CN100446855C - Method for in-situ synthesizing and synchronized loading composite semiconductor light-catalyst ZnO and ZnS - Google Patents
Method for in-situ synthesizing and synchronized loading composite semiconductor light-catalyst ZnO and ZnS Download PDFInfo
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- CN100446855C CN100446855C CNB2007100091462A CN200710009146A CN100446855C CN 100446855 C CN100446855 C CN 100446855C CN B2007100091462 A CNB2007100091462 A CN B2007100091462A CN 200710009146 A CN200710009146 A CN 200710009146A CN 100446855 C CN100446855 C CN 100446855C
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Abstract
The invention is concerned with the original compound and the synchronization load method of the composite semiconductor photocatalyzer such as ZnO and ZnS, includes the pre-process of the Nafion film, the characteristic is: leads Zn2+ in the precessed Nafion film by ion exchange, immerges the Nafion film into the sodium sulfide liquid, takes out after react a period of time in the indoor temperature, gets ZnO and ZnS composite semiconductor photocatalyzer. The invention predigests the technics, is with better active stability, high using efficiency.
Description
Technical field
The present invention relates to the photocatalysis technology in the environmental improvement, the synthetic and synchronized loading method of the original position of a kind of specifically composite semiconductor light-catalyst ZnO and ZnS.
Background technology
Along with the development of photocatalysis technology, photochemical catalyst is obtaining increasingly extensive application aspect the environmental improvements such as air cleaning and wastewater treatment.Can't reclaim, be difficult to shortcomings such as separation, post processing complexity, operation operating cost height is difficult to use in practice owing to powder photocatalyst in use exists.Doing a lot of work aspect the immobilization of photochemical catalyst at this technical barrier Chinese scholars.People utilize powder sintering method, liquid phase deposition, sol-gel process, chemical vapour deposition technique, physical vaporous deposition, Molecular Adsorption method, magnetron sputtering method, the whole bag of tricks such as cathode electrodeposition method on carriers such as nickel sheet, aluminium flake, titanium sheet, copper sheet, stainless steel substrates, simple glass sheet, lucite, quartz glass plate, silicon chip, potsherd, active carbon, bead, foamed plastics, molecular sieve load various photochemical catalysts.But the photochemical catalyst of these support types exists not strong for load solid again, and the photochemical catalyst load capacity is very few, the loading process complexity, and deficiencies such as apparatus expensive have influenced their industrial applications.Particularly higher for photocatalytic activity, can more effectively promote of the load of light induced electron-hole to the composite photocatalyst of separation, difficulty is bigger, and application is more difficult.
Shangguan Wen Feng etc. have introduced a kind of nano compound photocatalyst for cleaning air and preparation method thereof at Chinese patent bulletin 1394674: photochemical catalyst is made up of carrier and nano particle or film, and wherein carrier is made up of spherical silica gel or granular colloidal silica or KSG or silochrom or Kiselgel A; The catalytic activity body adopts slurry dipping, gel-sol technology with TiO
2Nano particle or film are carried in carrier surface and the space, form the composite nano photochemical catalyst.Gu Hongchen etc. disclose a kind of preparation method of support type light catalytic purifying net piece in Chinese patent bulletin 1515352: adopt active carbon as adsorbent, efficient composite catalyst is as photochemical catalyst, tourmaline is as auxiliary material, with active carbon, composite photo-catalyst and tourmaline powder carry out the effectively compound multifunctional efficient photochemical catalyst for preparing by the physical mechanical mixed method, adopt water-based latex as adhesive then, the multifunctional efficient photochemical catalyst is mixed with the water-base cement emulsion, disperse, make stable suspension slurry, adopt spraying or dipping process that the catalyst cupport carrier is evenly covered catalyst coat at last, obtain support type light catalytic purifying net piece.These support type composite photo-catalysts more have practical value for powder photocatalyst, but it still can not solve the shortcoming of aforesaid general loadization.
Summary of the invention
The objective of the invention is to provide the synthetic and synchronized loading method of original position of a kind of composite semiconductor light-catalyst ZnO and ZnS, this method manufacturing process is simple, does not need cost and complex equipment; The synthesis condition gentleness can make the synthetic and load of composite semiconductor light-catalyst ZnO and ZnS carry out synchronously, finishes simultaneously; And the composite photo-catalyst ratio of synthetic load can be regulated easily.
Synthetic and the synchronized loading method of the original position of composite semiconductor light-catalyst ZnO of the present invention and ZnS comprises the preliminary treatment of Nafion film, it is characterized in that: by ion-exchange with Zn
2+Introduce in the good Nafion film of preliminary treatment, then the Nafion film is immersed in the sodium sulfide solution, room temperature reaction takes out after a period of time, forms ZnO and ZnS composite semiconductor light-catalyst.
Benefit of the present invention and superiority are: the present invention is by synthetic ZnO of original position in the Nafion film and ZnS composite semiconductor light-catalyst, finished simultaneously the pay(useful) load of photochemical catalyst again, simplify the synthetic load process of photochemical catalyst greatly, had industry to apply meaning.The composite semiconductor light-catalyst that utilizes the present invention to prepare can carry out light-catalyzed reaction efficiently, have good active stability, can carry out separating treatment easily in the liquid-phase reaction system, the photochemical catalyst power of regeneration is strong, recycling efficient height has very high practical value and application prospect.
Description of drawings:
Fig. 1 is X-ray diffraction (XRD) figure of the Nafion film of loading ZnO of the present invention and ZnS composite semiconductor; The synthetic processing time of curve a is that 30 minutes, synthetic processing time of curve b are that 60 minutes, synthetic processing time of curve c are that 90 minutes, synthetic processing time of curve d are 120 minutes among the figure.
Fig. 2 is that the Nafion film of loading ZnO of the present invention and ZnS composite semiconductor is as photochemical catalyst light degradation rhodamine B, curve a is the light degradation situation of blank film when not having load, the light degradation rhodamine B situation when curve b-e is loading ZnO and ZnS composite semiconductor light-catalyst.
The specific embodiment
Synthetic and the synchronized loading of composite semiconductor light-catalyst ZnO that the present invention proposes and the original position of ZnS is based in the use of the Nafion film that du pont company produces.The Nafion film has excellent light transmission, the mechanical strength height, and chemical stability and Heat stability is good are serving as the synthetic template of composite semiconductor light-catalyst and the effect of carrier in the present invention.
Ion-exchange Zn of the present invention
2+The raw material of solution is one or more in zinc nitrate, zinc sulfate or the zinc halide water-soluble zinc salt; Zn in the solution
2+Concentration＞0.2 mol; Ion-exchange time 〉=12 hour, the concentration of sodium sulfide solution＞0.5 mol; The room temperature reaction time is 5～300 minutes.
Concrete steps of the present invention are:
(1) Nafion film pre-treatment step is: the Nafion film is cut into suitable size and shape, soaking and stirring is 24 hours in 60 ℃ of red fuming nitric acid (RFNA)s, immerse mass fraction then successively and be to stir respectively in 60 ℃ of aqueous solution of nitric acid of 60%, 40% and 20% after 2 hours to clean repeatedly to being dipped to few 24 hours with deionized water again after water is neutrality and remove free nitric acid, change it into water white H by this processing with deionized water
+Type Nafion film is with described H
+Type Nafion film places 100 ℃ of vacuum drying chambers must test at least 3 hours with doing H
+Type Nafion film.
(2) H that preliminary treatment is good
+Type Nafion film immerses the Zn (NO with 14.87g
3)
26H
2Carry out ion-exchange in the solution that O and 100 ml deionized water are made into, exchange equilibrium takes out film with deionized water clean surface repeatedly after 24 hours, soaked 24 hours for 300 milliliters with deionized water again; Having exchanged Zn
2+The Nafion film immerse by 12g vulcanized sodium Na
2S9H
2In the solution that O and 100 ml deionized water are made into, room temperature reaction took out after 5～300 minutes, with deionized water clean surface repeatedly, be immersed in the Nafion membrane sample that obtains light blue or pale loading ZnO and ZnS composite semiconductor in the deionized water after 24 hours.
Embodiment 1
The preparation of ZnO and ZnS composite semiconductor light-catalyst and load
The 15mm that a slice preliminary treatment is good * 600mm H
+Type Nafion film immerses the Zn (NO with 14.87g
3)
26H
2Carry out ion-exchange in the solution that O and 100 ml deionized water are made into, exchange equilibrium takes out film with deionized water clean surface repeatedly after 24 hours, soaked 24 hours with deionized water again.Having exchanged Zn
2+The Nafion film immerse by 12g vulcanized sodium (Na
2S9H
2O) in the solution that is made into 100 ml deionized water, room temperature reaction took out after 5～300 minutes, with deionized water clean surface repeatedly, be immersed in the Nafion membrane sample that obtains light blue or pale loading ZnO and ZnS composite semiconductor in the deionized water after 24 hours.Fig. 1 has showed X-ray diffraction (XRD) figure of the Nafion film of loading ZnO of the present invention and ZnS composite semiconductor, and as can be seen from the figure, along with the variation of reacting treatment time, the ratio of ZnO and ZnS changes in ZnO and the ZnS composite semiconductor.Specifically, along with the increase of reacting treatment time, the amount of ZnO and ZnS composite semiconductor ZnO reduces gradually in the Nafion film, and the amount of ZnS increases gradually.So just reached the purpose of regulating both ratios by the conditioned reaction processing time.
Embodiment 2
The ZnO of load and ZnS composite semiconductor are as photochemical catalyst light degradation rhodamine B
The Nafion that the load that obtains is had ZnO and ZnS composite semiconductor light-catalyst is as the photocatalytic degradation rhodamine B, select 15mm * 600mm load Nafion film a slice during light degradation for use, the rhodamine B solution concentration is about 5ppm, Philips TL/05 type 4W uviol lamp is used in light degradation, and rhodamine B light degradation amount utilizes Cary-500 type spectrophotometer to detect.Rhodamine B light degradation situation as shown in Figure 2 under the different condition.Curve a is the light degradation rhodamine B situation of blank film when not having load, shows rhodamine B quite stable under ultraviolet light.Light degradation rhodamine B situation when curve b is 30 minutes loading ZnO and ZnS composite semiconductor light-catalyst for the synthetic processing time.Light degradation rhodamine B situation when curve c is 60 minutes loading ZnO and ZnS composite semiconductor light-catalyst for the synthetic processing time.Light degradation rhodamine B situation when curve d is 90 minutes loading ZnO and ZnS composite semiconductor light-catalyst for the synthetic processing time.Light degradation rhodamine B situation when curve e is 120 minutes loading ZnO and ZnS composite semiconductor light-catalyst for the synthetic processing time.The activity of photocatalytic degradation rhodamine B is very high when showing Nafion film loading ZnO and ZnS composite semiconductor light-catalyst, and wherein the sample activity in synthetic 60 minutes processing times is the highest.
Claims (4)
1. the synthetic and synchronized loading method of the original position of composite semiconductor light-catalyst ZnO and ZnS is characterized in that: by ion-exchange with Zn
2+Introduce in the good Nafion film of preliminary treatment, then the Nafion film is immersed in the sodium sulfide solution, room temperature reaction takes out after a period of time, forms ZnO and ZnS composite semiconductor light-catalyst; Wherein the preprocessing process of Nafion film is: the Nafion film is cut into suitable size and shape, soaking and stirring is 24 hours in 60 ℃ of red fuming nitric acid (RFNA)s, immerse mass fraction then successively and be to stir respectively in 60 ℃ of aqueous solution of nitric acid of 60%, 40% and 20% after 2 hours to clean repeatedly to being dipped to few 24 hours with deionized water again after water is neutrality and remove free nitric acid, change it into water white H by this processing with deionized water
+Type Nafion film is with described H
+Type Nafion film places 100 ℃ of vacuum drying chambers must test at least 3 hours with doing H
+Type Nafion film.
2. the synthetic and synchronized loading method of the original position of a kind of composite semiconductor light-catalyst ZnO according to claim 1 and ZnS is characterized in that: ion-exchange Zn
2+The raw material of solution is one or more in zinc nitrate, zinc sulfate or the zinc halide water-soluble zinc salt; Zn in the solution
2+Concentration＞0.2 mol; Ion-exchange time 〉=12 hour.
3. the synthetic and synchronized loading method of the original position of a kind of composite semiconductor light-catalyst ZnO according to claim 1 and ZnS is characterized in that: the concentration of described sodium sulfide solution＞0.5 mol; The room temperature reaction time is 5～300 minutes.
4. synthesize and the synchronized loading method according to the original position of claim 1,2 or 3 described a kind of composite semiconductor light-catalyst ZnOs and ZnS, it is characterized in that: concrete synthetic load technology scheme is as follows: the Nafion film that preliminary treatment is good immerses the Zn (NO with 14.87g
3)
26H
2Carry out ion-exchange in the solution that O and 100 ml deionized water are made into, exchange equilibrium takes out film with deionized water clean surface repeatedly after 24 hours, soaked 24 hours for 300 milliliters with deionized water again; Having exchanged Zn
2+The Nafion film immerse by 12g vulcanized sodium Na
2S9H
2In the solution that O and 100 ml deionized water are made into, room temperature reaction took out after 5～300 minutes, with deionized water clean surface repeatedly, was immersed in the composite semiconductor light-catalyst that obtains light blue or pale loading ZnO and ZnS in the deionized water after 24 hours.
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| CNB2007100091462A CN100446855C (en) | 2007-06-26 | 2007-06-26 | Method for in-situ synthesizing and synchronized loading composite semiconductor light-catalyst ZnO and ZnS |
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| CNB2007100091462A CN100446855C (en) | 2007-06-26 | 2007-06-26 | Method for in-situ synthesizing and synchronized loading composite semiconductor light-catalyst ZnO and ZnS |
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| CN100446855C true CN100446855C (en) | 2008-12-31 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394674A (en) * | 2002-06-27 | 2003-02-05 | 上海交通大学 | Nano compound photocatalyst for cleaning air and its preparation method |
| WO2003051512A1 (en) * | 2001-12-19 | 2003-06-26 | Japan Science And Technology Corporation | Thin-film photocatalyst, its production method, hydrogen sulfide processing method using the thin-film optical catalyst, and hydrogen producing method |
| CN1515352A (en) * | 2003-08-28 | 2004-07-28 | 上海交通大学 | Preparation method of load type photocatalytic purification net block |
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2007
- 2007-06-26 CN CNB2007100091462A patent/CN100446855C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003051512A1 (en) * | 2001-12-19 | 2003-06-26 | Japan Science And Technology Corporation | Thin-film photocatalyst, its production method, hydrogen sulfide processing method using the thin-film optical catalyst, and hydrogen producing method |
| CN1394674A (en) * | 2002-06-27 | 2003-02-05 | 上海交通大学 | Nano compound photocatalyst for cleaning air and its preparation method |
| CN1515352A (en) * | 2003-08-28 | 2004-07-28 | 上海交通大学 | Preparation method of load type photocatalytic purification net block |
Non-Patent Citations (4)
| Title |
|---|
| Photoassisted Hydrogen Production Using VisibleLight andCopreclpitated ZnS·CdS without a Noble Metal. N. Kakuta et al.Journal of Physical Chemistry,Vol.89 . 1985 |
| Photoassisted Hydrogen Production Using VisibleLight andCopreclpitated ZnS·CdS without a Noble Metal. N. Kakuta et al.Journal of Physical Chemistry,Vol.89 . 1985 * |
| ZnO/ ZnS 复合超微粒有序组装的研究. 刘成林等.半导体杂志，第22卷第4期. 1997 |
| ZnO/ ZnS 复合超微粒有序组装的研究. 刘成林等.半导体杂志，第22卷第4期. 1997 * |
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