CN105536758A - Preparation method of floatable type recoverable photocatalyst based on single-crystal titanium dioxide - Google Patents
Preparation method of floatable type recoverable photocatalyst based on single-crystal titanium dioxide Download PDFInfo
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- CN105536758A CN105536758A CN201610108764.1A CN201610108764A CN105536758A CN 105536758 A CN105536758 A CN 105536758A CN 201610108764 A CN201610108764 A CN 201610108764A CN 105536758 A CN105536758 A CN 105536758A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 55
- 239000013078 crystal Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title abstract description 3
- 239000010881 fly ash Substances 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007667 floating Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000010954 inorganic particle Substances 0.000 abstract description 2
- 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 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 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
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a floatable type recoverable photocatalyst based on single-crystal titanium dioxide. Lightweight inorganic particle fly ash is taken as a carrier, and single-crystal titanium dioxide is synthesized on the surface of the carrier. Due to the special morphology of single-crystal titanium dioxide, single-crystal titanium dioxide has a larger specific surface area when growing on the surface of the carrier, so that the catalyst can be sufficiently contacted with organic matters, and the catalytic activity is higher. The preparation method of the catalyst is simple, adopts mild conditions and is easy to control; the density of the lightweight carrier is far smaller than that of water, the catalyst can float on the water surface, is not required to be stirred during use, is not affected by water turbidity, is easy to recover after being used and can be repeatedly used.
Description
Technical field
The present invention relates to a kind of preparation method of photochemical catalyst, specifically a kind of preparation method of the recyclable photochemical catalyst of float type of based single crystal titanium dioxide, belongs to photocatalysis technology field.
Background technology
Titanium dioxide has nontoxic, inexpensive, that catalytic activity is high advantage, is the photochemical catalyst be most widely used.Compared with ordinary titanium dioxide, single crystal titanium dioxide is owing to possessing direct electron channel, and electronics and hole good separating effect, thus have higher catalytic activity.Although titanium dioxide has good catalytic activity, when it uses under field conditions (factors), be subject to larger restriction: (1) owing to lacking Keep agitation condition, titanium dioxide free settling and reduce its catalytic effect; (2) catalytic effect affects greatly by water body light transmittance; (3) catalyst recovery difficulty, easily causes waste and secondary pollution.Be the effective means solved the problem in carrier surface by titanium dichloride load, carrier comprises glass fibre, high polymer, inorganic light weight carrier etc.The preparation of current loaded photocatalyst adopts the mode of dip-coating at carrier surface load commercial powder titanium dioxide substantially, although technique is simple, but its shortcoming also clearly: powdered titanium dioxide forms absorption at carrier surface, and between catalyst and carrier, adhesion is more weak, and stability is not high; Absorption gained catalyst surface area is less, and catalytic action is a greater impact.In addition, dip-coating utilizes nanoscale commodity titanium dioxide to mix with carrier, and utilize the nanoparticle surface large feature of energy and carrier to be formed and adsorb, this mode is not suitable for the load of single crystal titanium dioxide.
Summary of the invention
For problems of the prior art, the invention provides a kind of preparation method of the recyclable photochemical catalyst of float type of based single crystal titanium dioxide.The present invention adopts light-weight inorganic particle flyash to be carrier, at carrier surface synthetic single crystal titanium dioxide, due to the special appearance of single crystal titanium dioxide, it has larger specific area when carrier surface grows, catalyst more fully can be contacted with organic matter, and catalytic activity is higher.
The present invention is by the following technical solutions:
A preparation method for the recyclable photochemical catalyst of float type of based single crystal titanium dioxide, it is characterized in that, it comprises the following steps:
1) surface modification of flyash carrier: fully mixed with 1% VTES (KH171) ethanolic solution by flyash particle, leaves standstill, by floating flyash separate particles;
2) Spawn preparation: by the isolated flyash particle transfer of step 1) institute in alcohol solution, slowly adding butyl titanate to its concentration is 1%, abundant stirring, leave standstill, the flyash particle of separating floating, 80 DEG C of oven dry, then 500 DEG C of roastings 2 hours, obtain the flyash particle of carried titanium dioxide crystal seed;
3) preparation of single crystal titanium dioxide: butyl titanate or titanium tetrachloride and concentrated hydrochloric acid are mixed with solution by 1:1 volume ratio, are stirred well to system transparent, proceed to autoclave, add step 2) gained flyash particle, 200 DEG C of reactions 12 hours;
4) be separated end-product: after reaction terminates, separating obtained flyash particle, surface clean is also dried and obtains the single crystal titanium dioxide catalyst that end product is carried on flyash surface.
Described step 2) in alcohol solution be that ethanol and water are made according to volume ratio 49:1.
Described single crystal titanium dioxide is rutile-type mono-crystalline structures.
In described step 3), the flyash particle addition of carried titanium dioxide crystal seed is be 1/3 of amount of solution in autoclave according to volume ratio.
In described step 4), bake out temperature is 100 DEG C.
The invention provides a kind of appendix of preparing in the method for the single crystal titanium dioxide on inorganic carrier surface.Single crystal titanium dioxide possesses direct electron channel, effectively can prevent the compound in electronics and hole, has higher light utilization ratio; Due to the special appearance of single crystal titanium dioxide, it has larger specific area when carrier surface grows, and catalyst more fully can be contacted with organic matter, and catalytic activity is higher.For improving single crystal titanium dioxide in the adhesive strength of carrier surface, the load of crystal seeds and the control preparing hydrothermal condition are keys of the present invention.
With the preparation of traditional photochemical catalyst compared with use, catalyst tool of the present invention has the following advantages:
(1) catalyst surface area prepared of the present invention is large, and institute's carried titanium dioxide is rutile-type mono-crystalline structures.Because single crystal titanium dioxide grows with stereoscopic-state on flyash surface, the specific area of catalyst can be significantly improved.After tested, specific surface area of catalyst (quality is catalyst and flyash gross mass) reaches 174.8m
2/ g.
(2) adopt the mode of surface modification at the preset titanium dioxide crystal seed in flyash surface in the preparation process of catalyst of the present invention, time prepared by hydro-thermal, titanium dioxide, along this seeded growth, solves because flyash structure is not mated with titanium dioxide lattice and causes synthesizing failed problem.Adopt the preset crystal seed of mode of surface modification, the adhesive strength of titanium dioxide crystallite at flyash particle surface can be improved, be beneficial to the synthesis of next step single crystal titanium dioxide.
(3) catalytic activity is high.Although prepared titanium dioxide is the rutile-type lower to ultraviolet light response, but because titanium dioxide is mono-crystalline structures, there is good electron-hole separating effect, there is larger specific area simultaneously, thus still have good catalytic activity, it is good to the catalytic degradation effect of organic pollutants.
(4) preparation method is simple, mild condition, is easy to control.Light carrier density is much smaller than water, and catalyst may float on the water surface, without the need to stirring during use, does not affect by water turbidity, uses rear recovery easy, can recycle.
Accompanying drawing explanation
Fig. 1 is the single crystal titanium dioxide shape appearance figure and the partial enlarged drawing that are carried on flyash surface.
Fig. 2 is the XRD result figure of prepared catalyst.
Fig. 3 is the high-resolution-ration transmission electric-lens resolution chart of rutile titanium dioxide mono-crystalline structures, a) is wherein electron diffraction analysis collection of illustrative plates; B) be partial enlarged drawing.
Fig. 4 is catalyst using state figure of the present invention.
Fig. 5 is the experimental result picture of catalyst degradation rhodamine B under uviol lamp and sunshine respectively.
Detailed description of the invention
Embodiment 1
This experimental procedure describes merely concrete preparation process, and the amount of single Kaolinite Preparation of Catalyst is relevant with autoclave volume.
The recyclable photochemical catalyst of float type of based single crystal titanium dioxide, its preparation method is as follows:
1) flyash particle is fully mixed with 1% VTES (KH171) ethanolic solution, leave standstill, by floating flyash separate particles;
2) by step 1) isolated flyash particle transfer in alcohol solution (volume ratio of ethanol and water is 49:1), slowly adding butyl titanate to its concentration is 1%, abundant stirring, leave standstill, the flyash particle of separating floating, 80 DEG C of oven dry, then 500 DEG C of roastings 2 hours, obtain the flyash particle of carried titanium dioxide crystal seed;
3) butyl titanate and concentrated hydrochloric acid are mixed with solution by 1:1 volume ratio, be stirred well to system transparent, proceed to autoclave, add step 2) gained flyash particle, flyash particle addition is be 1/3,200 DEG C of amount of solution in autoclave reactions 12 hours according to volume ratio;
4), after reaction terminates, separating obtained flyash particle, surface clean also dries and obtains at 80 DEG C the single crystal titanium dioxide catalyst that end product is carried on flyash surface.
Embodiment 2
This experimental procedure describes merely concrete preparation process, and the amount of single Kaolinite Preparation of Catalyst is relevant with autoclave volume.
The recyclable photochemical catalyst of float type of based single crystal titanium dioxide, its preparation method is as follows:
1) flyash particle is fully mixed with 1% VTES (KH171) ethanolic solution, leave standstill, by floating flyash separate particles;
2) by step 1) isolated flyash particle transfer in alcohol solution (volume ratio of ethanol and water is 49:1), slowly adding butyl titanate to its concentration is 1%, abundant stirring, leave standstill, the flyash particle of separating floating, 80 DEG C of oven dry, then 500 DEG C of roastings 2 hours, obtain the flyash particle of carried titanium dioxide crystal seed;
3) titanium tetrachloride and concentrated hydrochloric acid are mixed with solution by 1:1 volume ratio, be stirred well to system transparent, proceed to autoclave, add step 2) gained flyash particle, flyash particle addition is be 1/3,200 DEG C of amount of solution in autoclave reactions 12 hours according to volume ratio;
4), after reaction terminates, separating obtained flyash particle, surface clean also dries and obtains at 80 DEG C the single crystal titanium dioxide catalyst that end product is carried on flyash surface.
For further illustrating the design feature of institute of the present invention controlling catalyst, carry out various test to the catalyst obtained by the present invention and characterize, wherein ESEM collection of illustrative plates as shown in Figure 1.As can be seen from Figure 1 be covered with one-dimensional rod-like titanium dioxide at flyash particle surface, its diameter is about 100nm, length about 2 μm.Fig. 2 is the X-ray diffraction analysis result of prepared catalyst, as can be seen from Figure 2, although there is stronger flyash ambient interferences, still can observe obvious diffraction maximum at the crystal face such as (110), (101), (211), wherein based on (110) crystal face, the prepared titanium dioxide of display is rutile-type.Fig. 3 is the high-resolution-ration transmission electric-lens analysis result of prepared titanium dioxide, and illustration a is wherein its electron diffraction analysis collection of illustrative plates, and known prepared titanium dioxide is mono-crystalline structures; Illustration b is the high-resolution-ration transmission electric-lens partial enlarged drawing of prepared titanium dioxide, shows its interplanar distance and is about 0.25nm.
Application example
This application example is the experiment of laboratory room small-sized photocatalytic degradation.
Rhodamine B (RhB) solution that 50mL concentration is 5mg/L is added respectively in two 100mL beakers, transparent membrane (prevent moisture content from volatilizing and affect mensuration) is covered on beaker surface, the floating catalyst that 0.2g is prepared by embodiment 1 is respectively added in solution, respectively with ultraviolet light (power be 125W, fixed wave length be the high-pressure sodium lamp of 365nm) and sunshine (period noon in summer) for light source degraded RhB solution, experimental result is as shown in Figure 5.
As can be seen from accompanying drawing 5, prepared catalyst has good catalytic activity, especially under sunlight conditions during catalytic degradation RhB, 2.5h can reach the degradation rate of about 95%, significantly better than 125W fixed wave length uviol lamp, this is on the one hand relevant with intensity of illumination height at noon in summer, on the other hand also narrow with rutile titanium dioxide energy gap, can visible ray be utilized better relevant.Photochemical catalyst prepared by patent of the present invention has good response to sunshine, the use under natural conditions preferably.
Claims (5)
1. a preparation method for the recyclable photochemical catalyst of the float type of based single crystal titanium dioxide, it is characterized in that, it comprises the following steps:
1) surface modification of flyash carrier: fully mixed with 1% VTES ethanolic solution by flyash particle, leaves standstill, by floating flyash separate particles;
2) Spawn preparation: by the isolated flyash particle transfer of step 1) institute in alcohol solution, slowly adding butyl titanate to its concentration is 1%, abundant stirring, leave standstill, the flyash particle of separating floating, 80 DEG C of oven dry, then 500 DEG C of roastings 2 hours, obtain the flyash particle of carried titanium dioxide crystal seed;
3) preparation of single crystal titanium dioxide: butyl titanate or titanium tetrachloride and concentrated hydrochloric acid are mixed with solution by 1:1 volume ratio, are stirred well to system transparent, proceed to autoclave, add step 2) gained flyash particle, 200 DEG C of reactions 12 hours;
4) be separated end-product: after reaction terminates, separating obtained flyash particle, surface clean is also dried and obtains the single crystal titanium dioxide catalyst that end product is carried on flyash surface.
2. the preparation method of photochemical catalyst according to claim 1, is characterized in that, described step 2) in alcohol solution be that ethanol and water are made according to volume ratio 49:1.
3. the preparation method of photochemical catalyst according to claim 1, is characterized in that, described single crystal titanium dioxide is rutile-type mono-crystalline structures.
4. the preparation method of photochemical catalyst according to claim 1, is characterized in that, in described step 3), the flyash particle addition of carried titanium dioxide crystal seed is be 1/3 of amount of solution in autoclave according to volume ratio.
5. the preparation method of photochemical catalyst according to claim 1, is characterized in that, in described step 4), bake out temperature is 100 DEG C.
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| CN201610108764.1A CN105536758A (en) | 2016-02-26 | 2016-02-26 | Preparation method of floatable type recoverable photocatalyst based on single-crystal titanium dioxide |
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| CN201610108764.1A CN105536758A (en) | 2016-02-26 | 2016-02-26 | Preparation method of floatable type recoverable photocatalyst based on single-crystal titanium dioxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268939A (en) * | 2016-08-09 | 2017-01-04 | 长安大学 | A kind of supported ionic liquids carrier, preparation method and applications |
| CN107486203A (en) * | 2017-09-11 | 2017-12-19 | 浙江工商大学 | A kind of recyclable float type composite photocatalyst ball and its preparation method and application |
| CN110180496A (en) * | 2019-06-06 | 2019-08-30 | 济南大学 | Light-weight inorganic particle surface loads the preparation method of the reversible oil slick recovery catalyst of rodlike titanium dioxide array |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268939A (en) * | 2016-08-09 | 2017-01-04 | 长安大学 | A kind of supported ionic liquids carrier, preparation method and applications |
| CN106268939B (en) * | 2016-08-09 | 2018-12-28 | 长安大学 | A kind of supported ionic liquids carrier, preparation method and applications |
| CN107486203A (en) * | 2017-09-11 | 2017-12-19 | 浙江工商大学 | A kind of recyclable float type composite photocatalyst ball and its preparation method and application |
| CN107486203B (en) * | 2017-09-11 | 2019-12-24 | 浙江工商大学 | Recyclable floating type composite photocatalytic ball and preparation method and application thereof |
| CN110180496A (en) * | 2019-06-06 | 2019-08-30 | 济南大学 | Light-weight inorganic particle surface loads the preparation method of the reversible oil slick recovery catalyst of rodlike titanium dioxide array |
| CN110180496B (en) * | 2019-06-06 | 2022-01-25 | 济南大学 | Preparation method of reversible floating oil recovery agent with rod-shaped titanium dioxide array loaded on surface of light inorganic particle |
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