CN109772325A - Cu2+Doped hollow-structure microsphere Fenton catalyst and preparation method and application thereof - Google Patents
Cu2+Doped hollow-structure microsphere Fenton catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000004005 microsphere Substances 0.000 title abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 20
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 claims abstract description 19
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 abstract description 8
- 239000007790 solid phase Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 11
- 239000010949 copper Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 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 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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Abstract
The invention relates to Cu2+The preparation method of the doped hollow structure microsphere Fenton catalyst comprises the following steps: s1, mixing SiO2@TiO2Dispersing the core-shell structure microspheres in NaOH solution for heating reaction, cooling, washing and drying to obtain Na2Ti3O7Microspheres with hollow structures; s2, mixing Na2Ti3O7The hollow structure microspheres are dispersed in Cu-containing microspheres2+Stirring in the aqueous solution of (1), centrifuging, washing with water, and drying to obtain Cu2+The doped hollow structure microsphere Fenton catalyst. The method is simple to operate, the prepared hollow-structure microsphere solid-phase Fenton catalyst is wide in application range, and the Cu is2+And (5) stably doping.
Description
Technical field
The present invention relates to the synthesis field of solid phase fenton catalyst more particularly to a kind of Cu2+The hollow structure microballoon of doping
Fenton catalyst and its preparation method and application.
Background technique
The world today, with the propulsion of economic fast development and industrial process, water pollution problems is got worse.In recent years
Fenton oxidation water treatment technology is comparatively fast developed, and attacks organic contamination using the hydroxyl radical free radical (OH) of strong oxidizing property
Organic molecule is gradually degraded as small-molecule substance, such as carbon dioxide, water and inorganic salts by object, and realizing efficiently removal has
The purpose of machine pollutant.
Fenton catalysis oxidation water treatment technology key is the research and development of efficient stable catalyst, is catalyzed reaction in traditional Fenton
In, catalyst is free metal ion, although catalytic efficiency is higher, exists and is difficult to recycle, metal ion hydrogen easy to form
Oxide sludge causes secondary pollution problems.To overcome disadvantage of the conventional homogeneous fenton catalyst in practical water process, grind
Metal ion immobilization is formed metal oxide, metal simple-substance, the solid-phase catalysts such as metal ion mixing by the persons of studying carefully, then and
H2O2Heterogeneous Fenton-like system is constituted, the recycling and reusing of catalyst is realized.
Current domestic and international developed heterogeneous fenton catalyst is mostly iron-based solid-phase catalyst, such as ferriferous oxide and metal
Composite oxides, iron ion or ferriferous oxide are carried on molecular sieve etc., and there are living under the conditions of the usual soda acid of water body (pH > 6)
The low problem of property.Some results of study show copper have with redox characteristic as iron phase, can also be catalyzed H2O2It decomposes and generates
OH, and there is the broader pH scope of application, there is preferable catalytic performance under neutral temperate condition.
Said from the appearance structure of catalyst material, hollow structure material compared with block materials have lower density and
Bigger specific surface area, internal " huge " space are even more to provide wide platform, energy for material filling, transport and reaction
It is enough to increase the active site and improve mass transfer velocity that catalysis is reacted, promote the catalytic performance of material.
In conclusion being opened to improve the scope of application of Fenton oxidation reaction and the treatment effect to organic pollutants
Sending out novel has the copper-based catalysts of hollow structure, such as Cu2+The hollow structure catalyst of doping, is of great significance, but how
Realize Cu2+The regulation of stabilization doping and doping content be still current difficult point, be rarely reported.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, a kind of easy to operate, catalysis is provided and is applicable in
The wide Cu of range2+Stablize the hollow structure microballoon fenton catalyst and its preparation method and application of doping.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of Cu2+The preparation method of the hollow structure microballoon fenton catalyst of doping, comprising the following steps:
S1, by SiO2@TiO2Core-shell structure microballoon, which is scattered in NaOH solution, carries out heating reaction, through cooling, washing, drying
Afterwards, Na is obtained2Ti3O7Hollow structure microballoon；
S2, by Na2Ti3O7Hollow structure microballoon is scattered in containing Cu2+Aqueous solution in stir, through centrifugation, washing, drying, obtain
To Cu2+The hollow structure microballoon fenton catalyst of doping.
As further improvement to above-mentioned technical proposal:
In the step S2, the Na2Ti3O7The concentration of hollow structure microballoon is the g/L of 8 g/L~12, described to contain Cu2+'s
Aqueous solution and Na2Ti3O7The molar ratio of hollow structure microballoon is 1: 0.06~10；The time of the stirring is the h of 2 h~10.
It is described to contain Cu2+Aqueous solution be Cu (NO3)2Solution or CuCl2Solution.
In the step S1, the SiO2@TiO2Concentration after core-shell structure microballoon is dispersed in NaOH solution is 8 g/L
~14 g/L, the concentration of the NaOH solution are the mol/L of 2 mol/L~5；The temperature of heating reaction is 120 DEG C~160 DEG C, when
Between be the h of 8 h~16.
Preferably, the NaOH and SiO2@TiO2The molar ratio of core-shell structure microballoon is greater than 2.
The SiO2@TiO2The preparation step of core-shell structure microballoon is as follows:
By SiO2Microballoon, which is added into dehydrated alcohol, to be uniformly mixed, and ammonium hydroxide is added and stirs evenly, adds titanium source and is hydrolyzed instead
It answers, is centrifuged, obtains SiO2@TiO2Core-shell structure microballoon.
The SiO2Mass concentration of the microballoon in dehydrated alcohol is the g/L of 1.0 g/L~1.5；The temperature of the stirring
It is 40 DEG C~50 DEG C, the time is 20~60 min；The time of the hydrolysis is the h of 8 h~24；The titanium source is metatitanic acid four
Butyl ester.
The SiO2The preparation step of microballoon is as follows: silicon source being divided into silicon source I and silicon source II, silicon is added dropwise into alkaline solution
Source I, is stirred to react, and adds silicon source II and continues to react, and centrifugation obtains SiO2Microballoon, the volume of the silicon source I and silicon source II
Than being 1: 7~10.
The alkaline solution is the mixed solution of deionized water, isopropanol and ammonium hydroxide, and the silicon source is ethyl orthosilicate, institute
The volume ratio for stating ethyl orthosilicate, deionized water, isopropanol and ammonium hydroxide is 1: 4.2: 11.3: 2.3.
The inventive concept total as one, the present invention also provides a kind of Cu2+The hollow structure microballoon fenton catalyst of doping,
It is prepared by aforementioned preparation process.
The inventive concept total as one, the present invention also provides a kind of Cu that aforementioned preparation process is prepared2+Doping
The application in degradation of organic dyes field in water of hollow structure microballoon fenton catalyst.
Compared with the prior art, the advantages of the present invention are as follows:
The present invention has hollow structure Na using hard template method preparation2Ti3O7Hollow structure microballoon, passes through Cu2+With Na2Ti3O7In
Na+It swaps to obtain Cu2+The microballoon of the hollow structure of doping, Cu2+It is acted on by chemical bonding and stable is present in material
In, this method is simply controllable, and the pattern of material is held essentially constant after ion exchange, still has hollow structure, wherein Cu2+It mixes
Miscellaneous content can be by changing Cu2+With Na2Ti3O7Molar ratio regulated and controled.
Cu of the invention2+The hollow structure microballoon fenton catalyst of doping handles organic contamination in water in neutral conditions
Excellent property is presented when object, overcomes iron-based solid phase fenton catalyst under the conditions of the usual soda acid of water body (pH > 6)
The low problem of activity, applied widely, hollow structure can increase the active site of catalysis reaction and improve mass transfer velocity, to mentioning
Material catalytic performance is risen to be of great significance.
Detailed description of the invention
Fig. 1 is SiO in the embodiment of the present invention 12The scanning electron microscope (SEM) photograph of microballoon.
Fig. 2 is SiO in the embodiment of the present invention 12@TiO2The scanning electron microscope (SEM) photograph of core-shell structure microballoon.
Fig. 3 is Na in the embodiment of the present invention 12Ti3O7The scanning electron microscope (SEM) photograph of hollow structure microballoon.
Fig. 4 is Cu in the embodiment of the present invention 12+The scanning electron microscope (SEM) photograph of doped hollow structure microspheres.
Fig. 5 be ultraviolet-visible absorption spectroscopy in the embodiment of the present invention 1 in organic dyestuff methyl orange solution degradation process and
The corresponding dye solution color of different time points.
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment, in following embodiment
Used material and instrument are commercially available.
Embodiment 1
A kind of Cu of the invention2+The preparation method of the hollow structure microballoon fenton catalyst of doping, specifically includes the following steps:
(1) hard template SiO2The preparation of microballoon: 23.5 mL water, 63.3 mL isopropanols and 13 mL ammonium hydroxide are mixed and are added 250
ML conical flask is simultaneously stirred at room temperature, and 0.6 mL ethyl orthosilicate (TEOS) is added dropwise, and is stirred to react 5 mL after 0.5 h
TEOS solution is added drop-wise in reaction system, the reaction was continued 2 h.Product is collected by centrifugation.
Fig. 1 is SiO in the present embodiment2The scanning electron microscope (SEM) photograph of microballoon, as can be seen from Figure SiO2The diameter of microballoon 300~
Uniform in size between 400 nm, surface is smooth.
(2) SiO2@TiO2The preparation of core-shell structure microballoon: by 0.1 g SiO2Microballoon is added in 80 mL dehydrated alcohols,
20 min of ultrasound, are added 0.4 mL ammonium hydroxide, and 0.8 mL butyl titanate (TBOT) is added drop-wise to by 45 DEG C of 20 min of stirring in water bath
In mixed solution, the reaction was continued 8 h.Product is collected by centrifugation.Obtain SiO of the size between 500~600 nm2@TiO2Nucleocapsid knot
Structure microballoon.
Fig. 2 a, 2b are the present embodiment SiO respectively2@TiO2The scanning nuclear microprobe figure of core-shell structure microballoon, can from Fig. 2
Find out, relative to SiO2Microballoon, SiO2@TiO2Core-shell structure microsphere diameter becomes larger, and size has bright between 500~600 nm
Aobvious core-shell structure.
(3) Na2Ti3O7The preparation of hollow structure microballoon: by 0.1 g SiO2@TiO2Core-shell structure microballoon evenly spreads to 8
ML NaOH concentration is to be placed in 140 DEG C of baking ovens and react 12 hours in 2 mol/L solution.It is centrifugated and produces after being cooled to room temperature
Object is washed 5 times, is dried to obtain Na2Ti3O7Hollow structure microballoon.The purpose of washing is to remove remaining OH-, avoid to subsequent reality
It tests and impacts.In the present embodiment, NaOH in addition to SiO2Reaction, and also while and TiO2Reaction obtains Na2Ti3O7。
Fig. 3 a, Fig. 3 b are Na in the present embodiment respectively2Ti3O7The scanning nuclear microprobe figure of hollow structure microballoon, from Fig. 3
In can be seen that, Na2Ti3O7Microballoon has apparent hollow structure, relative to SiO2@TiO2Core-shell structure microballoon, Na2Ti3O7Microballoon
Surface becomes coarse by smooth, Na2Ti3O7Microstructure, be conducive to next step Cu2+It is compound with material.
(4) Cu2+The preparation of the hollow structure microballoon fenton catalyst of doping: 0.1 g Na is taken2Ti3O7Hollow structure microballoon,
It is added to 10 mL1 mol/L CuCl2In aqueous solution, stir 2 hours.Product is collected by centrifugation, washes 5 times, is dried to obtain Cu2+It mixes
Miscellaneous hollow structure microballoon fenton catalyst.
In the prior art, metal ion is that TiO is carried on by way of physical absorption2The surface of nanometer cup catalyst,
It is sticked to the surface of clothes similar to dust, is easier to be desorbed.And in the present invention, Cu2+Be by way of ion exchange, with
Na2Ti3O7In Na+Exchange, similar on the clothes that decorative pattern is embroidered on, there are the effect of chemical bonding, Cu2+Stable presence
In the surface and inside of material, and Cu2+Doping content can be by changing Cu2+With Na2Ti3O7Molar ratio regulated and controled.
Fig. 4 is the present embodiment Cu2+The scanning electron microscope (SEM) photograph of the hollow structure microballoon fenton catalyst of doping.It can from Fig. 4
Out, Cu2+The hollow structure microballoon fenton catalyst and Na of doping2Ti3O7Hollow structure microballoon pattern is similar, illustrates to hand in ion
After changing, the spherical morphology and hollow structure of microballoon do not have significant change.
By Cu in the present embodiment2+Degradation of the hollow structure microballoon fenton catalyst of doping for organic dyestuff in water, tool
Steps are as follows for body:
(1) by 20 mg Cu2+It is the organic of 10 mg/L that the hollow structure microballoon fenton catalyst of doping, which is added to 40 mL concentration,
In methyl orange aqueous solution, the H that 0.8 mL concentration is 30%wt is added after stirring 0.5 h2O2。
(2) H is added2O2At the time of be zero point, the concentration of the moment dyestuff is as reaction initial concentration, by 0 min, 20
Min, 40 min, 60 min, the sampling of 90 min time intervals remove solid sample with 0.45 μm of membrane filtration, using it is ultraviolet can
See that absorption spectrum determines the concentration of residual dye in solution.It takes pictures under identical light condition, obtains dye solution color
Situation of change.
Fig. 5 is that ultraviolet-visible absorption spectroscopy in organic dyestuff methyl orange solution degradation process and different time points are corresponding
Solution colour.It can be seen that from Fig. 5 a, characteristic absorption peaks of the methyl orange solution at 463 nm are with the extension of reaction time
It is substantially reduced, can be seen that in Fig. 5 b, the color of solution obviously shoals.
Embodiment 2
The present embodiment is roughly the same with embodiment 1, the difference is that:
Step (4) Cu2+The preparation of doped hollow structure microspheres fenton catalyst: 0.1 g Na is taken2Ti3O7Hollow structure microballoon,
It is added to 10 mL, 0.05 mol/L CuCl2In aqueous solution, stir 2 hours.Product is collected by centrifugation, washes 5 times, is dried to obtain
Cu2+The hollow structure microballoon fenton catalyst of doping.
Embodiment 3
The present embodiment is roughly the same with embodiment 1, the difference is that:
Step (4) Cu2+The preparation of doped hollow structure microspheres fenton catalyst: 0.1 g Na is taken2Ti3O7Hollow structure microballoon,
It is added to 10 mL, 0.01 mol/L CuCl2In aqueous solution, stir 2 hours.Product is collected by centrifugation, washes 5 times, is dried to obtain
Cu2+The hollow structure microballoon fenton catalyst of doping.
Although the present invention has been disclosed as a preferred embodiment, however, it is not intended to limit the invention.It is any to be familiar with ability
The technical staff in domain, without deviating from the scope of the technical scheme of the present invention, all using the technology contents pair of the disclosure above
Technical solution of the present invention makes many possible changes and modifications or equivalent example modified to equivalent change.Therefore, all
Without departing from the content of technical solution of the present invention, according to the present invention technical spirit any simple modification made to the above embodiment,
Equivalent variations and modification, all shall fall within the protection scope of the technical scheme of the invention.
Claims (10)
1. a kind of Cu2+The preparation method of the hollow structure microballoon fenton catalyst of doping, it is characterised in that: the following steps are included:
S1, by SiO2@TiO2Core-shell structure microballoon, which is scattered in NaOH solution, carries out heating reaction, after cooling, washing, drying,
Obtain Na2Ti3O7Hollow structure microballoon；
S2, by Na2Ti3O7Hollow structure microballoon is scattered in containing Cu2+Aqueous solution in stir, through centrifugation, washing, drying, obtain
Cu2+The hollow structure microballoon fenton catalyst of doping.
2. preparation method according to claim 1, it is characterised in that: in the step S2, the Na2Ti3O7Hollow structure
The concentration of microballoon is the g/L of 8 g/L~12, described to contain Cu2+Aqueous solution and Na2Ti3O7The molar ratio of hollow structure microballoon is 1
: 0.06~10；The time of the stirring is the h of 2 h~10.
3. preparation method according to claim 2, it is characterised in that: described to contain Cu2+Aqueous solution be Cu (NO3)2Solution
Or CuCl2Solution.
4. preparation method according to claim 2, it is characterised in that: in the step S1, the SiO2@TiO2Nucleocapsid knot
Concentration after structure microballoon is dispersed in NaOH solution is the g/L of 8 g/L~14, and the concentration of the NaOH solution is 2 mol/L~5
mol/L；The temperature of heating reaction is 120 DEG C~160 DEG C, and the time is the h of 8 h~16.
5. preparation method according to any one of claim 1 to 4, it is characterised in that: the SiO2@TiO2Core-shell structure
The preparation step of microballoon is as follows:
By SiO2Microballoon, which is added into dehydrated alcohol, to be uniformly mixed, and ammonium hydroxide is added and stirs evenly, adds titanium source and is hydrolyzed instead
It answers, is centrifuged, obtains SiO2@TiO2Core-shell structure microballoon.
6. preparation method according to claim 5, it is characterised in that: the SiO2Quality of the microballoon in dehydrated alcohol
Concentration is the g/L of 1.0 g/L~1.5；The temperature of the stirring is 40 DEG C~50 DEG C, and the time is 20~60 min, the hydrolysis
The time of reaction is the h of 8 h~24；The titanium source is butyl titanate.
7. preparation method according to claim 6, it is characterised in that: the SiO2The preparation step of microballoon is as follows: by silicon source
It is divided into silicon source I and silicon source II, silicon source I is added dropwise into alkaline solution, is stirred to react, adds silicon source II and continue to react, from
The heart obtains SiO2The volume ratio of microballoon, the silicon source I and silicon source II is 1: 7~10.
8. preparation method according to claim 7, it is characterised in that: the alkaline solution be deionized water, isopropanol and
The mixed solution of ammonium hydroxide, the silicon source be ethyl orthosilicate, the ethyl orthosilicate, deionized water, isopropanol and ammonium hydroxide body
Product is than being 1: 4.2: 11.3: 2.3.
9. a kind of Cu2+The hollow structure microballoon fenton catalyst of doping, it is characterised in that: prepared by any one of claim 1 to 8
Method is prepared.
10. a kind of according to claim 1 to the Cu that any one of 8 preparation methods are prepared2+The hollow structure microballoon Fenton of doping
The catalyst application in degradation of organic dyes field in water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583138A (en) * | 2022-03-18 | 2022-06-03 | 杭州怡莱珂科技有限公司 | Sodium ion carrier-carbon composite powder, self-isolation electrode and preparation method |
| RU2818559C1 (en) * | 2023-12-06 | 2024-05-02 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method of producing copper-doped sodium trititanate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941736A (en) * | 2010-10-21 | 2011-01-12 | 北京科技大学 | Preparation method of echinoid titanium dioxide microspheres in single/double layer cavity structure |
| WO2017062197A1 (en) * | 2015-10-08 | 2017-04-13 | Nanotek Instruments, Inc. | Continuous process for producing electrodes and alkali metal batteries having ultra-high energy densities |
| CN106745205A (en) * | 2016-11-23 | 2017-05-31 | 吕梁学院 | A kind of synthetic method of bar-shaped Mg2+ doping SrTiO3 |
| CN107335418A (en) * | 2017-06-20 | 2017-11-10 | 浙江工业大学 | Novel hollow TiO2Preparation method of nano cup catalyst and application of nano cup catalyst after metal loading |
| CN108993570A (en) * | 2018-07-30 | 2018-12-14 | 南京工业大学 | Preparation method and application of copper-doped graphite-phase carbon nitride composite material |
-
2019
- 2019-03-01 CN CN201910155666.7A patent/CN109772325A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941736A (en) * | 2010-10-21 | 2011-01-12 | 北京科技大学 | Preparation method of echinoid titanium dioxide microspheres in single/double layer cavity structure |
| CN101941736B (en) * | 2010-10-21 | 2012-07-25 | 北京科技大学 | Preparation method of single/double layer cavity structure and echinoid titanium dioxide microspheres |
| WO2017062197A1 (en) * | 2015-10-08 | 2017-04-13 | Nanotek Instruments, Inc. | Continuous process for producing electrodes and alkali metal batteries having ultra-high energy densities |
| CN106745205A (en) * | 2016-11-23 | 2017-05-31 | 吕梁学院 | A kind of synthetic method of bar-shaped Mg2+ doping SrTiO3 |
| CN107335418A (en) * | 2017-06-20 | 2017-11-10 | 浙江工业大学 | Novel hollow TiO2Preparation method of nano cup catalyst and application of nano cup catalyst after metal loading |
| CN108993570A (en) * | 2018-07-30 | 2018-12-14 | 南京工业大学 | Preparation method and application of copper-doped graphite-phase carbon nitride composite material |
Non-Patent Citations (4)
| Title |
|---|
| GUNDEBOINA,R ET AL.: ""Synthesis of Cu2+ and Ag+ doped Na2Ti3O7 by a facile ion-exchange method as visible-light-driven photocatalysts"", 《CERAMICS INTERNATIONAL》 * |
| PEDRO FARDIM: "《纤维化学和技术 化学制浆 1 第7卷 中文版》", 30 June 2017, 北京：中国轻工出版社 * |
| ZHANG YE ET AL.: ""Synthesis of hierarchical hollow sodium titanate microspheres and their application for selective removal of organic dyes"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 周毅: ""层状三钛酸盐光催化剂的掺杂与插层改性研究"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583138A (en) * | 2022-03-18 | 2022-06-03 | 杭州怡莱珂科技有限公司 | Sodium ion carrier-carbon composite powder, self-isolation electrode and preparation method |
| RU2818559C1 (en) * | 2023-12-06 | 2024-05-02 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method of producing copper-doped sodium trititanate |
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