CN104667878A - Bi2O2CO3-Bi(OHC2O4).2H2O heterojunction and preparation method and application thereof - Google Patents

Bi2O2CO3-Bi(OHC2O4).2H2O heterojunction and preparation method and application thereof Download PDF

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CN104667878A
CN104667878A CN201510030292.8A CN201510030292A CN104667878A CN 104667878 A CN104667878 A CN 104667878A CN 201510030292 A CN201510030292 A CN 201510030292A CN 104667878 A CN104667878 A CN 104667878A
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ohc
junctions
hetero
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bismuth
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CN104667878B (en
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彭银
俞翩翩
周海燕
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Anhui Normal University
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Anhui Normal University
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    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention relates to a Bi2O2CO3-Bi(OHC2O4).2H2O heterojunction and a preparation method and application thereof. The method comprises the following steps: (1) dissolving a bismuth salt in water; (2) adding aqueous solution of sodium oxalate into bismuth nitrate solution; (3) reacting at a certain temperature for a certain time; (4) cooling; (5) washing and drying; (6) dissolving a proper amount of precursor, a surfactant and carbonate in a certain amount of water; (7) adding a certain amount of bismuth salt; (8) cooling; and (9) washing and drying, thereby obtaining the Bi2O2CO3-Bi(OHC2O4).2H2O heterojunction. The one-dimensional Bi2O2CO3-Bi(OHC2O4).2H2O heterojunction is synthesized, and the performances of catalysis and adsorption are integrated into a whole. The catalyst has an excellent visible light catalytic degradation effect on high-concentration dye rhodamine B (RhB) and has high optical stability and reusability. More important, the Bi2O2CO3-Bi(OHC2O4).2H2O heterojunction has good adsorption function on the dye rhodamine B (RhB) and methylene blue (MB) in a short time (within 5 minutes), and also has excellent adsorption performance on the dye methyl orange (MO). The saturated adsorption amount of 40mg of Bi2O2CO3-Bi(OHC2O4).2H2O nanometer composite material on MO is 94mg/g, the MO can be desorbed by adding ethanol to wash, and the adsorbent can be repeatedly used.

Description

A kind of Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions, Preparation Method And The Use
Technical field
The present invention relates to Nano-composite materials method, be specifically related to a kind of Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions, Preparation Method And The Use.
Background technology
In recent years, along with the continuous increase of the size of population, the exploitation of the mankind to earth resource also grow with each passing day, thus cause that renewable resource is in short supply, environmental pollution (as water pollutions, atmosphere pollution etc.) aggravation.Current sewage water treatment method mainly contains biological treatment, chemical oxidization method and active carbon adsorption and combines.Biological treatment is difficult to adapt to the actual state that waste water from dyestuff water quality varies, kind of dyes is many, toxicity is high, and microorganism itself also also exists safety issue.Chemical oxidization method easily causes secondary pollution in the process of waste water from dyestuff, and operating cost is relatively higher, makes its extensive use receive larger restriction.Along with the development of nanometer technology, it is found that, photocatalysis technology can become the green approach solving current environment pollution problem.The maximum advantage of this technology is: (i), for traditional energy-intensive processing method, photocatalysis technology better make use of solar energy.(ii) traditional processing method is that pollutant is converted to another kind of intermediate from a kind of intermediate, but photocatalysis technology is by solar energy oxidation Decomposition organic matter, killing pathogenic bacteria and elimination peculiar smell effectively.(iii) a large amount of toxic compounds can be degraded thoroughly by photocatalytic process in various wastewater treatment.Poisonous heavy metal ion can be reduced to nontoxic oxidation state.(iv) can be used for treatment fluid phase system and gas phase system, can also solid system be applied to a certain extent simultaneously.V () reaction condition is gentle, the reaction time is controlled, does not need chemical addition agent, basic non-secondary pollution.Based on above advantage, photocatalysis technology has traditional Conventional catalytic technology and the incomparable advantage of adsorption technology, is a kind of green environment Treatment process with broad prospect of application.
One-dimensional nano structure (as nano wire, nanometer rods, nanotube etc.) can provide higher specific area, thus can ensure that a high active site density is beneficial to surface reaction or absorption.In addition, in the structure that photogenerated charge is separated and transmits, one-dimensional nano structure has very high charge carrier transport speed, carrier can move freely along one dimension long axis direction, reduce the recombination rate in electronics and hole, decrease and lose photoelectronic possibility due to the existence of a large amount of crystal boundary, thus improve the photoelectric properties of material.Meanwhile, one-dimentional structure also can play skeleton function in hetero-junctions, makes heterogeneously to have larger specific area, is not only conducive to photocatalytic activity and improves, also improve the absorption property of material simultaneously.But up to the present, the synthesis having excellent photocatalysis performance and absorption property one-dimensional nano-composite material concurrently still has huge challenge.
Summary of the invention
The object of the present invention is to provide a kind of Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions, Preparation Method And The Use.First technical problem to be solved is to provide a kind of preparation method.Second technical problem to be solved is to provide excellent, stable, reusable Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o heterojunction photocatalyst.3rd technical problem to be solved is to provide high adsorption capacity, efficient, reusable Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions adsorbent.Concrete technical scheme is as follows:
A kind of Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, comprises the steps:
(1) bismuth salt is dissolved in water;
(2) aqueous solution of sodium oxalate is joined in zinc nitrate solution;
(3) certain hour is reacted at a certain temperature;
(4) cool;
(5) washing is also dry;
(6) by appropriate presoma, surfactant and dissolves carbonate are in a certain amount of water;
(7) a certain amount of bismuth salt is added;
(8) cool;
(9) washing is also dry, obtains Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions.
Further, in step (1), take 2-3 part bismuth salt and add water and dissolve completely.
Further, in step (2), the aqueous solution of 1-2 part sodium oxalate is dropwise joined in bismuth nitrate solution, mix.
Further, 30-40 hour is reacted at 100-150 DEG C in step (3).
Further, in step (4) and (8), after reaction terminates, naturally cool to room temperature; And/or in step (5) and (9), product distilled water, ethanol washs, and is dried to constant weight, obtains presoma.
Further, in step (6), take 0.1-1 part presoma, 0.1-1 part surfactant and 0.01-0.1 part dissolves carbonate are in the water of 20-100ml.
Further, in step (7), add the bismuth salt of 0.01-0.1 part again, stir 1-10h.
Further, described bismuth salt is bismuth chloride, bismuth nitrate, one or several mixture of bismuth sulfate; And/or described carbonate is one or several mixing of organic and inorganic carbonate.
A kind of Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions, adopts as said method prepares.
Above-mentioned Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2the purposes of O hetero-junctions, for the absorption of dyestuff and visible light photocatalytic degradation.
Compared with currently available technology, the present invention has synthesized one dimension Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions, it has catalysis and adsorption performance concurrently.This catalyst has excellent visible light photocatalytic degradation effect to high concentration dye, rhodamine B (RhB), and has photostability and reusing.What is more important, Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions shows good absorption property in the short time (in 5 minutes) to dye, rhodamine B (RhB) and methylene blue (MB), shows excellent absorption property to methyl orange (MO).The Bi of 40 milligrams 2o 2cO 3-Bi (OHC 2o 4) 2H 2the saturated extent of adsorption of O nano composite material to MO reaches 94mg/g.Can make MO desorption with ethanol washing, adsorbent can repeatedly use.Described Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions synthetic method is novel, has excellent visible light catalysis activity and stronger adsorptivity, will have practical value in dye wastewater process.
Accompanying drawing explanation
Fig. 1 is Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2the powder diagram (XRD) of O hetero-junctions;
Fig. 2 is Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2the electron scanning video picture figure (SEM) of O hetero-junctions;
Fig. 3 is Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2the transmission plot (TEM) of O hetero-junctions;
Fig. 4 is Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions (40mg) is to the degradation rate figure of RhB (20mg/L);
Fig. 5 is Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2the ultraviolet-visible light spectrogram of O hetero-junctions (40mg) photocatalytic degradation rhodamine B (20mg/L);
Fig. 6 is Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions is to rhodamine B (20mg/L) photocatalytic degradation recycling rate of waterused figure;
Fig. 7 is Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions is to the powder diagram (XRD) after rhodamine B (20mg/L) photocatalytic degradation;
Fig. 8 is Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions (40mg) is to the absorption figure of different dyes (20mg/L).
Detailed description of the invention
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
At the preferred Bi of one 2o 2cO 3-Bi (OHC 2o 4) 2H 2following steps are included in the preparation method of O hetero-junctions, take bismuth salt (2-3g), add water and dissolve completely, the aqueous solution of sodium oxalate (1-2g) is dropwise joined in zinc nitrate solution, mix, at 100-150 DEG C of reaction 30-40 hour, after reaction terminates, naturally cool to room temperature, product distilled water, ethanol washs, and is dried to constant weight, obtains presoma; Take appropriate presoma (0.1-1g), surfactant (0.1-1g) and carbonate (0.01-0.1g) are dissolved in a certain amount of water (20-100ml), add a certain amount of bismuth salt (0.01-0.1g) again, stir certain hour (1-10h), after reaction terminates, naturally cool to room temperature, product distilled water, ethanol washs, and is dried to constant weight, obtains Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions.Bismuth salt is bismuth chloride, bismuth nitrate, one or several mixture of bismuth sulfate.Carbonate is one or several mixing of organic and inorganic carbonate.
With reference to the sample (S1) that Fig. 2, A load capacity is minimum, the sample (S2, S3) of b, c high load amount successively, can it is evident that nanometer sheet is long in nanometer rods equably, form homogeneous Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions.As shown in Figure 5, under simulated solar irradiation irradiates, in 0.5 hour, rhodamine B (20mg/L) is completely degraded.As shown in Figure 6, circulate to lose afterwards for 5 times and only have 7%.As Fig. 7 can find out Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions is highly stable.Bi as can be seen in Figure 8 2o 2cO 3-Bi (OHC 2o 4) 2H 2the adsorption effect of O hetero-junctions to MO is best.Through 5 minutes, methyl orange (75mg/l) was adsorbed completely.Can find out that adsorbent has excellent reusing.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.

Claims (10)

1. a Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, is characterized in that, comprises the steps:
(1) bismuth salt is dissolved in water;
(2) aqueous solution of sodium oxalate is joined in zinc nitrate solution;
(3) certain hour is reacted at a certain temperature;
(4) cool;
(5) washing is also dry;
(6) by appropriate presoma, surfactant and dissolves carbonate are in a certain amount of water;
(7) a certain amount of bismuth salt is added;
(8) cool;
(9) washing is also dry, obtains Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions.
2. Bi as claimed in claim 1 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, is characterized in that, in step (1), takes 2-3 part bismuth salt and adds water and dissolve completely.
3. Bi as claimed in claim 1 or 2 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, is characterized in that, is dropwise joined in bismuth nitrate solution by the aqueous solution of 1-2 part sodium oxalate, mix in step (2).
4. the Bi according to any one of claim 1-3 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, is characterized in that, at 100-150 DEG C of reaction 30-40 hour in step (3).
5. the Bi according to any one of claim 1-4 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, is characterized in that, in step (4) and (8), after reaction terminates, naturally cools to room temperature; And/or in step (5) and (9), product distilled water, ethanol washs, and is dried to constant weight, obtains presoma.
6. the Bi according to any one of claim 1-5 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, is characterized in that, in step (6), takes 0.1-1 part presoma, and 0.1-1 part surfactant and 0.01-0.1 part dissolves carbonate are in the water of 20-100ml.
7. the Bi according to any one of claim 1-6 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, is characterized in that, adds the bismuth salt of 0.01-0.1 part in step (7) again, stirs 1-10h.
8. the Bi according to any one of claim 1-7 2o 2cO 3-Bi (OHC 2o 4) 2H 2the preparation method of O hetero-junctions, is characterized in that, described bismuth salt is bismuth chloride, bismuth nitrate, one or several mixture of bismuth sulfate; And/or described carbonate is one or several mixing of organic and inorganic carbonate.
9. a Bi 2o 2cO 3-Bi (OHC 2o 4) 2H 2o hetero-junctions, is characterized in that, adopts method as described in claim 1-8 to prepare.
10. Bi as claimed in claim 9 2o 2cO 3-Bi (OHC 2o 4) 2H 2the purposes of O hetero-junctions, is characterized in that, for the absorption of dyestuff and visible light photocatalytic degradation.
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CN107433196A (en) * 2017-07-24 2017-12-05 安徽师范大学 Bismuth oxide pucherite hetero-junctions and its preparation method and application
CN109967109A (en) * 2019-04-18 2019-07-05 安徽师范大学 One-dimensional Bi2O2CO3Nanometer rods and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107433196A (en) * 2017-07-24 2017-12-05 安徽师范大学 Bismuth oxide pucherite hetero-junctions and its preparation method and application
CN107433196B (en) * 2017-07-24 2020-07-03 安徽师范大学 Bismuth oxide-bismuth vanadate heterojunction and preparation method and application thereof
CN109967109A (en) * 2019-04-18 2019-07-05 安徽师范大学 One-dimensional Bi2O2CO3Nanometer rods and preparation method thereof

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