CN106964358B - A kind of cadmium ferrite/concave convex rod nanocomposite and its preparation method and application of carbon quantum dot modification - Google Patents
A kind of cadmium ferrite/concave convex rod nanocomposite and its preparation method and application of carbon quantum dot modification Download PDFInfo
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- CN106964358B CN106964358B CN201710270150.8A CN201710270150A CN106964358B CN 106964358 B CN106964358 B CN 106964358B CN 201710270150 A CN201710270150 A CN 201710270150A CN 106964358 B CN106964358 B CN 106964358B
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Abstract
The invention belongs to denitration catalyst manufacture technology fields in environmental protection, and in particular to a kind of cadmium ferrite/concave convex rod nanocomposite and its preparation method and application of carbon quantum dot modification.Lanthanum nitrate, ferric nitrate, citric acid and concave convex rod are add to deionized water stirring sufficiently, are then transferred into water-bath, evaporation obtains wet gel at 50 DEG C~100 DEG C, is impregnated in carbon quantum dot solution after drying calcining, grinds after drying.Photocatalysis denitration is carried out as catalyst using the composite material, compared with traditional SCR denitration, energy consumption is greatly reduced, and is significantly improved under low temperature to the transformation efficiency of NO.
Description
Technical field
The invention belongs to denitration catalyst manufacture technology fields in environmental protection, and in particular to a kind of iron of carbon quantum dot modification
Sour lanthanum/concave convex rod nanocomposite and its preparation method and application.
Background technique
Air pollution is increasingly severe in recent years, major pollutants one of of the nitrogen oxides as atmosphere, to the body of the mankind
Body Health and Living environment causes great harm, such as respiratory disease, acid rain, photochemical fog and solid particulate matter PM
2.5 etc., therefore, the prevention and cure of pollution of nitrogen oxides become especially urgent.
The method of traditional denitration is mainly selective catalytic reduction (SCR), mainly utilizes vanadium titanium catalyst, ammonia or
Nitrogen oxides is decomposed into harmless nitrogen as reducing agent by urea, but that there are low temperature actives is lower, and the disadvantage that energy consumption is larger.
Using solar energy catalyzing and degrading pollutant matter as novel, the potential denitration technology of tool, becomes environmental protection science and grind
The hot spot studied carefully.
Summary of the invention
NO is converted to N under the irradiation of visible light by the technical issues of in order to solve photocatalysis denitration to the greatest extent2,
The present invention provides a kind of cadmium ferrite/concave convex rod nanocomposites of carbon quantum dot modification, and the composite material is with carbon quantum dot
Modify concave convex rod and the compound LaFeO of cadmium ferrite3The composition general formula of/ATP, the composite material indicate are as follows: μ %CQDs/LaFeO3/
ATP, in formula, μ % is carbon quantum dot relative to cadmium ferrite/concave convex rod mass percent, μ=1~5.
The present invention also provides a kind of cadmium ferrite/concave convex rod nanocomposite preparation sides of above-mentioned carbon quantum dot modification
Method:
(1) lanthanum nitrate, ferric nitrate, citric acid and concave convex rod are add to deionized water stirring sufficiently, are then transferred into
In water-bath, evaporation obtains wet gel at 50 DEG C~100 DEG C, grinds after drying calcining up to LaFeO3The nano combined material of/ATP
Material；
(2) by LaFeO obtained in step (1)3/ ATP nanocomposite is impregnated in carbon quantum dot solution, after drying
Grinding obtains cadmium ferrite/concave convex rod nanocomposite of carbon quantum dot modification,
Wherein, by citric acid, the hydro-thermal method in hydrogen peroxide is prepared carbon quantum dot, hydrogen peroxide and lemon in hydrogen peroxide
The molar ratio of lemon acid is 0.3~0.6:1, and hydro-thermal method is specially 160 DEG C of reaction 8h,
Dip time be 15~for 24 hours, drying temperature be 60 DEG C~100 DEG C.
The present invention also provides a kind of cadmium ferrite/concave convex rod nanocomposite applications of above-mentioned carbon quantum dot modification:
Photocatalysis denitration is carried out using the composite material as catalyst.
The beneficial effects of the present invention are:
Often partial size is excessive for the existing obtained carbon quantum dot of preparation process, in this regard, the present invention is in citric acid carbon source water
Hydrogen peroxide is added in thermal process and effectively controls carbon amounts generated after discovery provides hydroxyl environment as hydrothermal system
The partial size of son point is less than 5nm；
Carbon quantum dot/cadmium ferrite/palygorskite nano composite material is prepared using infusion process, perovskite partial size is small,
The microcellular structure of Load Balanced, concave convex rod surface molecular sieve analog promotes to NH3Absorption, while reducing costs, play
The effect of three's concerted catalysis；
Carbon quantum dot has good absorption to visible light, both can be used as electron donor or can be used as electron acceptor, can
It conducts light induced electron faster, is conducive to the raising of catalytic activity；
The present invention has given full play to the excellent photocatalytic activity that carbon quantum dot modification perovskite generates, so that NOx need not be borrowed
Help high temperature SCR react, directly at low temperature can reduction decomposition, low temperature active is good, at the same energy consumption reduce.
Detailed description of the invention
Fig. 1 is raw material ATP, prepared CQDs, CQDs/LaFeO in embodiment 13The XRD spectra of/ATP.
Fig. 2 is CQDs/LaFeO prepared by embodiment 13The TEM photo of/ATP in 5nm scale range.
Fig. 3 is CQDs/LaFeO prepared by embodiment 13The TEM photo of/ATP in 50nm scale range.
Fig. 4 (a) is 3%CQDs/LaFeO prepared by comparative example 13In/ATP, CQD is in 10nm scale range
TEM photo；Fig. 4 (b) is 3%CQDs/LaFeO prepared by embodiment 13In/ATP, CQD shines in the TEM of 10nm scale range
Piece.
The LaFeO that Fig. 5 is 1 raw material A TP of embodiment, prepared by 1 step of embodiment (1)3/ ATP, 1 step of embodiment (2) preparation
3%CQDs/LaFeO34%CQDs/LaFeO prepared by/ATP, embodiment 435%CQDs/ prepared by/ATP, embodiment 5
LaFeO3/ ATP is respectively to the inversion cuver of nitrogen oxides.
Specific embodiment
Embodiment 1
The preparation of carbon quantum dot:
The citric acid for weighing 0.53g is dissolved in the hydrogen peroxide that 20ml concentration of hydrogen peroxide is 0.055mol/L, ultrasonic dissolution
10min obtains colourless solution；Above-mentioned solution is put into 100ml ptfe autoclave, then 160 DEG C of hydro-thermal reaction 8h；Instead
Reaction kettle is taken out after answering, obtained solution is first centrifuged, and transfers to bag filter (molecular cut off MWCO=1000) two
Dialyse 12h in secondary water, is finally transferred to 70 DEG C of vacuum ovens dryings, obtains carbon quantum dot particle CQDs；
(1) 0.4012g lanthanum nitrate, 0.4988g ferric nitrate, 0.5g citric acid 1g concave convex rod are added to 100ml deionization
It stirs sufficiently, is then transferred into water-bath in water, 18h is evaporated at 60 DEG C and obtains wet gel, with 600 DEG C after 80 DEG C of drying
(heating rate is 1 DEG C/min) calcining 2h, grinds up to LaFeO3/ ATP nanocomposite；
(2) the carbon quantum dot particle 0.03g of above-mentioned preparation is dissolved in the deionized water of 20ml and obtains carbon quantum dot solution,
Take LaFeO obtained in step (1)3/ ATP nanocomposite 1g impregnates under room temperature (25 DEG C) in the carbon quantum dot solution
18h, grinding obtains cadmium ferrite/concave convex rod nanocomposite 3%CQDs/ of carbon quantum dot modification after 80 DEG C of drying
LaFeO3/ATP。
X-ray powder is carried out to cadmium ferrite/concave convex rod nanocomposite of the modification of carbon quantum dot prepared by the present embodiment
Last diffraction experiment, and its pattern and structure are observed under transmission electron microscope,
XRD spectrum is as shown in Figure 1, there is carbon quantum dot, cadmium ferrite and the respective spy of concave convex rod in the XRD of composite material
Diffraction maximum is levied, in combination with TEM photo Fig. 2, it was demonstrated that carbon quantum dot successfully loads to LaFeO3Above/ATP；
Shown in TEM photo such as Fig. 3, Fig. 4 (b), it can be seen from the figure that cadmium ferrite particle be less than 10nm and with concave convex rod compared with
To be equably combined with each other；The CQDs for preparing of hydrogen peroxide is added, particle size is uniform, and partial size is less than 5nm, with concave convex rod compared with
It is consistent with the result of XRD to be equably combined with each other.
The present embodiment raw material A TP, this reality of 150mg are separately added into photocatalysis auxiliary-SCR denitration device quartz ampoule
Apply the LaFeO of a step (1) preparation3CQDs/LaFeO prepared by/ATP, the present embodiment step (2)3/ATP；NH3, NO, O2Just
Beginning concentration is respectively 1000ppm, 1000ppm, 3% (relative to total gas flow rate), remaining is nitrogen, air speed 25000h-1, gas
For the control of body total flow in 100ml/min, used light source is the xenon lamp (adding ultraviolet filter plate) of 200W；Flue gas is used after reaction 8h
Detector test residue NO concentration, measures ATP, LaFeO3/ATP、CQDs/LaFeO3The inversion cuver such as Fig. 5 institute of/ATP to NO
Show, it can be seen from the figure that ATP is about 20%, LaFeO to the conversion ratio of NOx3/ ATP to the conversion ratio of NO up to 50% or more,
And CQDs/LaFeO3/ ATP is to the conversion ratio of NO up to 95% or more.
Comparative example 1
Compared to embodiment 1, any hydrogen peroxide is not added in the preparation process of carbon quantum dot, remaining operation is the same as implementation
Example 1:
The preparation of carbon quantum dot:
The citric acid for weighing 0.53g is dissolved in 20ml deionized water, and ultrasonic dissolution 10min obtains colourless solution；It will be above-mentioned
Solution is put into 100ml ptfe autoclave, then 160 DEG C of hydro-thermal reaction 8h；Reaction kettle is taken out after reaction, will be obtained
Solution be first centrifuged, transfer in bag filter (molecular cut off MWCO=1000) secondary water the 12h that dialyses, be finally transferred to 70
DEG C vacuum oven is dry, obtains carbon quantum dot particle CQDs；
(1) with embodiment 1；
(2) with embodiment 1.
It is electric in transmission to cadmium ferrite/concave convex rod nanocomposite of the modification of carbon quantum dot prepared by this comparative example
Its pattern and structure under the microscope:
Shown in TEM photo such as Fig. 4 (a), it can be seen from the figure that the CQDs of hydrogen peroxide preparation is not added, particle size point
The case where cloth is uneven, is significantly greater than 10nm there are partial size.
Photocatalysis auxiliary-SCR denitration test experience is with embodiment 1, the CQDs/LaFeO for preparing in comparative example 13/
ATP only reaches 82% to the conversion ratio of NO.
Embodiment 2
(1) with embodiment 1；
(2) the carbon quantum dot particle 0.01g prepared in embodiment 1 is dissolved in the deionized water of 20ml and obtains carbon quantum dot
Solution takes LaFeO obtained in step (1)3/ ATP nanocomposite 1g is in the carbon quantum dot solution under room temperature (25 DEG C)
For 24 hours, grinding obtains cadmium ferrite/concave convex rod nanocomposite of carbon quantum dot modification to dipping after 100 DEG C of drying.
Embodiment 3
(1) with embodiment 1；
(2) the carbon quantum dot particle 0.02g prepared in embodiment 1 is dissolved in the deionized water of 20ml and obtains carbon quantum dot
Solution takes LaFeO obtained in step (1)3/ ATP nanocomposite 1g is in the carbon quantum dot solution under room temperature (25 DEG C)
20h is impregnated, grinding obtains cadmium ferrite/concave convex rod nanocomposite of carbon quantum dot modification after 80 DEG C of drying.
Embodiment 4
(1) with embodiment 1；
(2) the carbon quantum dot particle 0.04g prepared in embodiment 1 is dissolved in the deionized water of 20ml and obtains carbon quantum dot
Solution takes LaFeO obtained in step (1)3/ ATP nanocomposite 1g is in the carbon quantum dot solution under room temperature (25 DEG C)
18h is impregnated, grinding obtains cadmium ferrite/concave convex rod nanocomposite of carbon quantum dot modification after 80 DEG C of drying.
Embodiment 5
(1) with embodiment 1；
(2) the carbon quantum dot particle 0.05g prepared in embodiment 1 is dissolved in the deionized water of 20ml and obtains carbon quantum dot
Solution takes LaFeO obtained in step (1)3/ ATP nanocomposite 1g is in the carbon quantum dot solution under room temperature (25 DEG C)
15h is impregnated, grinding obtains cadmium ferrite/concave convex rod nanocomposite of carbon quantum dot modification after 60 DEG C of drying.
Claims (5)
1. a kind of cadmium ferrite/concave convex rod nanocomposite of carbon quantum dot modification, it is characterised in that: the composite material is
The concave convex rod and ferrous acid lanthanide composite material of carbon quantum dot modification, the composition general formula of the composite material are CQDs/LaFeO3/ ATP,
Middle carbon quantum dot content is 1-5wt%.
2. a kind of cadmium ferrite/concave convex rod nanocomposite preparation method of carbon quantum dot modification as described in claim 1,
It is characterized by: the preparation method is that,
(1) lanthanum nitrate, ferric nitrate, citric acid and concave convex rod are add to deionized water stirring sufficiently, are then transferred into water-bath
In pot, evaporation obtains wet gel at 50 DEG C -100 DEG C, grinds after drying calcining up to LaFeO3/ ATP nanocomposite；
(2) by LaFe0 obtained in step (1)3/ ATP nanocomposite is impregnated in carbon quantum dot solution, is ground after drying
Obtain cadmium ferrite/concave convex rod nanocomposite of carbon quantum dot modification；The carbon quantum dot is by citric acid in dioxygen
Hydro-thermal method is prepared in water；In the hydrogen peroxide, the molar ratio of hydrogen peroxide and citric acid is 0.3-0.6:1.
3. cadmium ferrite/concave convex rod nanocomposite preparation method of carbon quantum dot modification as claimed in claim 2, special
Sign is: the hydro-thermal method is specially 160 DEG C of reaction 8h.
4. cadmium ferrite/concave convex rod nanocomposite preparation method of carbon quantum dot modification as claimed in claim 2, special
Sign is: in step (2), dip time 15-24h, drying temperature is 60 DEG C -100 DEG C.
5. a kind of cadmium ferrite/concave convex rod nanocomposite application of carbon quantum dot modification as described in claim 1, special
Sign is: carrying out photocatalysis denitration for the composite material as catalyst.
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| CN111185178B (en) * | 2020-02-03 | 2022-11-04 | 齐齐哈尔大学 | Preparation method of carbon quantum dot modified denitration catalyst |
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| CN115427349A (en) * | 2020-05-21 | 2022-12-02 | 株式会社吴羽 | Composition and method for producing the same |
| JP2022047294A (en) * | 2020-09-11 | 2022-03-24 | 株式会社クレハ | Photocatalyst composite |
| CN115259233B (en) * | 2022-07-29 | 2023-12-19 | 安徽工业大学 | SnO-based 2 Quantum dot doped LaFeO 3 Nanomaterial, gas sensor, and preparation method and application of nanomaterial |
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