CN109759121A - A kind of preparation method of two dimension Z-type hetero-junctions visible light catalyst - Google Patents
A kind of preparation method of two dimension Z-type hetero-junctions visible light catalyst Download PDFInfo
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- CN109759121A CN109759121A CN201910184154.3A CN201910184154A CN109759121A CN 109759121 A CN109759121 A CN 109759121A CN 201910184154 A CN201910184154 A CN 201910184154A CN 109759121 A CN109759121 A CN 109759121A
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Abstract
The invention discloses a kind of preparation methods of two-dimentional Z-type hetero-junctions visible light catalyst.The following steps are included: preparing block g-C3N4 material using thermal polymerization, it is scattered in heated at constant temperature in concentrated hydrochloric acid and stirs to get white solution；Centrifugation is washed, dry, obtains white powder A；Gained white powder A is added in dispersant solution and is removed by ultrasonic liquid-phase, obtains milky white solution；Centrifugation, washing obtain white powder B after dry；It disperses gained white powder B in deionized water, the mixed solution of five water bismuth nitrates and potassium bromide is added dropwise, heating stirring obtains two-dimentional Z-type hetero-junctions visible light catalyst after centrifugation gained precipitating is dry after reaction.Preparation method simple process of the present invention, low for equipment requirements, raw material is easy to get, low in cost, and operability is good, meets environmental requirement.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of system of two dimension Z-type hetero-junctions visible light catalyst
Preparation Method.
Background technique
With the quickening of urbanization process and the increase of vehicle guaranteeding organic quantity so that vehicle exhaust discharge quantity sharp increase,
Become low concentration of NO in the semi-closed structures such as vcehicular tunnel and underground parking spacexOne of place most concentrated, to human body
Health, which produces, greatly to threaten.Conventional method of denitration such as absorption method, ventilation, biodegrade etc. is since the device is complicated, denitration
The reasons such as condition is harsh, be not thorough, demand is big are not able to satisfy increasing ecological requirements more and more, therefore, exploitation
A kind of efficient, inexpensive, free of contamination removal low concentration of NOxMethod it is most important.
Low concentration of NOxPhotocatalysis oxidation technique be the presently method that can be carried out denitration most convenient using the sun, i.e.,
Make to work as NOxConcentration when being down to ppb level, can also effectively remove NOx.Graphite phase carbon nitride (g-C3N4) as a kind of to can
The semiconductor light-catalyst of light-exposed sensitivity, abundance, preparation cost is lower, has preferable absorbability in visible light region,
Under normal temperature and pressure also have preferable chemical stability, can antiacid, alkali, light corrosion, thus become current semiconductor material grind
Study carefully the hot spot in field.But due to g-C3N4Exciton binding energy is high, crystallinity is low, so that photo-generate electron-hole is to being difficult to separate, light
Raw carrier mobility is small, low to 460nm above wavelength absorptivity, causes photocatalytic process quantum efficiency relatively low, reduces
To the utilization rate of solar energy.Therefore it develops the simple and reliable method of one kind and removes modified g-C3N4, improving its photocatalytic activity seems more
Send out important.
g-C3N4Unique two-dimensional layered structure, make it be easy it is compound with other components, especially with other semiconductors couplings
Heterojunction composite photocatalyst is formed, the heterojunction structure at phase interface can effectively prevent the compound of electrons and holes,
Accelerate the separative efficiency of photo-generated carrier, to improve photocatalytic activity, this is also current solution g-C3N4Photo-generate electron-hole
The problems such as to low separation efficiency one of most efficient method.But two semiconductors due to constituting hetero-junctions are in electric charge transfer mistake
Cheng Zhong, conduction band and valence band potential are lower, so the carrier participated in catalytic process is difficult to realize strong redox ability, limit
Its application in terms of photocatalysis has been made, has there is researcher's discovery recently, can obviously have been overcome by the Z-type hetero-junctions for constructing novel
This deficiency.
The formation mechenism of Z-type hetero-junctions is mainly from following reason: from position calibration conduction band (CB) of two semiconductors
The electronics set and occur at heterojunction boundary compared with the hole of the position negative valency band (VB) it is compound after, in solid-solid circle of semiconductor
It is easy that there are a large amount of defects at face, at this moment the energy level of interface is quasi-continuous, similar to the energy level situation of conductor.This makes
Contact interface shows property similar with conductor, is similar to Ohmic contact face, the complex centre of the electron hole Yi Chengwei makes more
The remaining photohole in remaining light induced electron and corrigendum VB in negative CB remains simultaneously, thus guaranteeing Strong oxdiative also
It can promote efficiently separating for carrier under the premise of proper energy power as far as possible again.
Summary of the invention
It is an object of that present invention to provide a kind of preparation method of two-dimentional Z-type hetero-junctions visible light catalyst, simple process is right
Equipment requirement is low, and raw material is easy to get, low in cost, and operability is good.
In order to achieve the above objectives, as follows using technical solution:
A kind of preparation method of two dimension Z-type hetero-junctions visible light catalyst, comprising the following steps:
1) block g-C is prepared using thermal polymerization3N4Material, be scattered in heated at constant temperature in concentrated hydrochloric acid stir to get it is white
Color solution；Centrifugation is washed, dry, obtains white powder A；
2) gained white powder A is added in dispersant solution and is removed by ultrasonic liquid-phase, obtains milky white solution；From
The heart, washing obtain white powder B after dry；
3) it is dispersed gained white powder B in deionized water using in situ synthesis, five water bismuth nitrate (Bi is added dropwise
(NO3)3·5H2O it) is obtained after centrifugation gained precipitating is dry after reaction with the mixed solution of potassium bromide (KBr), heating stirring
Two-dimentional Z-type hetero-junctions visible light catalyst.
The temperature that heated at constant temperature in concentrated hydrochloric acid is scattered in above scheme, in step 1 is 60 DEG C, and the time is 4~15h.
In above scheme, dispersant solution is the isopropanol water solution that volume fraction is 75%, ultrasonic liquid-phase stripping in step 2
It is 6~15h from the time.
In above scheme, five water bismuth nitrates and the mass ratio of potassium bromide are (0.2~5.5): (0.05~1.4) in step 3.
It is 1:4 that the dosage of five water bismuth nitrates and potassium bromide, which accounts for the mass ratio of white powder B, in above scheme, in step 3.
In above scheme, heating temperature is 80 DEG C in step 3, mixing time 2h.
Beneficial effects of the present invention:
Two dimension Z-type hetero-junctions visible light catalyst produced by the present invention, the interface cohesion mode with 2D/2D are conducive to
Shorten g-C3N4The transmission range of photo-generate electron-hole pair reduces interface resistance, while the building of Z-type heterojunction structure is guaranteeing
In the case that photo-generate electron-hole is to efficiently separating, semiconductor is made to be provided simultaneously with strong redox ability, is conducive to improve it
Gas phase catalysis performance.
Preparation method simple process of the present invention, low for equipment requirements, raw material is easy to get, low in cost, and operability is good,
Meet environmental requirement, provide feasible thinking and means for the preparation of high-efficient visible-light photocatalyst, is conducive to that light is pushed to urge
Application of the change technology in gas phase catalysis field.
Detailed description of the invention
Fig. 1: two-dimentional Z-type hetero-junctions visible light catalyst BiOBr/g-C prepared by embodiment 13N4XRD spectrum.
Fig. 2: two-dimentional Z-type hetero-junctions visible light catalyst BiOBr/g-C prepared by embodiment 13N4FT-IR spectrum.
Fig. 3: block g-C3N4、g-C3N41 gained BiOBr/g-C of nanometer sheet and embodiment3N4SEM image.
Fig. 4: 1 gained visible light catalyst BiOBr/g-C of embodiment3N4Photocatalysis performance after different capturing agents are added
Figure.
Fig. 5: BiOBr nanometer sheet and g-C3N4Z-type charge transfer mechanism figure between nanometer sheet.
Specific embodiment
Following embodiment further illustrates technical solution of the present invention, but not as limiting the scope of the invention.
Embodiment 1
Weigh the block g-C of a certain amount of thermal polymerization preparation3N4Material, according still further to g-C3N4Material and concentrated hydrochloric acid quality
Than being 1:3, the concentrated hydrochloric acid of corrresponding quality is measured, and by g-C3N4Material is mixed with concentrated hydrochloric acid, is stirred under conditions of 60 DEG C
9h is then centrifuged for washing, and is centrifuged product and obtains white powder after dry 12h in 80 DEG C of baking ovens.Above-mentioned white powder is dissolved in
In the aqueous isopropanol that volume ratio is 75%, 10h is removed by ultrasound and obtains removing product, by removing product centrifugation, first
G-C can be obtained after dry 12h in 80 DEG C of baking ovens in 3000rmp centrifuging and taking supernatant, then 9000rmp taking precipitate3N4Nanometer
Piece.Weigh a certain amount of g-C3N4Nanometer sheet is dissolved in 100ml deionized water, and ultrasonic disperse 30min makes it dissolve, and obtains white solution,
Labeled as A liquid；According to BiOBr and g-C3N4Nanometer sheet mass ratio is 1:4, weighs a certain amount of Bi (NO3)3·5H2O and KBr are molten
In 100ml ethylene glycol solvent, quickly stirs 60min and obtain colourless solution, be labeled as B liquid；B liquid is added drop-wise to dropwise in A liquid, is filled
After point stirring 1h, being deposited in 80 DEG C of baking ovens of obtaining is dried finally by centrifuge washing, is obtained by 80 DEG C of oil bath heating 2h
White powder is two-dimentional Z-type hetero-junctions visible light catalyst sample.
Fig. 1 is two-dimentional Z-type hetero-junctions visible light catalyst BiOBr/g-C prepared by embodiment 13N4XRD spectrum, from figure
In as can be seen that g-C3N4There are two apparent diffraction maximums for nanometer sheet tool, and the diffraction maximum positioned at 13 ° is g-C3N4Characteristic peak, it is right
The basic repetitive unit of 3-s- triazine ring structure is answered, the diffraction maximum at 27.4 ° corresponds to the interlayer heap of aromatic compound
Long-pending characteristic peak.Two dimension BiOBr/g-C in figure3N4In Z-type hetero-junctions visible light catalyst 2 θ be located at 10.9 °, 21.9 °, 25.2 °,
31.7 °, 32.2 °, 34.1 °, 39.3 °, 46.2 °, 47.7 °, 50.7 °, 53.4 °, 56.2 °, 57.2 ° of diffraction maximum respectively corresponds
(001) of BiOBr (JCPDS No.01-078-0348), (002), (101), (102), (110), (111), (112), (200),
(201), (104), (211), (114) and (212) crystal face.Meanwhile g-C3N4Diffraction peak intensity obviously weaken, the reason is that g-
C3N4Nanometer sheet is covered by BiOBr, illustrates that two-dimentional Z-type hetero-junctions visible light catalyst is successfully prepared.
Fig. 2 is two-dimentional Z-type hetero-junctions visible light catalyst BiOBr/g-C prepared by embodiment 13N4FT-IR spectrum, figure
Middle 1250-1630cm-1The absorption peak at place corresponds to the stretching vibration of CN heterocycle, is located at 810cm-1The absorption peak at place is 3-s- tri-
The characteristic peak of piperazine ring structure corresponds to the eigen vibration of 3-s- triazine ring, is located at 518cm-1The absorption peak at place is attributed to bromine oxidation
The symmetrical stretching vibration peak of the Bi-O of bismuth in two-dimentional Z-type hetero-junctions visible light catalyst, is located at 518cm compared with BiOBr-1Place
The intensity of absorption peak obviously die down, furthermore apparent offset also has occurred in the absorption peak in CN heterocycle, illustrates BiOBr nanometer sheet
With g-C3N4There is the effect of chemical bond, two-dimentional Z-type hetero-junctions visible light catalyst BiOBr/g-C between nanometer sheet3N4Success
Synthesis, it is consistent with XRD result.
Fig. 3 (a) is block g-C3N4The SEM image of material, has apparent lamella microscopic appearance, and marginal fold has a large amount of
Hole is accumulated to exist.Fig. 3 (b) is g-C3N4The SEM image of nanometer sheet, with block g-C3N4Material is compared, g-C3N4The thickness of nanometer sheet
Degree is thinner, about in 9nm or so.Fig. 3 (c) is two-dimentional Z-type hetero-junctions visible light catalyst prepared by the embodiment of the present invention 1
BiOBr/g-C3N4SEM image, as seen from the figure, two-dimentional Z-type hetero-junctions visible light catalyst still has nanometer sheet form.
Fig. 4 is two-dimentional Z-type hetero-junctions visible light catalyst BiOBr/g-C prepared by the embodiment of the present invention 23N4It is being added not
With the photocatalysis performance figure after capturing agent.Benzoquinones (BQ), triethanolamine (TEA) and the tert-butyl alcohol (TBA) are O respectively2 -, h+With
The capturing agent of OH.It can be seen from the figure that under visible light illumination, catalytic efficiency is declined after benzoquinones is added, three second are added
Catalytic efficiency is remarkably decreased after hydramine, and after tert-butyl alcohol capture OH is added, catalytic efficiency variation is little.Therefore illustrate h+
With O2 -It is two-dimentional Z-type hetero-junctions visible light catalyst BiOBr/g-C3N4Main active substances.
Fig. 5 shows the Z-type charge transfer mechanism schematic diagram between BiOBr and g-C3N4 nanometer sheet.In the built-in electricity in interface
With the help of, photo-generated carrier, which can be better achieved, to be spatially separating and shifts, wherein the photoproduction in the conduction (CB) of BiOBr
Electronics can be transferred to the valence band (VB) of g-C3N4 and compound with its photohole, promote the photoproduction electricity with higher reducing power
Son can be retained on the CB of g-C3N4, and the photohole of more high oxidative capacity may remain on the VB of BiOBr.Together
When, the interfacial contact mode of 2D/2D reduces interface resistance between BiOBr and g-C3N4 nanometer sheet, is more advantageous to interface charge
Between transfer.
Embodiment 2
Referring to embodiment 1, using condition concentrated hydrochloric acid processing in the same manner as in Example 1, ultrasonic liquid-phase removing preparation g-C3N4
Nanometer sheet, except that: BiOBr and g-C3N4Nanometer sheet mass ratio is 2:3, is then washed by further stirring, centrifugation
It washs, dry, obtaining white powder product is the two-dimentional Z-type hetero-junctions visible light catalyst sample.
Embodiment 3
Referring to embodiment 1, using condition concentrated hydrochloric acid processing in the same manner as in Example 1, ultrasonic liquid-phase removing preparation g-C3N4
Nanometer sheet, except that: BiOBr and g-C3N4Nanometer sheet mass ratio is 3:2, is then washed by further stirring, centrifugation
It washs, dry, obtaining white powder product is the two-dimentional Z-type hetero-junctions visible light catalyst sample.
Embodiment 4
Referring to embodiment 1, using condition concentrated hydrochloric acid processing in the same manner as in Example 1, ultrasonic liquid-phase removing preparation g-C3N4
Nanometer sheet, except that: BiOBr and g-C3N4Nanometer sheet mass ratio is 4:1, is then washed by further stirring, centrifugation
It washs, dry, obtaining white powder product is the two-dimentional Z-type hetero-junctions visible light catalyst sample.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (6)
1. a kind of preparation method of two dimension Z-type hetero-junctions visible light catalyst, it is characterised in that the following steps are included:
1) block g-C is prepared using thermal polymerization3N4Material, be scattered in heated at constant temperature in concentrated hydrochloric acid stir to get white it is molten
Liquid；Centrifugation is washed, dry, obtains white powder A；
2) gained white powder A is added in dispersant solution and is removed by ultrasonic liquid-phase, obtains milky white solution；Centrifugation,
Washing obtains white powder B after dry；
3) it disperses gained white powder B in deionized water, the mixed solution of five water bismuth nitrates and potassium bromide is added dropwise, heating is stirred
It mixes, obtains two-dimentional Z-type hetero-junctions visible light catalyst after centrifugation gained precipitating is dry after reaction.
2. the preparation method of two dimension Z-type hetero-junctions visible light catalyst as described in claim 1, it is characterised in that divide in step 1
The temperature for dissipating the heated at constant temperature in concentrated hydrochloric acid is 60 DEG C, and the time is 4~15h.
3. the preparation method of two dimension Z-type hetero-junctions visible light catalyst as described in claim 1, it is characterised in that divide in step 2
Dispersant solution is the isopropanol water solution that volume fraction is 75%, and ultrasonic liquid-phase splitting time is 6~15h.
4. the preparation method of two dimension Z-type hetero-junctions visible light catalyst as described in claim 1, it is characterised in that five in step 3
Water bismuth nitrate and the mass ratio of potassium bromide are (0.2~5.5): (0.05~1.4).
5. the preparation method of two dimension Z-type hetero-junctions visible light catalyst as described in claim 1, it is characterised in that five in step 3
The mass ratio that the dosage of water bismuth nitrate and potassium bromide accounts for white powder B is 1:4.
6. the preparation method of two dimension Z-type hetero-junctions visible light catalyst as described in claim 1, it is characterised in that add in step 3
Hot temperature is 80 DEG C, mixing time 2h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116282476A (en) * | 2023-03-27 | 2023-06-23 | 重庆大学 | Method for removing organic pollutants in water by catalyzing persulfate through carbon nitride/bismuth oxybromide heterojunction material |
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| CN116282476A (en) * | 2023-03-27 | 2023-06-23 | 重庆大学 | Method for removing organic pollutants in water by catalyzing persulfate through carbon nitride/bismuth oxybromide heterojunction material |
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Application publication date: 20190517 |