CN107737597A - A kind of titanium doped indium sulfide zinc flower-like microsphere and its preparation method and application - Google Patents
A kind of titanium doped indium sulfide zinc flower-like microsphere and its preparation method and application Download PDFInfo
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- CN107737597A CN107737597A CN201710942895.4A CN201710942895A CN107737597A CN 107737597 A CN107737597 A CN 107737597A CN 201710942895 A CN201710942895 A CN 201710942895A CN 107737597 A CN107737597 A CN 107737597A
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- microsphere
- indium sulfide
- sulfide zinc
- titanium
- zinc flower
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- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000004005 microsphere Substances 0.000 title claims abstract description 50
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 37
- 239000010936 titanium Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 150000003608 titanium Chemical class 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical group [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001802 infusion Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 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
-
- B01J35/39—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of titanium doped indium sulfide zinc flower-like microsphere and its preparation method and application, the preparation method of titanium doped indium sulfide zinc flower-like microsphere, methods described are as follows：Indium sulfide zinc flower-like microsphere is placed in titanium salt solution, 0.25~3h of heating stirring at 30~150 DEG C；Then mixed liquor is centrifuged, the titanium doped indium sulfide zinc flower-like microsphere is produced after removing a layer washing of precipitate, drying；The mass ratio of the indium sulfide zinc flower-like microsphere and titanium salt is 100：0.01~10.Indium sulfide zinc flower-like microsphere is placed in titanium salt solution by the present invention, is carried out titanium ion doping to indium sulfide zinc flower-like microsphere by infusion process, is further improved the photocatalytic activity of indium sulfide zinc.The titanium doped indium sulfide zinc flower-like microsphere that the present invention is prepared has stable pattern, larger specific surface area, and higher Photocatalyzed Hydrogen Production activity, available for photocatalysis Decomposition aquatic products hydrogen.
Description
Technical field
The present invention relates to catalysis technical field, in particular it relates to a kind of titanium doped indium sulfide zinc flower-like microsphere and its preparation
Methods and applications.
Background technology
With the mankind science and technology development and living standard growth, energy problem be increasingly becoming human society face it is main
Problem.In addition to energy crisis caused by the growth year by year of energy-output ratio, greenhouse effects caused by combustion of fossil fuel are also urgently
It is to be solved.For the continuity and stably of human kind sustainable development, it is extremely urgent to develop a kind of new energy of clean environment firendly.The sun
Energy, wind energy, Hydrogen Energy, nuclear energy, and biological energy source etc. are the object of researchers developmental research in the last few years, wherein Hydrogen Energy
Environment-protecting and non-poisonous, combustion heat value is high, and storable form is varied, is the energy that generally acknowledged future society most has development potentiality.
At present industrially using hydrogen manufacturing the methods of Coal Gasification hydrogen manufacturing, heavy oil and gas water steam catalytic reforming hydrogen manufacturing, still
Not only efficiency is low for these methods, and also needs to expend more energy, does not reach the effect of environment-protecting clean.Water is on ground
Store and enrich on ball, the method that hydrogen or oxygen are prepared using decomposition water is even more ideal, also more economical feasible.
1972, Fujishima and Honda delivered one on TiO2Can be with ultraviolet light as optoelectronic pole
Decomposition water produces the article of hydrogen, has pulled open the prelude of photocatalysis New Times since then, photocatalysis technology initially enters regarding for people
Open country simultaneously causes extensive concern and research.Photocatalysis technology only needs sunshine to provide energy in mechanism, without external energy
Device, it is possible to by water decomposition be hydrogen and oxygen.ZnIn2S4It is a kind of novel photocatalyst occurred in the last few years, forbidden band is wide
2.4eV is spent, has to visible ray good corresponding, there is very high hydrogen-producing speed.But sulfide has light in light-catalyzed reaction
The phenomenon of corrosion, and then influence the speed that photochemical catalyst light decomposes aquatic products hydrogen.In order to improve this defect, need further to vulcanization
Indium zinc is modified processing.
Therefore, need badly and research and develop high indium sulfide zinc flower-like microsphere of a kind of catalysis hydrogen-producing speed and preparation method thereof.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of system of titanium doped indium sulfide zinc flower-like microsphere
Preparation Method, the titanium doped indium sulfide zinc flower-like microsphere that preparation method provided by the invention is prepared have stable pattern, compared with
Big specific surface area, and higher Photocatalyzed Hydrogen Production activity.
The titanium doped indium sulfide zinc flower-like microsphere being prepared another object of the present invention is to provide above-mentioned preparation method.
Another object of the present invention is to provide a kind of above-mentioned titanium doped indium sulfide zinc flower-like microsphere as photochemical catalyst to exist
Application in Photocatalyzed Hydrogen Production.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of titanium doped indium sulfide zinc flower-like microsphere, methods described are as follows：
Indium sulfide zinc flower-like microsphere is placed in titanium salt solution, 0.25~3h of heating stirring at 30~150 DEG C；Then will mixing
Liquid is centrifuged, and the titanium doped indium sulfide zinc flower-like microsphere is produced after removing a layer washing of precipitate, drying；The indium sulfide zinc is flower-shaped micro-
The mass ratio of ball and titanium salt is 100：0.01~10.
Indium sulfide zinc flower-like microsphere is placed in titanium salt solution by the present invention, and indium sulfide zinc flower-like microsphere is entered by infusion process
Row titanium ion adulterates, and further improves the photocatalytic activity of indium sulfide zinc.The titanium doped indium sulfide zinc flower that the present invention is prepared
Shape microballoon has stable pattern, larger specific surface area, and higher Photocatalyzed Hydrogen Production activity, available for photocatalysis Decomposition
Aquatic products hydrogen.
Preferably, heating-up temperature is 80 DEG C, mixing time 1h.
Preferably, the mass ratio of the indium sulfide zinc flower-like microsphere and titanium salt is 100：0.2.
Preferably, the titanium salt is titanium sulfate.
Preferably, the concentration of the titanium salt is 0.05~10g/L.
Preferably, the indium sulfide zinc flower-like microsphere is prepared by hydro-thermal method.
Specifically, using zinc chloride or zinc nitrate as zinc source, using inidum chloride as indium source, thioacetamide is sulphur source, by them
It is dissolved according to certain ratio in deionized water, the indium sulfide zinc that above-mentioned flower-like structure is prepared by hydro-thermal method is flower-shaped micro-
Ball.
Preferably, the mol ratio of the zinc source, indium source and sulphur source is 1:2:5.The condition of hydro-thermal reaction is at 80~150 DEG C
Insulation naturally cools to room temperature after 8~12 hours.
Preferably, the drying is that the lower sediment after washing is placed in air dry oven into 60 DEG C to dry 5~10 hours
Until dry.
The present invention protects the titanium doped indium sulfide zinc flower-like microsphere that above-mentioned preparation method is prepared and its as light simultaneously
Application of the catalyst in Photocatalyzed Hydrogen Production.
Compared with prior art, the present invention has the advantages that：
There is very big specific surface area in the indium sulfide zinc flower-like microsphere that the present invention is prepared by hydro-thermal method, in light-catalyzed reaction
There are more avtive spots；After carrying out titanium ion doping to it, the phenomenon of indium sulfide zinc photoetch is improved, is further increased
The ability of the Photocatalyzed Hydrogen Production of indium sulfide zinc flower-like microsphere.Preparation method whole preparation process provided by the invention is simply controllable,
Required experimental facilities is simple, workable, and there is very high commercial introduction to be worth.
Brief description of the drawings
Fig. 1 be prepare flower-shaped indium sulfide zinc and it is titanium doped after indium sulfide zinc SEM figure；
Fig. 2 is the XRD of the different titanium doped amounts prepared；
Fig. 3 is the mapping photos of the titanium doped indium sulfide zinc composite photo-catalyst prepared；
Fig. 4 is the production hydrogen design sketch of different samples；
Fig. 5 is the EDS figures that sample is made in comparative example 1.
Embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the reagent of the invention used, method and apparatus is the art conventional reagent, methods
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are purchased in market.
The present invention carries out titanium ion doping by infusion process to indium sulfide zinc flower-like microsphere, to improve its fast light corrosive nature
It is used for photocatalysis aquatic products hydrogen with photocatalytic activity and as photochemical catalyst.
Embodiment 1
1mmol zinc chloride are weighed, 2mmol inidum chlorides, 5mmol thioacetamides, adds in 80mL deionized waters and stirs, are turned
Autoclave is put into after moving in polytetrafluoroethyltank tank, 80 DEG C of hydro-thermal reactions 12 hours in air dry oven；Hydro-thermal terminates
Afterwards, supernatant liquor is outwelled, takes the orange-yellow precipitation in bottom, drying 8 is small in 60 DEG C of air dry ovens after deionized water washing three times
When, obtain the indium sulfide zinc flower-like microsphere of flower-like structure.
The titanium sulfate solution that 10mL concentration is 0.1g/L is taken, adds 1g indium sulfide zinc powders, 30 DEG C of sides are stirred on warm table
Side is mixed to heat 3 hours；Mixed liquor is centrifuged, 60 DEG C of drying in air dry oven after lower sediment washing three times is taken, obtains
To 0.1% titanium doped indium sulfide zinc flower-like microsphere composite photo-catalyst.
Embodiment 2
1mmol zinc chloride are weighed, 2mmol inidum chlorides, 5mmol thioacetamides, adds in 80mL deionized waters and stirs, are turned
Autoclave is put into after moving in polytetrafluoroethyltank tank, 80 DEG C of hydro-thermal reactions 10 hours in air dry oven；Hydro-thermal terminates
Afterwards, supernatant liquor is outwelled, takes the orange-yellow precipitation in bottom, drying 8 is small in 60 DEG C of air dry ovens after deionized water washing three times
When, obtain the indium sulfide zinc flower-like microsphere of flower-like structure.
The titanium sulfate solution that 10mL concentration is 0.15g/L is taken, adds 1g indium sulfide zinc powders, 80 DEG C of sides are stirred on warm table
Side is mixed to heat 1 hour；Mixed liquor is centrifuged, 60 DEG C of drying in air dry oven after lower sediment washing three times is taken, obtains
To 0.15% titanium doped indium sulfide zinc flower-like microsphere composite photo-catalyst.
Embodiment 3
1mmol zinc nitrates are weighed, 2mmol inidum chlorides, 5mmol thioacetamides, adds in 80mL deionized waters and stirs, are turned
Autoclave is put into after moving in polytetrafluoroethyltank tank, 80 DEG C of hydro-thermal reactions 12 hours in air dry oven；Hydro-thermal terminates
Afterwards, supernatant liquor is outwelled, takes the orange-yellow precipitation in bottom, drying 10 is small in 60 DEG C of air dry ovens after deionized water washing three times
When, obtain the indium sulfide zinc flower-like microsphere of flower-like structure.
The titanium sulfate solution that 10mL concentration is 0.2g/L is taken, adds 1g indium sulfide zinc powders, 150 DEG C of sides are stirred on warm table
Side is mixed to heat 0.25 hour；Mixed liquor is centrifuged, takes 60 DEG C of drying in air dry oven after lower sediment washing three times,
Obtain 0.2% titanium doped indium sulfide zinc flower-like microsphere composite photo-catalyst.
Embodiment 4
1mmol zinc nitrates are weighed, 2mmol inidum chlorides, 5mmol thioacetamides, adds in 80mL deionized waters and stirs, are turned
Autoclave is put into after moving in polytetrafluoroethyltank tank, 80 DEG C of hydro-thermal reactions 12 hours in air dry oven；Hydro-thermal terminates
Afterwards, supernatant liquor is outwelled, takes the orange-yellow precipitation in bottom, drying 10 is small in 60 DEG C of air dry ovens after deionized water washing three times
When, obtain the indium sulfide zinc flower-like microsphere of flower-like structure.
The titanium sulfate solution that 10mL concentration is 0.25g/L is taken, adds 1g indium sulfide zinc powders, 80 DEG C of sides are stirred on warm table
Side is mixed to heat 1 hour；Mixed liquor is centrifuged, 60 DEG C of drying in air dry oven after lower sediment washing three times is taken, obtains
To 0.25% titanium doped indium sulfide zinc flower-like microsphere composite photo-catalyst.
Comparative example 1
1mmol zinc nitrates are weighed, 2mmol inidum chlorides, 5mmol thioacetamides, adds in 80mL deionized waters and stirs, are turned
Autoclave is put into after moving in polytetrafluoroethyltank tank, 80 DEG C of hydro-thermal reactions 12 hours in air dry oven；Hydro-thermal terminates
Afterwards, supernatant liquor is outwelled, takes the orange-yellow precipitation in bottom, drying 10 is small in 60 DEG C of air dry ovens after deionized water washing three times
When, obtain the indium sulfide zinc flower-like microsphere of flower-like structure.
The titanium sulfate solution that 10mL concentration is 0.5g/L is taken, 1g indium sulfide zinc powders is added, is impregnated 1 hour at 20 DEG C；
Mixed liquor is centrifuged, takes 60 DEG C of drying in air dry oven after lower sediment washing three times, obtained sample passes through EDS
Test understands and loads upper titanium ion not successfully（See accompanying drawing 5）.
In the various embodiments described above and comparative example, tested using commercially available solar energy photocatalytic production hydrogen test system,
The sodium sulfite that 200ml concentration is 0.2mol/L and the Na that concentration is 1mol/L are added in system2S mixed solution is done
Sacrifice agent, add appropriate chlorine paper tinsel acid and do co-catalyst, the concentration of chlorine paper tinsel acid be 0.5mg/L in system, adds prepared by 0.2g
Photochemical catalyst rear enclosed system, is vacuumized, and is reached and is carried out illumination to it with xenon lamp simulated visible light after certain vacuum degree, passes through gas
The concentration of hydrogen is produced in chromatography detection different periods system, draws the decomposition aquatic products hydrogen of different samples under visible light illumination
Volume, and then calculate its Photocatalyzed Hydrogen Production speed.
Fig. 1 be the embodiment of the present invention 1 prepare flower-shaped indium sulfide zinc and it is titanium doped after indium sulfide zinc SEM figure, its
Middle figure a）It is the simple indium sulfide zinc flower-like microsphere prepared in embodiment 1, schemes b）Be carried out in embodiment 1 it is titanium doped after vulcanization
Indium zinc flower-like microsphere.It can be seen that it is carried out by infusion process it is titanium doped after, the flower-like structure of indium sulfide zinc does not occur
Change, therefore do not influence its appearance structure and specific surface area.
Fig. 2 is the XRD of different titanium doped amounts prepared by embodiment 1~4, it can be seen that 21.6,27.7,30.4,
The characteristic peak of 47.2,52.4,56.3 ° of appearance corresponds to hexagonal crystal phase indium sulfide zinc respectively（006）,（102）,（104）,（110）,
（116）With（203）Crystal face.Obvious change does not occur for crystalline structure after carrying out titanium doped to indium sulfide zinc, is because mixing
Miscellaneous amount is very small, and the crystalline structure of indium sulfide zinc is not had an impact.
Fig. 3 is the mapping photos of the titanium doped indium sulfide zinc composite photo-catalyst prepared in embodiment 1, it can be seen that
Can be by titanium ion uniform load on the surface of indium sulfide zinc flower-like microsphere by infusion process.But due in embodiment 1 titanium from
The load capacity of son is relatively low, is not reaching to EDS limit of identification, so in figure b）In EDS results on there is not the spy of titanium
Levy peak.
Fig. 4 is the production hydrogen design sketch that embodiment 1~4 prepares different samples, it can be seen that single because of its larger specific surface area
Pure indium sulfide zinc flower-like microsphere has the ability of good photocatalysis Decomposition aquatic products hydrogen under visible light, and Photocatalyzed Hydrogen Production speed can
Reach 2335.5 μm of olh-1·g-1.After carrying out titanium ion doping to it, Photocatalyzed Hydrogen Production speed has obtained further raising,
It can reach 3685.2 μm of olh-1·g-1, be 1.57 times of simple indium sulfide zinc flower-like microsphere Photocatalyzed Hydrogen Production speed it
It is high.When the doping of titanium further improves, hydrogen-producing speed has declined again, therefore can draw titanium doped most ratio of greater inequality relatively
Example is 0.2%.
Fig. 5 is the EDS figures that sample is made in comparative example 1, and impregnation is carried out when temperature is too low, can not be successfully by titanium
It is supported on the surface of indium sulfide zinc flower-like microsphere.
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of titanium doped indium sulfide zinc flower-like microsphere, it is characterised in that methods described is as follows：
Indium sulfide zinc flower-like microsphere is placed in titanium salt solution, 0.25~3h of heating stirring at 30~150 DEG C；Then will mixing
Liquid is centrifuged, and the titanium doped indium sulfide zinc flower-like microsphere is produced after removing a layer washing of precipitate, drying；The indium sulfide zinc is flower-shaped micro-
The mass ratio of ball and titanium salt is 100：0.01~10.
2. preparation method according to claim 1, it is characterised in that heating-up temperature is 80 DEG C, mixing time 1h.
3. preparation method according to claim 1, it is characterised in that the mass ratio of the indium sulfide zinc flower-like microsphere and titanium salt
For 100：0.2.
4. preparation method according to claim 1, it is characterised in that the titanium salt is titanium sulfate and/or titanium chloride.
5. preparation method according to claim 1, it is characterised in that the concentration of the titanium salt is 0.05~10g/L.
6. preparation method according to claim 1, it is characterised in that the indium sulfide zinc flower-like microsphere is prepared by hydro-thermal method
Obtain.
7. preparation method according to claim 6, it is characterised in that for preparing zinc source, the indium of indium sulfide zinc flower-like microsphere
The mol ratio of source and sulphur source is 1:2:5, the condition of hydro-thermal reaction is to be naturally cooled to after being incubated 8~12 hours at 80~150 DEG C
Room temperature.
8. the titanium doped indium sulfide zinc flower-like microsphere that any preparation method of claim 1~7 is prepared.
9. application of the titanium doped indium sulfide zinc flower-like microsphere as photochemical catalyst in Photocatalyzed Hydrogen Production described in claim 8.
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