described in claim 1, which is characterized in that described
CaCO3And Na2HPO4Molar ratio be 1:0.55-0.65.
7. the preparation method of the hollow Porous HAP microballoon composite material of CdS/ as described in claim 1, which is characterized in that described
CdS and hollow Porous HAP microballoon weight ratio be 1:9.5-10.5.
8. the preparation method of the hollow Porous HAP microballoon composite material of CdS/ as described in claim 1, which is characterized in that described
Step 3 in hydro-thermal reaction temperature be 75-85 DEG C.
9. the hollow Porous HAP microballoon composite material of CdS/ prepared by preparation method of any of claims 1-8.
10. the application method of the hollow Porous HAP microballoon composite material of CdS/ as claimed in claim 9 characterized by comprising
The hollow Porous HAP microballoon composite material of CdS/ as claimed in claim 9 is placed in tetracycline, dark reaction reaches suction
Attached-desorption equilibrium, illumination degrade to tetracycline.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111514853A (en) * | 2020-04-30 | 2020-08-11 | 合肥学院 | Preparation method of calcium carbonate-waste coal-based activated carbon composite adsorbent |
| CN111672453A (en) * | 2020-06-12 | 2020-09-18 | 兰州大学 | High-value resource utilization method for pig bones |
| CN112125290A (en) * | 2020-09-15 | 2020-12-25 | 上海摩漾生物科技有限公司 | Calcium-phosphorus microsphere material containing defect sites and preparation and application thereof |
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| CN108786889A (en) * | 2018-06-21 | 2018-11-13 | 上海电力学院 | A kind of preparation method of the composite material of efficient absorption-photocatalytic degradation antibiotic |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111514853A (en) * | 2020-04-30 | 2020-08-11 | 合肥学院 | Preparation method of calcium carbonate-waste coal-based activated carbon composite adsorbent |
| CN111514853B (en) * | 2020-04-30 | 2022-08-26 | 合肥学院 | Preparation method of calcium carbonate-waste coal-based activated carbon composite adsorbent |
| CN111672453A (en) * | 2020-06-12 | 2020-09-18 | 兰州大学 | High-value resource utilization method for pig bones |
| CN111672453B (en) * | 2020-06-12 | 2022-05-06 | 兰州大学 | High-value resource utilization method for pig bones |
| CN112125290A (en) * | 2020-09-15 | 2020-12-25 | 上海摩漾生物科技有限公司 | Calcium-phosphorus microsphere material containing defect sites and preparation and application thereof |
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