CN105964275A - Microwave-assistant one-step synthesis method of CuS/CdIn2S4/ZnIn2S4 composite photocatalyst - Google Patents
Microwave-assistant one-step synthesis method of CuS/CdIn2S4/ZnIn2S4 composite photocatalyst Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000005855 radiation Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 15
- 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 abstract description 12
- 229940012189 methyl orange Drugs 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical compound [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 abstract description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000006303 photolysis reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production 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
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J27/045—Platinum group metals
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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Abstract
The invention discloses a microwave-assistant one-step synthesis method of a CuS/CdIn2S4/ZnIn2S4 composite photocatalyst and belongs to the technical field of a chemical industry. The method comprises mixing Zn(NO3)3. 6H2O, In(NO3)3. 4.5H2O, Cd(NO3)2. 4H2O, Cu(NO3)2. 3H2O and C2H5NS according to a mass ratio, putting the mixture into deionized water, carrying out uniform stirring, carrying out microwave radiation through a microwave reactor, repeatedly washing the product through deionized water and anhydrous ethanol and carrying out drying to obtain the CuS/CdIn2S4/ZnIn2S4 composite photocatalyst. Tests on surface morphology, a microstructure and photocatalytic activity prove that the product performances of organic pollutant methyl orange degradation and photocatalytically splitting of water into hydrogen are greatly improved. The microwave-assistant one-step synthesis method has the characteristics of short reaction time, uniform products and simple and practical production processes and has stable and reliable sample and volume production performances.
Description
Technical field
The present invention relates to a kind of CuS/CdIn2S4/ZnIn2S4The microwave-assisted one-step method for synthesizing of composite photo-catalyst, belongs to
In chemical industry technical field.
Background technology
Since Fujishima and Honda professor in 1972 finds to utilize TiO2Electrode can decompose under ultraviolet light irradiates
Since water generates hydrogen and oxygen, photocatalysis technology just causes the extensive concern of various countries scientist.But, the most most
Photocatalyst is merely able to only be accounted for the ultraviolet light of 3% ~ 5% in sunlight and excites, it is impossible to effectively utilize in sunlight most
Visible ray, so preparation has the research of visible light-responded high-efficiency photocatalysis material at photocatalysis degradation organic contaminant methyl
Orange and photolysis water hydrogen aspect then seem the most meaningful.
Summary of the invention
In order to solve the problems referred to above, it is an object of the invention to provide a kind of CuS/CdIn2S4/ZnIn2S4Composite photocatalyst
The microwave-assisted one-step method for synthesizing of agent, on the one hand, due to ZnIn2S4、CdIn2S4All there is narrower energy gap with CuS,
This can be effectively improved the composite absorption in visible region, to reach higher sunlight utilization rate.On the other hand,
ZnIn2S4With CdIn2S4With the compound flyway adding composite light induced electron of CuS, many ways of this light induced electron
Footpath migrates the recombination rate inherently reducing photo-generate electron-hole pair, improves the light-catalyzed reaction efficiency of composite.Adopt
With Zn (NO3)3·6H2O、In(NO3)3·4.5H2O、Cd(NO3)2·4H2O、Cu(NO3)2·3H2O、C2H5Five kinds of chemical reagent of NS
Raw material is put in deionized water by the mixing of quality proportioning and is stirred, and after being reacted by microwave reactor microwave radiation, then passes through
After deionized water and dehydrated alcohol cyclic washing respectively, then obtain end product CuS/CdIn through drying2S4/ZnIn2S4Compound
Photocatalyst.Production process brief and practical, properties of product are reliable and stable, have the response of relatively high visible.
The technical solution adopted for the present invention to solve the technical problems is: CuS/CdIn2S4/ZnIn2S4Composite photo-catalyst
Microwave-assisted one-step method for synthesizing, weigh Zn (NO3)3·6H2O, quality is 0.134 ± 0.001g, In (NO3)3·4.5H2O,
Quality is 0.382 ± 0.002g, Cd (NO3)2·4H2O, quality is 0.015 ± 0.001g, Cu (NO3)2·3H2O, quality is
0.001 ± 0.0002g and C2H5NS, quality is 0.225 ± 0.002g.20+ is put in above-mentioned five kinds of chemical reagent raw materials mixing
In 2mL deionized water, after being sufficiently stirred for 20+2min, pour in 100 mL teflon-lined microwave reactors, set
Microwave hydrothermal reaction temperature is 160 ± 2 DEG C, and the response time is 1.5+0.05h.After microwave radiation reaction terminates, the palm fibre that will generate
Cyclic washing 4-5 time respectively of color precipitate deionized water and dehydrated alcohol.Precipitate is put into drying baker, sets and dry temperature
Spending 60 ± 2 DEG C ,+0.1h, took out and obtained end product CuS/CdIn drying time 122S4/ZnIn2S4Composite photo-catalyst.
The invention has the beneficial effects as follows: use microwave-assisted one-step synthesis method to have the CuS/ of relatively high visible response
CdIn2S4/ZnIn2S4Composite photo-catalyst.Composite is by heterogeneous ZnIn2S4, Emission in Cubic CdIn2S4Form with hexagonal phase CuS,
And CdIn2S4Introducing with CuS improves the photocatalyst absorption in visible region.CuS/CdIn2S4/ZnIn2S4Maintain relatively
Good flower ball-shaped structure, has bigger specific surface area.Compared with P25, composite photo-catalyst is under simulation daylight and visible ray
Organic pollution methyl orange is had preferable light degradation effect.During it addition, Pt is as promoter, composite catalyst exists
Na2S-Na2SO3Having higher hydrogen-producing speed in solution and under the irradiation of visible ray, this is due to CdIn2S4With the introducing of CuS,
Expand the scope that composite is visible light-responded, add the flyway of light induced electron, it is suppressed that CuS/CdIn simultaneously2S4/
ZnIn2S4Photo-generate electron-hole is to being combined, thus improves its photocatalytic activity.Meanwhile, microwave-assisted one-step synthesis side is used
Method, has feature, sample and the batch production performances such as uniform, the production process brief and practical of product that the response time is short, generate steady
Fixed reliable.
Accompanying drawing explanation
The present invention will be further described with detailed description of the invention below in conjunction with the accompanying drawings.
Fig. 1 is CuS/CdIn2S4/ZnIn2S4One of composite photo-catalyst surface topography is schemed.
Fig. 2 is CuS/CdIn2S4/ZnIn2S4Two figures of composite photo-catalyst surface topography.
Fig. 3 is CuS/CdIn2S4/ZnIn2S4One of composite photo-catalyst microstructure is schemed.
Fig. 4 is CuS/CdIn2S4/ZnIn2S4Two figures of composite photo-catalyst microstructure.
Fig. 5 is CuS/CdIn2S4/ZnIn2S4One of HRTEM photo of composite photo-catalyst.
Fig. 6 is CuS/CdIn2S4/ZnIn2S4The two of the HRTEM photo of composite photo-catalyst.
Fig. 7 is direct light degradation, P25, ZnIn2S4、CdIn2S4/ZnIn2S4And CuS/CdIn2S4/ZnIn2S4Simulation daylight
Catalytic degradation methyl orange reaction rate figure.
Fig. 8 is direct light degradation, P25, ZnIn2S4、CdIn2S4/ZnIn2S4And CuS/CdIn2S4/ZnIn2S4Visible ray is urged
Change degraded methyl orange reaction rate figure.
Fig. 9 is direct light degradation, P25, ZnIn2S4、CdIn2S4/ZnIn2S4And CuS/CdIn2S4/ZnIn2S4Visible ray
Catalytic degradation methyl orange kinetic results figure.
Figure 10 is P25, ZnIn2S4、CdIn2S4/ZnIn2S4And CuS/CdIn2S4/ZnIn2S4At Na2Photocatalytic water in S solution
Hydrogen production rate figure.
Figure 11 is 0.2% wt Pt promoter loaded Cu S/CdIn2S4/ZnIn2S4At Na2S-Na2SO3Photodissociation in solution
Water hydrogen manufacturing lab diagram.
Figure 12 is 0.2% wt Pt promoter loaded Cu S/CdIn2S4/ZnIn2S4With Na2S-Na2SO3As sacrifice agent,
The catalyst stability result figure of photolysis water hydrogen under the radiation of visible light more than 420 nm.
Detailed description of the invention
CuS/CdIn2S4/ZnIn2S4The microwave-assisted one-step method for synthesizing of composite photo-catalyst, weighs and is purchased from east, Tianjin
Zn (the NO of the huge chemical reagent factory in beautiful district 99.0%3)3·6H2O, quality is 0.1339g, is purchased from the chemistry examination of Shanghai City traditional Chinese medicines group
In (the NO of agent company limited 99.5%3)3·4.5H2O, quality is 0.3819 g, it is limited to be purchased from Tianjin Ke Miou chemical reagent
Cd (the NO of public 99.0%3)2·4H2O, quality is 0.0154g, is purchased from the Cu of Tianjin Tian Li chemical reagent company limited 99.5%
(NO3)2·3H2O, quality is 0.001g and is purchased from the C of Tianjin Kermel Chemical Reagent Co., Ltd. 99.0%2H5NS, quality is
0.225 4g.Above-mentioned five kinds of chemical reagent raw materials mixing is put in 20mL deionized water, after being sufficiently stirred for 20min, pours 100 into
In mL teflon-lined microwave reactor, select the MDS-8G type microwave of Xinyi Microwave Chemistry Tech Co., Ltd.
Reactor, sets microwave hydrothermal reaction temperature as 160 DEG C, and the response time is 1.5 h.After microwave radiation reaction terminates, will generate
Brown precipitate deionized water and dehydrated alcohol respectively cyclic washing 4 times.Drying baker is put in precipitate filter only, sets and dry
Dry temperature 60 C, drying time, 12h, took out that to obtain end product be CuS/CdIn2S4/ZnIn2S4Composite photo-catalyst.
CuS/CdIn2S4/ZnIn2S4The structure of composite photo-catalyst and performance measurement:
One, surface topography and microstructure
CuS/CdIn2S4/ZnIn2S4Surface topography and the Micro-Structure Analysis result of sample are shown in Fig. 16.Can be clear by Fig. 1, Fig. 2
Observing to Chu, sample presents the petal chondritic of more rule, and the diameter of spheroid is about 600 nm, has between spheroid
There is good dispersibility.The TEM result of Fig. 3, Fig. 4 shows simultaneously, and the microstructure of sample is mainly by irregular block brilliant
The rhabdolith of body and length 100-200 nm is uniformly piled up and is formed, and the surface of bulk crystals and long rhabdolith is all distributed
The nano-particle of a large amount of diameter ~ 5 nm.Fig. 5, Fig. 6 are sample CuS/CdIn2S4/ZnIn2S4HRTEM photo, its illustration for choosing
Determine fast Fourier transform (FFT) image in region.
Two, photocatalysis performance measures
Commercially available P25, simple substance ZnIn2S4, double matter CdIn2S4/ZnIn2S4And CuS/CdIn2S4/ZnIn2S4Photocatalytic activity carry out
The photocatalysis experiment of degradable organic pollutant methyl orange and photolysis water hydrogen.
1, degradable organic pollutant methyl orange is shown in that Fig. 7, Fig. 8 show, CuS/CdIn2S4/ZnIn2S4Composite is in simulation
Under daylight and visible ray, the degraded to methyl orange all presents the highest photocatalytic activity, exceeds well over commercially available P25.It addition, it is different
Sample on degraded methyl orange speed impact as shown in Figure 9.According to experimental data, according to formula-ln (Ct/C0)=kt+b calculates, wherein, and CtFor dyestuff at concentration (the mg L in t moment-1), C0It is dyestuff initial concentration (mg L-1), k is
Speed constant (min-1), b is intercept.As seen from Figure 9 ,-ln (Ct/C0) the most linear with response time t,
Pseudo-first order reaction kinetics is followed in the degraded of this explanation methyl orange.It is computed, direct light degradation, P25, ZnIn2S4、
CdIn2S4/ZnIn2S4And CuS/CdIn2S4/ZnIn2S4The apparent reaction rate constant of Photocatalytic Activity for Degradation methyl orange divide
It is not 5.67 × 10-5、4.95×10-4、5.34×10-3、6.20×10-3With 8.96 × 10-3 min-1。
2, photolysis water hydrogen P25, ZnIn2S4、CdIn2S4/ZnIn2S4And CuS/CdIn2S4/ZnIn2S4Different samples exist
Na2In S solution, hydrogen-producing speed result is as shown in Figure 10.Result shows, CuS/CdIn2S4/ZnIn2S4Composite has best
Hydrogen production potential, its hydrogen-producing speed is 15 times of P25.Its illustration shows, CuS/CdIn2S4/ZnIn2S4At Na2S-Na2SO3Solution
In hydrogen-producing speed be higher than Na2S or Na2SO3Single solution, it was demonstrated that Na2S and Na2SO3Photocatalytic process exist collaborative
Effect.In order to improve the hydrogen production potential of photocatalyst further, Pt is supported on sample as promoter by photoreduction met hod
CuS/CdIn2S4/ZnIn2S4Surface, result is as indicated at 11.After 0.2% wt Pt load, CuS/CdIn2S4/ZnIn2S4Product
Hydrogen speed reaches 358.4 μm ol h-1·g-1, improve 6 times than before load.After using 420 nm cut-off filter plates, Pt loads
CuS/CdIn2S4/ZnIn2S4Hydrogen-producing speed still can reach 233.9 μm ol h-1·g-1, show sample have higher can
See photoresponse.In order to investigate Pt loaded Cu S/CdIn2S4/ZnIn2S4Photocatalysis stability, with Na2S-Na2SO3As sacrifice
Agent, persistently produces hydrogen 24 h under the wavelength radiation of visible light more than 420 nm.Figure 12 shows, sample still keeps after producing hydrogen 24 h
Certain photocatalysis stability, and the not bigger change of generation of the crystalline structure before and after light-catalyzed reaction, its illustration shows instead
The XRD spectra of sample before and after should.
Claims (2)
1. a CuS/CdIn2S4/ZnIn2S4The microwave-assisted one-step method for synthesizing of composite photo-catalyst, is characterized in that: weigh Zn
(NO3)3·6H2O, quality is 0.134 ± 0.001g, In (NO3)3·4.5H2O, quality is 0.382 ± 0.002g, Cd (NO3)2·
4H2O, quality is 0.015 ± 0.001g, Cu (NO3)2·3H2O, quality is 0.001 ± 0.0002g and C2H5NS, quality is
0.225 ±0.002g；Above-mentioned five kinds of chemical reagent raw materials mixing is put in 20+2mL deionized water, is sufficiently stirred for 20+
After 2min, pour in 100 mL teflon-lined microwave reactors, set microwave hydrothermal reaction temperature as 160 ± 2 DEG C,
Response time is 1.5+0.05h；After microwave radiation reaction terminates, by the brown precipitate deionized water generated and anhydrous second
Alcohol cyclic washing 4-5 time respectively；Precipitate is put into drying baker, sets and dry temperature 60 ± 2 DEG C, drying time 12+
0.1h, takes out and obtains end product CuS/CdIn2S4/ZnIn2S4Composite photo-catalyst.
CuS/CdIn the most according to claim 12S4/ZnIn2S4The microwave-assisted one-step method for synthesizing of composite photo-catalyst,
It is characterized in that: Zn (NO3)3·6H2O, quality is 0.1339g, In (NO3)3·4.5H2O, quality is 0.3819 g, Cd
(NO3)2·4H2O, quality is 0.0154g, Cu (NO3)2·3H2O, quality is 0.001g and C2H5NS, quality is 0.225 4g；Mixed
Conjunction is put in 20mL deionized water, after being sufficiently stirred for 20min, pours in 100 mL microwave reactors, and reaction temperature is 160 DEG C,
Response time is 1.5 h；After reaction terminates, by product deionized water and dehydrated alcohol cyclic washing 4 times respectively；Will precipitation
Drying baker is put in thing filter only, sets and dries temperature 60 C, drying time 12h.
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| CN106745199A (en) * | 2016-12-30 | 2017-05-31 | 东华大学 | A kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template |
| CN106964369A (en) * | 2017-03-21 | 2017-07-21 | 温州大学 | A kind of preparation method and application of heterojunction photocatalyst |
| CN109012699A (en) * | 2018-09-03 | 2018-12-18 | 辽宁大学 | Symmetrical anti-Z-type photochemical catalyst and its preparation method and application |
| CN109821562A (en) * | 2019-04-09 | 2019-05-31 | 淮北师范大学 | A kind of MoP-Zn3In2S6The preparation method of composite nano materials |
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| CN106745199A (en) * | 2016-12-30 | 2017-05-31 | 东华大学 | A kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template |
| CN106745199B (en) * | 2016-12-30 | 2018-10-23 | 东华大学 | A kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template |
| CN106964369A (en) * | 2017-03-21 | 2017-07-21 | 温州大学 | A kind of preparation method and application of heterojunction photocatalyst |
| CN106964369B (en) * | 2017-03-21 | 2019-09-24 | 温州大学 | A kind of preparation method and application of heterojunction photocatalyst |
| CN109012699A (en) * | 2018-09-03 | 2018-12-18 | 辽宁大学 | Symmetrical anti-Z-type photochemical catalyst and its preparation method and application |
| CN109847781A (en) * | 2019-01-30 | 2019-06-07 | 太原理工大学 | A kind of CdIn2S4/g-C3N4The preparation method and applications of composite photo-catalyst |
| CN109821562A (en) * | 2019-04-09 | 2019-05-31 | 淮北师范大学 | A kind of MoP-Zn3In2S6The preparation method of composite nano materials |
| CN109821562B (en) * | 2019-04-09 | 2021-08-24 | 淮北师范大学 | MoP-Zn3In2S6Preparation method of composite nano material |
| CN114130407A (en) * | 2021-12-17 | 2022-03-04 | 永高股份有限公司 | Cu2S/CuInS2/ZnIn2S4Preparation method and application of composite photocatalyst |
| CN115845877A (en) * | 2022-10-20 | 2023-03-28 | 厦门稀土材料研究所 | Photocatalyst, preparation method and application |
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