CN104841440B - A kind of heterojunction type tri compound semiconductor light-catalyst and preparation method thereof - Google Patents
A kind of heterojunction type tri compound semiconductor light-catalyst and preparation method thereof Download PDFInfo
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- CN104841440B CN104841440B CN201510230808.3A CN201510230808A CN104841440B CN 104841440 B CN104841440 B CN 104841440B CN 201510230808 A CN201510230808 A CN 201510230808A CN 104841440 B CN104841440 B CN 104841440B
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Abstract
The invention discloses a kind of heterojunction type tri compound semiconductor light-catalyst and preparation method thereof.The present invention uses constant pH coprecipitation to prepare ternary layered double-metal hydroxide as presoma, most obtains ternary heterojunction composite semiconductor through high-temperature roasting afterwards.Preparation technology of the present invention is easy, resulting materials have appropriate band structure, carrier separation and migration rate can be effectively improved, efficiently utilize visible ray, serial ternary heterojunction composite semiconductor is prepared by the relative amount of selective regulation metal ion, high-activity photocatalyst is filtered out, shows good dyestuff degradation capability under visible light.Ternary heterojunction composite semiconductor has higher catalytic activity to 1.6 4.1 times that the visible light photocatalytic degradation reaction rate constant of methylene blue is binary composite semiconductor, has good universality in terms of dyestuff degraded under visible light.
Description
Technical field
The invention belongs to semiconductor light-catalyst preparing technical field, more particularly to a kind of Zinc oxide-base heterojunction type ternary
Composite oxide semiconductor catalysis material and preparation method thereof, and it is anti-to be applied to visible light photocatalytic degradation organic dyestuff
Should.
Background technology
Photocatalysis technology receives significant attention in solar energy conversion and depollution of environment field, spread spectrum response range and carries
The photocatalysis quantum efficiency of high catalyst is the hot subject in photocatalysis chemical field.It is well known that TiO2It is most normal with ZnO
Semiconductor light-catalyst, still, it is low and can not be effectively using visible quantum efficiency to be present in both wide band gap semiconducters
The shortcomings of light, limit its application in field of environment pollution control.Therefore, the degraded of novel visible responsive photocatalyst is designed
Organic pollution is significant to solving environmental problem.
At present, photochemical catalyst research direction turns to from design single-phase structure photochemical catalyst and uses semiconductor coupling skill
Art constructs polynary semiconductors coupling structure.Because by wide band gap semiconducter TiO2Composition is coupled with narrow-band semiconductor with ZnO
Heterojunction structure, it is compound to suppress quantity of photogenerated charge, improves quantum efficiency, and the sensibilization of narrow-band semiconductor can expand
TiO2With ZnO response spectrum scope.In recent years, with TiO2Compare, heterojunction type zno-based compound semiconductor photocatalytic material exists
It is all less in species and quantity, up to the present, the preparation research of only a small amount of ZnO composite semiconductors heterojunction photocatalysis material
It is reported, e.g., in document Applied Catalysis B:Environmental,2014,160:In 408-414, Guo etc. is adopted
The ZnO-ZnFe with coaxial type heterojunction structure is prepared on sapphire substrate with template is sacrificed2O4Nano-cable array,
And it is applied to rhodamine B degradation reaction；In document Applied Surface Science, 2013,268:In 237-245,
Zhang etc. is done template with glucose, is prepared with hud typed hetero-junctions using the hydrothermal synthesis method of polyethylene glycol auxiliary
The ZnO-ZnAl of structure2O4Tiny balloon.The preparation technology of above-mentioned Zinc oxide-base composite semiconductor light-catalyst is complicated, due to using
Organic solvent causes preparation process not environmentally and cost is high.In recent years, double-metal hydroxide (LDHs) stratified material is due to it
The Modulatory character of laminate component, be advantageous to introduce functional ion in the material, the nano metal oxygen prepared by LDHs presomas
Compound is uniformly dispersed, is bigger than surface, and good application potential is presented in photocatalysis field.Heterojunction type tri compound semiconductor
The constructing of photochemical catalyst can not show a candle to that binary complex is extensive, be prepared using lamellar precursor roasting method with decentralized heterojunction structure
There is not been reported for zno-based tri compound semiconductor light-catalyst, therefore explores new ternary oxide semiconductor light-catalyst
Technology of preparing there is practical significance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of heterojunction type tri compound semiconductor light-catalyst.This hair
It is bright to use constant pH coprecipitation to prepare ternary layered double-metal hydroxide as presoma, most obtain ternary through high-temperature roasting afterwards
Metal composite oxide.Resulting materials can effectively utilize visible ray, have higher urge to the Visible Light Induced Photocatalytic of organic dyestuff
Change active and preferable universality.The reaction of degradation of methylene blue is as probe reaction using under visible ray, to heterojunction type ternary
Composite semiconductor light-catalyst carries out photocatalysis performance evaluation.
The preparation method of heterojunction type tri compound semiconductor light-catalyst of the present invention, its specific preparation technology step
It is rapid as follows：
A. the mixing salt solution of solvable divalent zinc salt and solvable trivalent metal salt is prepared, the total concentration of wherein metal ion is
The mol ratio of 0.1-0.5M, divalent zinc ion and trivalent metal ion is 2-4；Prepare NaOH and Na2CO3Mixed ammonium/alkali solutions,
The mol ratio of NaOH and divalent zinc ion is 0.8-3.2, Na2CO3Mol ratio with trivalent metal ion is 1-3；
B. mixing salt solution and mixed ammonium/alkali solutions are added drop-wise to by four-hole bottle using coprecipitation jointly under conditions of stirring
In, 25-40 DEG C of bath temperature, it is 8-11 that pH value in four-hole bottle is controlled during dropwise addition；After being added dropwise, in 60-90 DEG C of water-bath
Lower thermostatic crystallization 12-36h；
C. by reaction product deionized water centrifuge washing to neutrality, dried at 60-90 DEG C, it is finely ground with mortar, obtain
Ternary layered double-metal hydroxide presoma；
D. by the ternary layered double-metal hydroxide presoma of preparation in Muffle furnace, with 2-10 DEG C/min heating speed
Rate is warming up to 500-800 DEG C of sintering, after being incubated 2-4 hours, is cooled to room temperature, obtains heterojunction type tri compound semiconductor light and urge
Agent.
One or more of the described solvable divalent zinc salt in zinc nitrate, zinc chloride, zinc sulfate.
One or more of the described solvable trivalent metal salt in nitrate, villaumite, sulfate.
Described solvable trivalent metal salt is indium salts, and the mixing of any one of molysite, chromic salts, aluminium salt.
The heterojunction type tri compound semiconductor light-catalyst of above-mentioned preparation is dropped applied to visible light catalytic organic dyestuff
Solution reaction.
Described organic dyestuff selected from methylene blue, malachite green, crystal violet, safranine T and it is Congo red in any one.
The advantage of the invention is that：Preparation technology is easy, and resulting materials have appropriate band structure, can effectively improved
Carrier separation and migration rate, efficiently utilize visible ray.By ZnO and narrow-band semiconductor ZnFe2O4And In2O3Carry out coupling structure
Into hetero-junctions, and to suppress quantity of photogenerated charge compound for the built in field of hetero-junctions, so as to improve quantum efficiency；Utilize narrow-band semiconductor
Sensibilization expand the spectral response range of composite；The phase boundary potential ladder of ternary heterojunction structure semiconductor conduction band position
Degree promotes separation of charge, so as to be advantageous to the generation of active specy.Pass through the relative amount system of selective regulation metal ion
Standby serial heterojunction type ternary composite metal oxide, filters out high-activity photocatalyst, shows under visible light good
Dyestuff degradation capability.Ternary heterojunction composite semiconductor is binary to the visible light photocatalytic degradation reaction rate constant of methylene blue
1.6-4.1 times of composite semiconductor, there is higher catalytic activity, there is well pervasive in terms of dyestuff degraded under visible light
Property.
Brief description of the drawings
Fig. 1 is the gained Zn of the embodiment of the present invention 13In0.3Fe0.7The XRD spectra of-MMO composites.
Fig. 2 is the gained Zn of the embodiment of the present invention 13In0.3Fe0.7The TEM figures of-MMO composites.
Fig. 3 is the gained Zn of the embodiment of the present invention 13In0.3Fe0.7The UV-vis spectrograms of-MMO composites.
Fig. 4 is that trielement composite material is catalyzed methylene blue degraded under visible light with binary composite in present example
The concentration time curve figure of reaction.
Embodiment
Embodiment 1
Weigh 1.3387g Zn (NO3)2·6H2O、0.1759g In(NO3)3·5H2O and 0.4242g Fe (NO3)3·
9H2O is dissolved in 30mL deionized water wiring solution-formings, and mixed salt solution concentration is 0.2M；Weigh 0.48g NaOH and 0.53g
Na2CO3It is dissolved in 50mL deionized waters and is made into mixed solution, concentration is respectively the [Zn of [NaOH]=1.62+], [Na2CO3([the In of]=23 +]+[Fe3+]).Mixed salt solution is respectively placed in two constant pressure funnels with mixed ammonium/alkali solutions, 35 DEG C of bath temperature
Under, solution is added drop-wise in four-hole bottle while stirring, adjusts rate of addition, keeps pH in the range of 9.5~10.Then exist
Thermostatic crystallization 24h under 65 DEG C of water-baths.After reaction terminates, reaction product is centrifuged into (3500r/min) with deionized water and washed into
Property, gained slurries are dried overnight at 60 DEG C, it is finely ground with mortar, obtain [In through 500 DEG C of roastings3+]/[M3+]=0.3/0.7,
[Zn2+]/([In3+]+[M3+])=3/1 Zn3In0.3Fe0.7- ternary compound oxides material.
The reaction of degradation of methylene blue is as probe reaction using under visible ray, to prepared ternary composite metal oxide
Carry out photocatalysis performance evaluation.Light source uses 500W xenon lamp and additive filter (λ>420nm).Configure 100mL methylene blues
It is placed in the aqueous solution of (50~100ppm) in customization reactor, a certain amount of catalyst and ultrasonic disperse is added, without striation
60min is stirred at room temperature under part.Then device is connected, makes xenon source and liquid level of solution distance 10cm, is stirred continuously solution, beats
Drive xenon lamp and carry out radiation of visible light.In course of reaction, measured every 30min sampling ultraviolet specrophotometers at 663nm
Absorb value changes.The degradation curve of photocatalytic process is drawn, and carries out catalytic performance test analysis.After 2h being irradiated under its visible ray
97.8% is reached to the catalysis degradation modulus of methylene blue, reaction rate constant is 30.9 × 10-3min-1, it is Zn3Fe- binary is compound
4.11 times of oxide material.
Embodiment 2
Weigh 1.3387g Zn (NO3)2·6H2O、0.2932g In(NO3)3·5H2O and 0.3030g Fe (NO3)3·
9H2O is dissolved in 30mL deionized water wiring solution-formings, and mixed salt solution concentration is 0.2M；Weigh 0.48g NaOH and 0.53g
Na2CO3It is dissolved in 50mL deionized waters and is made into mixed solution, concentration is respectively the [Zn of [NaOH]=1.62+], [Na2CO3([the In of]=23 +]+[Fe3+]).[In is prepared in condition same as Example 13+]/[M3+]=0.5/0.5, [Zn2+]/([In3+]+[M3+])=
3/1 Zn3In0.5Fe0.5- ternary compound oxides material.To the catalysis degradation modulus of methylene blue after irradiation 2h under its visible ray
Reach 88.5%, reaction rate constant is 17.9 × 10-3min-1, it is Zn32.38 times of Fe- binary composite oxide materials.
Embodiment 3
Weigh 1.3387g Zn (NO3)2·6H2O、0.4105g In(NO3)3·5H2O and 0.1818g Fe (NO3)3·
9H2O is dissolved in 30mL deionized water wiring solution-formings, and mixed salt solution concentration is 0.2M；Weigh 0.48gNaOH and 0.53g
Na2CO3It is dissolved in 50mL deionized waters and is made into mixed solution, concentration is respectively the [Zn of [NaOH]=1.62+], [Na2CO3([the In of]=23 +]+[Fe3+]).[In is prepared in condition same as Example 13+]/[M3+]=0.7/0.3, [Zn2+]/([In3+]+[M3+])=
3/1 Zn3In0.7Fe0.3- ternary compound oxides material.To the catalysis degradation modulus of methylene blue after irradiation 2h under its visible ray
Reach 82.3%, reaction rate constant is 14.3 × 10-3min-1, it is Zn31.90 times of Fe- binary composite oxide materials.
Embodiment 4
Weigh 0.8925g Zn (NO3)2·6H2O、0.1759g In(NO3)3·5H2O and 0.4242g Fe (NO3)3·
9H2O is dissolved in 30mL deionized water wiring solution-formings, and mixed salt solution concentration is 0.2M；Weigh 0.32g NaOH and 0.53g
Na2CO3It is dissolved in 50mL deionized waters and is made into mixed solution, concentration is respectively the [Zn of [NaOH]=1.62+], [Na2CO3([the In of]=23 +]+[Fe3+]).[In is prepared in condition same as Example 13+]/[M3+]=0.3/0.7, [Zn2+]/([In3+]+[M3+])=
2/1 Zn2In0.3Fe0.7- ternary compound oxides material.To the catalysis degradation modulus of methylene blue after irradiation 2h under its visible ray
Reach 93.2%, reaction rate constant is 22.3 × 10-3min-1, it is Zn32.97 times of Fe-MMO binary composite oxide materials.
Claims (3)
- A kind of 1. preparation method of heterojunction type tri compound semiconductor light-catalyst, it is characterised in that its specific preparation technology Step is as follows：A. the mixing salt solution of solvable divalent zinc salt and solvable trivalent metal salt is prepared, the wherein total concentration of metal ion is 0.1- The mol ratio of 0.5M, divalent zinc ion and trivalent metal ion is 2-4；Prepare NaOH and Na2CO3Mixed ammonium/alkali solutions, NaOH with The mol ratio of divalent zinc ion is 0.8-3.2, Na2CO3Mol ratio with trivalent metal ion is 1-3；B. mixing salt solution and mixed ammonium/alkali solutions are added drop-wise in four-hole bottle jointly under conditions of stirring using coprecipitation, water 25-40 DEG C of bath temperature, it is 8-11 that pH value in four-hole bottle is controlled during dropwise addition；After being added dropwise, the constant temperature under 60-90 DEG C of water-bath Crystallization 12-36h；C. by reaction product deionized water centrifuge washing to neutrality, dried at 60-90 DEG C, it is finely ground with mortar, obtain ternary Layered double hydroxide presoma；D. by the ternary layered double-metal hydroxide presoma of preparation in Muffle furnace, with 2-10 DEG C/min heating rate liter Temperature after being incubated 2-4 hours, is cooled to room temperature, obtains heterojunction type tri compound conductor photocatalysis to 500-800 DEG C of sintering Agent；One or more of the described solvable divalent zinc salt in zinc nitrate, zinc chloride, zinc sulfate；Described solvable trivalent metal salt is the mixing of indium salts and molysite；One or more of the described solvable trivalent metal salt in nitrate, villaumite, sulfate.
- 2. the heterojunction type tri compound semiconductor light-catalyst that the method according to claim 11 is prepared is in visible ray The application being catalyzed in degradation of organic dyes reaction.
- 3. application according to claim 2, it is characterised in that described organic dyestuff be selected from methylene blue, malachite green, Crystal violet, safranine T and it is Congo red in any one.
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| CN110721695A (en) * | 2019-10-25 | 2020-01-24 | 郑州大学 | Preparation method of composite metal oxide with p-n heterostructure |
| CN114054025A (en) * | 2021-03-04 | 2022-02-18 | 中国科学院宁波材料技术与工程研究所 | Semiconductor nano material and preparation method and application thereof |
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| CN1544144A (en) * | 2003-11-13 | 2004-11-10 | �Ϻ���ͨ��ѧ | Visible light response photocatalyst and application thereof |
| CN103157457A (en) * | 2011-12-08 | 2013-06-19 | 北京化工大学 | Mg/Zn/In composite metal oxide photocatalyst, preparation method and applications thereof |
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