CN107115885B - A kind of modified g-C of PEG3N4-Cu2The preparation method and applications of O composite catalyst - Google Patents
A kind of modified g-C of PEG3N4-Cu2The preparation method and applications of O composite catalyst Download PDFInfo
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Abstract
The present invention provides a kind of with the modified g-C of PEG3N4‑Cu2The preparation method and applications of O composite catalyst, described method includes following steps: obtaining one first solution, first solution includes the Cu of dissolved state2+Ion and PEG-400；The g-C of protonation is added in first solution3N4, stirring, ultrasound, acquisition suspension；Xylitol is added into the suspension under stirring, adjusts pH value to 10-12, stirs to obtain mixed liquor；The mixed liquor is heated to 150-200 DEG C, isothermal reaction 25-35h in high-pressure reaction vessel, natural cooling obtains reactant；Reactant after cooling is separated by solid-liquid separation, is cleaned, vacuum drying obtains solid product；The solid product is heated to 150-250 DEG C of holding constant temperature 1h-3h under inert atmosphere protection, g-C is made3N4‑Cu2O composite catalyst.The composite catalyst has stronger visible light absorption capacity, photocatalysis performance and stability enhancing.
Description
Technical field
The invention belongs to water-treatment technology field more particularly to a kind of modified g-C of PEG3N4-Cu2O composite catalyst
Preparation method and applications.
Background technique
With the rapid development of modern industry, the fossil energies such as matchmaker, petroleum, natural gas are utilized by exhaustive exploitation, are caused tight
The energy crisis and problem of environmental pollution of weight.Therefore, the control technology for seeking a kind of environmental pollution of low energy consumption is extremely urgent.Too
Sun can develop and use it and be of great significance as a kind of cleaning, cheap renewable energy.Photocatalysis technology is as a kind of
Effective method is handled to environmental pollutants with it and has generated preferable effect, is urged using sunlight catalytic semiconductor light
Agent control environmental contaminants are expected to solve energy crisis and environmental problem that society faces, and nano-photocatalyst material is applied to light
Organic pollutant in catalytic degradation waste water has obtained wide confirmation.Cuprous oxide is the New Generation Optical after titanium dioxide
Catalyst, due to preferable photocatalysis performance, in terms of attention by researcher, be kind great
The green photochemical catalyst of development prospect.But Cu2O easily inactivated in degradation of contaminant and photo-generate electron-hole pairs it is rapid
It is compound so that Cu2The photocatalysis efficiency of O is to be improved.
Summary of the invention
In view of the above-mentioned drawbacks in the prior art, the main purpose of the present invention is to provide a kind of with the modified g-C of PEG3N4-
Cu2The preparation method and applications of O composite catalyst, the catalyst have stronger visible light absorption capacity, photocatalytic
Energy and stability enhancing.
In order to achieve the above object, the present invention adopts the following technical scheme: a kind of modified g-C of PEG3N4-Cu2O is compound
The preparation method of catalyst, described method includes following steps:
The first solution is obtained, first solution includes the Cu of dissolved state2+And polyethylene glycol PEG-400；
The g-C of protonation is added in first solution3N4, stirring, ultrasound, acquisition suspension；
Xylitol is added into the suspension under stirring, adjusts pH value to 10-12, stirs to obtain mixed liquor；
The mixed liquor is heated to 150-200 DEG C in high-pressure reaction vessel, isothermal reaction 25-35h is reacted
Object；
The reactant after cooling is separated by solid-liquid separation, is cleaned, vacuum drying obtains solid product；
The solid product is heated to 150-250 DEG C of holding constant temperature 1h-3h under atmosphere protection, g-C is made3N4-
Cu2O composite catalyst.
As a further preference, in the composite catalyst, the g-C3N4With Cu2The mass ratio of O is 1:1-1:5.
As a further preference, the rate of heat addition of the solid product is 2-3k/min.
As a further preference, the g-C of the protonation3N4Preparation method include: to be in heating rate by dicyandiamide
After being warming up to 500-600 DEG C under conditions of 1-3K/min, 3-5h is calcined, cooling obtains powder, grinds；In powder after grinding
Concentrated sulfuric acid mixing, stirring is added, ultrasound obtains mixture；The mixture and water are mixed, milky is obtained and suspends
Liquid, the g-C by milk-white coloured suspension centrifugation, washing and drying, after being acidified3N4；By the g-C after the acidification3N4?
50-75 DEG C of heat reflux 4-8h, filters, the g-C of washing and dry protonation3N4。
As a further preference, the mixing time is 6-10h, and the ultrasonic time is 1-3h.
A kind of g-C3N4-Cu2The application of O composite catalyst, the g-C3N4-Cu2O composite catalyst is made in radiation of visible light
With the organic pollutant in lower treating wastewater through catalysis of connected.
As a further preference, described handle includes:
G-C is added in waste water3N4-Cu2O composite catalyst, stirring form mixture；
The mixture is placed in the range of exposures of visible light；
Visible light cooperates with g-C3N4-Cu2Organic pollutant in O composite catalyst degrading waste water.
As a further preference, having comprising Anthraquinones, quinone imides, oxa anthracenes and azo in the waste water
One of machine pollutant is a variety of.
As a further preference, the organic pollutant in the waste water be selected from reactive brilliant bule, methylene blue, rhodamine B,
Reactive brilliant red and methyl orange.
As a further preference, the initial concentration of the Organic Pollutants in Wastewater is 10-30mg/L.
As a further preference, the g-C in the mixture3N4-Cu2The additional amount of O composite catalyst is 0.3-1g/
L。
The beneficial effects of the present invention are: coupling between the semiconductor material that the present invention passes through narrow band gap promotes
Cu2O photocatalytic activity has been successfully prepared g-C using solvent-thermal method and in conjunction with high-temperature calcination3N4-Cu2O composite photocatalyst
Agent, the composite catalyst g-C3N4And Cu2O is closely grown together, and two phase compositions coexist and have in close contact circle
Face forms g-C3N4-Cu2The heterojunction structure of O plane-plane contact.Compared to the g-C of pure phase3N4And Cu2O, g-C3N4-Cu2O is multiple
Condensation material has stronger visible light absorption capacity, and specific surface area is bigger, and crystallinity is more preferable.g-C3N4-Cu2O hetero-junctions is preferable
Energy band mating structure ensures that the photocatalysis performance of compound, than single-phase g-C3N4Or Cu2O is greatly improved.
Wherein, the present invention is using the g-C protonated3N4, there is apparent dispersibility, it is bigger specific surface area to be formed
Flaky nanometer structure, to more fully contact Cu2O forms even closer heterojunction structure.In addition, the present invention is in preparation side
PEG-400 is added in method, PEG-400 is not only to Cu2The particle and pattern of O has preferable stabilization, and has simple, warp
Ji has the characteristics that Green Chemistry.
Detailed description of the invention
Fig. 1 is g-C3N4、Cu2G-C in O and the embodiment of the present invention3N4-Cu2The XRD diagram of O composite catalyst.
Fig. 2 a-2b is g-C in the embodiment of the present invention 13N4-Cu2The SEM of O composite catalyst schemes.
Fig. 3 is g-C in the embodiment of the present invention 13N4-Cu2The BET test chart of O composite catalyst.
Fig. 4 is in Vis, g-C3N4And Cu2The degradation situation schematic diagram of methyl orange in the various combination reaction system of O.Fig. 5
For the g-C in the embodiment of the present invention 13N4-Cu2O composite catalyst is under visible light to the circulation experiment knot of methyl orange degradation performance
Fruit schematic diagram.
Specific embodiment
The present invention is by providing a kind of modified g-C of PEG3N4-Cu2The preparation method and applications of O composite catalyst, solution
Determined existing Cu2The defect that O photocatalyst treatment Organic Pollutants in Wastewater photocatalysis performance is poor, cycle performance is unstable etc.,
G-C prepared by the present invention3N4-Cu2O composite photo-catalyst has stronger visible light absorption capacity, photochemical catalyst catalytic performance
Enhance with stability.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is:
The modified g-C of PEG of the embodiment of the present invention3N4-Cu2The preparation method of O composite catalyst, the method includes as follows
Step:
The first solution is obtained, first solution includes the Cu of dissolved state2+And PEG-400；
The g-C of protonation is added in first solution3N4, stirring, ultrasound, acquisition suspension；
Xylitol is added into the suspension under stirring, adjusts pH value to 10-12, stirs to obtain mixed liquor；
The mixed liquor is heated to 150-200 DEG C in high-pressure reaction vessel, isothermal reaction 25-35h is reacted
Object；
The reactant after cooling is separated by solid-liquid separation, is cleaned, vacuum drying obtains solid product；
The solid product is heated to 150-250 DEG C of holding constant temperature 1h-3h under atmosphere protection, g-C is made3N4-
Cu2O composite catalyst.
g-C3N4With good chemical stability and high-temperature stability, most of visible light can be absorbed.And g-C3N4's
Forbidden bandwidth is moderate, can be matched by good energy band and be coupled with a variety of semiconductor materials, and improves light induced electron and hole
Separative efficiency.And p-type semiconductor Cu2O and n-type semiconductor g-C3N4Two kinds of semiconductor combinations can form p-n heterojunction.For p-n
For type hetero-junctions, p-type semiconductor fermi level is close to valence band, and the fermi level of n-type semiconductor is led close to conduction band, two and half
Body reaches thermodynamical equilibrium in combination, and fermi level time is gradually close, can be because of photo-generated carrier at the both ends of hetero-junctions
Movement and form internal electric field.The presence of internal electric field can promote the separation in light induced electron and hole, thus heterojunction photocatalyst
There is better photocatalysis performance than single semiconductor catalyst.Different preparation conditions and method can directly affect the micro- of material
Structure, particle size and performance are seen, and influences its application.
The embodiment of the present invention is based on solvent-thermal method and high-temperature calcination by g-C3N4Grow into Cu2G- has been made in the surface O
C3N4-Cu2O composite photo-catalyst has many advantages, such as that mild condition, particle are uniform, pattern is easy to control.Pairing of the embodiment of the present invention
At photochemical catalyst carried out the characterization of structure, pattern and optical property, and had evaluated so that methyl orange etc. is simulating pollution object
The photocatalytic degradation capability of composite catalyst.The experimental results showed that g-C3N4And Cu2Two phase composition of O coexists and has close
Contact interface forms g-C3N4-Cu2The heterojunction structure of O plane-plane contact.In addition to this g-C3N4-Cu2O hetero-junctions is preferable
Energy band mating structure ensures that the photocatalysis performance of compound, than single-phase g-C3N4Or Cu2O is greatly improved, and
And there is good photochemical stability.It tests and analyzes in conjunction with free radical capture, propose g-C3N4-Cu2O composite photocatalyst
The possible photocatalytic mechanism of agent.
The whole of composite catalyst catalytic performance of the embodiment of the present invention improves due to p-n junction hetero-junctions effectively facilitates charge
Separation, inhibit electron-hole compound and absorb the extension of optical wavelength range, compared to homogenous material, it is urged with higher
Change activity and stability.
G-C of the embodiment of the present invention3N4-Cu2O composite catalyst can effectively give up in catalytic treatment under radiation of visible light effect
Organic pollutant in water.
The embodiment of the present invention has studied catalyst of the embodiment of the present invention for having in treating wastewater through catalysis of connected by taking methyl orange as an example
When machine pollutant, to the degradation effect of organic pollutant in water environment, but the embodiment of the present invention is not limited to only to first
Base orange works, other pollutants of degrading also can achieve the effect of similar catalytic degradation.
In order to which above and other purpose, feature and the advantage of the present invention can be clearer and more comprehensible, several implementations are cited below particularly
Example, to illustrate g-C of the present invention3N4-Cu2The preparation method and applications of O composite catalyst.
Embodiment 1
Raw material and reagent
Dicyanodiamine (C2H4N4), Salzburg vitriol (CuSO4·5H2O), sodium hydroxide (NaOH), hydrochloric acid (HCl) are equal
To analyze pure (AR), it is purchased from Sinopharm Chemical Reagent Co., Ltd.；Xylitol (C5H1205), methyl orange (C14H14N3NaO3S)
It is to analyze pure (AR), is purchased from Shanghai Aladdin biochemical technology limited liability company.
g-C3N4Preparation
G-C is prepared using the method for high temperature pyrolysis dicyandiamide3N4: it weighs 4g dicyandiamide and is placed in corundum crucible with cover, and
Crucible is put into Muffle furnace, in air atmosphere with the heating rate temperature programming of 2k/min to 550 DEG C, and keeps the temperature 4h, to
Resulting yellow powder is ground into 30min after product natural cooling, grinding gained primary product is spare.The mixing 10ml concentrated sulfuric acid adds
Enter in 50ml flask, stir 8h, ultrasonic 1h at room temperature, the mixture after stirring is slowly poured into 100ml deionized water while being stirred
It mixes.The milk-white coloured suspension 3000r centrifugation 10min of acquisition is simultaneously washed with deionized.80 DEG C of dryings.G- after weighing acidification
C3N40.4g is poured into equipped in 200ml flask, 65 DEG C of heat reflux 6h, filtering and washing and 80 DEG C of dry g-C3N4。
g-C3N4-Cu2The preparation of O composite catalyst
First under magnetic stirring by 1.25gCuSO4·5H2O is added in 35mL deionized water, then plus 5mlPEG-
400, when solution becomes navy blue, continue that g-C is added into above-mentioned solution3N4(g-C3N4: Cu2The mass ratio of O is 1:5), magnetic
Ultrasonic 1h is further continued for after power stirring 1h, uniform suspension is made, and then to above-mentioned suspension under conditions of magnetic agitation
The middle xylitol that 1.5g is added is later 12 with the pH that 1mol/L NaOH solution adjusts above-mentioned suspension, after magnetic agitation 1h,
The autoclave (pressure 0.8MPa) that above-mentioned mixed liquor is transferred to polytetrafluoroethyllining lining is heated to 180 DEG C of isothermal reactions
After 30h, natural cooling after reaction kettle is taken out, the sample suction filtration in liner is separated, three times with deionized water repeated flushing,
60 DEG C of dry 8h in a vacuum drying oven.Resulting sample is finally heated to 200 DEG C of guarantors under protection of argon gas with 2.3k/min
Constant temperature 2h is held, g-C is made3N4-Cu2O hetero-junctions.
Raw material is similar to Example 1 with reagent, repeats no more.
g-C3N4Preparation
G-C is prepared using the method for high temperature pyrolysis dicyandiamide3N4: it weighs 4g dicyandiamide and is placed in corundum crucible with cover, and
Crucible is put into Muffle furnace, in air atmosphere with the heating rate temperature programming of 1k/min to 500 DEG C, and keeps the temperature 5h, to
Resulting yellow powder is ground into 30min after product natural cooling, grinding gained primary product is spare.The mixing 10ml concentrated sulfuric acid adds
Enter in 50ml flask, stir 6h, ultrasonic 2h at room temperature, the mixture after stirring is slowly poured into 100ml deionized water while being stirred
It mixes.The milk-white coloured suspension 3000r centrifugation 10min of acquisition is simultaneously washed with deionized.80 DEG C of dryings.G- after weighing acidification
C3N40.4g is poured into equipped in 200ml flask, 50 DEG C of heat reflux 8h, filtering and washing and 80 DEG C of dry g-C3N4。
g-C3N4-Cu2The preparation of O composite catalyst
First under magnetic stirring by 1.25gCuSO4·5H2O is added in 35mL deionized water, then plus 5ml PEG-
400, when solution becomes navy blue, continue that g-C is added into above-mentioned solution3N4(g-C3N4: Cu2The mass ratio of O is 1:1), magnetic
Ultrasonic 1h is further continued for after power stirring 1h, uniform suspension is made, and then to above-mentioned suspension under conditions of magnetic agitation
The middle xylitol that 1.5g is added is later 10 with the pH that 1mol/L NaOH solution adjusts above-mentioned suspension, after magnetic agitation 1h,
The autoclave (pressure 0.6MPa) that above-mentioned mixed liquor is transferred to polytetrafluoroethyllining lining is heated to 150 DEG C of isothermal reactions
After 35h, natural cooling after reaction kettle is taken out, the sample suction filtration in liner is separated, three times with deionized water repeated flushing,
60 DEG C of dry 8h in a vacuum drying oven.Resulting sample is finally heated to 150 DEG C of holdings under protection of argon gas with 1k/min
G-C is made in constant temperature 3h3N4-Cu2O hetero-junctions.
Raw material is similar to Example 1 with reagent, repeats no more.
g-C3N4Preparation
G-C is prepared using the method for high temperature pyrolysis dicyandiamide3N4: it weighs 4g dicyandiamide and is placed in corundum crucible with cover, and
Crucible is put into Muffle furnace, in air atmosphere with the heating rate temperature programming of 3k/min to 600 DEG C, and keeps the temperature 3h, to
Resulting yellow powder is ground into 30min after product natural cooling, grinding gained primary product is spare.The mixing 10ml concentrated sulfuric acid adds
Enter in 50ml flask, stir 10h, ultrasonic 3h at room temperature, the mixture after stirring is slowly poured into 100ml deionized water while being stirred
It mixes.The milk-white coloured suspension 3000r centrifugation 10min of acquisition is simultaneously washed with deionized.80 DEG C of dryings.G- after weighing acidification
C3N40.4g is poured into equipped in 200ml flask, 75 DEG C of heat reflux 4h, filtering and washing and 80 DEG C of dry g-C3N4。
g-C3N4-Cu2The preparation of O composite catalyst
First under magnetic stirring by 1.25gCuSO4·5H2O is added in 35mL deionized water, then plus 5ml PEG-
400, when solution becomes navy blue, continue that g-C is added into above-mentioned solution3N4(g-C3N4: Cu2The mass ratio of O is 3:5), magnetic
Ultrasonic 1h is further continued for after power stirring 1h, uniform suspension is made, and then to above-mentioned suspension under conditions of magnetic agitation
The middle xylitol that 1.5g is added is later 12 with the pH that 1mol/L NaOH solution adjusts above-mentioned suspension, after magnetic agitation 1h,
The autoclave (pressure 0.5MPa) that above-mentioned mixed liquor is transferred to polytetrafluoroethyllining lining is heated to 200 DEG C of isothermal reactions
After 25h, natural cooling after reaction kettle is taken out, the sample suction filtration in liner is separated, three times with deionized water repeated flushing,
60 DEG C of dry 8h in a vacuum drying oven.Resulting sample is finally heated to 250 DEG C of holdings under protection of argon gas with 3k/min
G-C is made in constant temperature 1h3N4-Cu2O hetero-junctions.
g-C3N4-Cu2The characterization of O composite catalyst
Fig. 1 is g-C3N4、Cu2G-C in O and the embodiment of the present invention3N4-Cu2The XRD diagram of O composite catalyst.It can from figure
See, pure phase g-C3N4Sample has 2 diffraction maximums, corresponds respectively to g-C3N4(002) in (JCPDS 87-1526) card and
(100) crystal face, wherein 12.86 ° of diffraction maximum corresponds to gC in position3N4(100) crystal face diffraction, be by graphite phase carbon nitride layer
Interior basic structural unit s-triazine ring periodic arrangement and generate, diffracted intensity is weaker.Positioned at 27.46 ° of diffraction maximum pair
Ying Yu has the g-C of layer structure feature3N4(002) crystal face diffraction, be accumulated to be formed by the interlayer of cyclic aromatic object, therefore its
Diffracted intensity is stronger.When we are by g-C3N4And Cu2O according to different dopings carry out it is compound after, with Cu2O doping is not
It is disconnected to increase, g-C3N4The two feature peak intensities constantly weakening.In g-C3N4-Cu22 θ of the angle of diffraction in O composite sample are as follows:
It is a series of at 29.582 °, 36.441 °, 42.328 °, 61.406 °, 73.556 °, 77.414 ° six sharp and narrow then to correspond to
Cu2110,111,200,220,311,222 crystal faces in O (JCPDS 78-2076), show Cu2The crystallinity of O is preferable.By two
After kind of Material cladding, their diffraction maximum all occurs in the composite photocatalyst, illustrate composite photo-catalyst be strictly by
g-C3N4And Cu2Two phase composition of O, while each corresponding diffraction peak intensity of phase content ratio is directly proportional.
Fig. 2 a-2b is g-C in the embodiment of the present invention 13N4-Cu2The SEM of O composite catalyst schemes.By the embodiment of the present invention
The modified g-C in the surface PEG3N4-Cu2O shows apparent dispersibility, g-C3N4And Cu2O is closely grown together, shape
At close heterojunction structure, to promote efficiently separating for electrons and holes, to show excellent photocatalysis performance.
Fig. 3 is g-C in the embodiment of the present invention 13N4-Cu2The BET test chart of O composite catalyst.It can be found that compared to not
The g-C for adding PEG to prepare3N4-Cu2O (does not add PEG-400, other steps are similar, and make in 1 method of the embodiment of the present invention
Standby obtained original g-C3N4-Cu2O), the g-C of embodiment 13N4-Cu2O composite catalyst specific surface area expands 3 times or more,
This is likely to be the g-C prepared with SEM embodiment 1 shown in figure3N4-Cu2It is related that O forms polymolecularity.BET analyzes result
As shown in the following table 1:
Table 1
Visible light of the embodiment of the present invention cooperates with g-C in order to obtain3N4-Cu2O composite catalyst handles organic contamination in waste water
The effect of object, carrying out following a series of experiments to composite catalyst prepared by embodiment is proved:
g-C3N4-Cu2The research of the photocatalysis performance of O
Photocatalytic degradation experiment is using self-designed L ED lamp as light source, and a set of cups outer layer is by condensed water to ensure that photocatalysis is anti-
It should carry out at a constant temperature.Be 20mg/L with concentration, volume for methyl orange (MO) solution of 50mL does target degradation product, catalyst
Dosage is 0.025g.The absorption stirring 30min under first dark unglazed environment before light-catalyzed reaction, to ensure to reach absorption
Balance, sampling is primary at regular intervals after turning on light, every sub-sampling 1.2mL, reaction time 30min.With 0.45 μm after sampling
Water system syringe membrane filtration removes remaining a small amount of catalyst in sample, is placed in the centrifuge tube of oiling 0.1mL ethyl alcohol, uses purple
The absorbance of outer visible spectrophotometer detection filtrate.With the degradation rate C/C of pollutant0Characterize the photocatalysis performance of composite catalyst.
Pass through the g-C prepared to the embodiment of the present invention 1 under different systems3N4-Cu2Discussion of the O to the degradation situation of MO, knot
Fruit is as shown in Figure 4, it has been found that in the control experiment that photochemical catalyst is not added, MO is hardly degraded, this shows that MO is quite steady
It is fixed, to eliminate the possibility of MO self-degradation process generation.As single-phase g-C3N4Or Cu2After O is added, although the degradation to MO
Have certain facilitation, but 30min to the degradation of MO also less than 20%, and the g-C of the embodiment of the present invention 13N4-Cu2O
After composite catalyst addition system, there are significant facilitation, under visible light illumination, 30min to the degrading activity of MO
The MO of degradation 85%.These are the result shows that g-C3N4-Cu2O/Vis system is compared to its single-phase photocatalytic system to the drop of MO
Solution is more efficient, and photocatalysis performance under visible light is good.
g-C3N4-Cu2The research of O stability
The stability of solid photocatalysts is extremely important in solid-liquid reaction.In order to test g-C3N4/Cu2O's is steady
Qualitative and recyclability, the catalyst after each reaction is collected again to be re-added in circular response next time.
As shown in figure 5, reaction 30min is basically unchanged the degradation rate of MO after circulation 6 times, catalyst stability is high.
Technical solution in above-mentioned the embodiment of the present application, at least have the following technical effects or advantages:
The coupling between semiconductor material that the present invention passes through narrow band gap promotes Cu2O photocatalytic activity, utilizes solvent
Thermal method has simultaneously been successfully prepared g-C in conjunction with high-temperature calcination3N4-Cu2O composite photo-catalyst, the composite catalyst neutral body six
Angle star Cu2O is dispersed into independent angle small one by one, g-C by PEG3N4In Cu2The surface O quickly grows into surface-to-surface composite junction
Structure, two phase compositions coexist and have close contact interface, form g-C3N4-Cu2The heterojunction structure of O plane-plane contact.Phase
Than in the g-C of pure phase3N4And Cu2O, g-C3N4-Cu2O composite material has stronger visible light absorption capacity, and specific surface area is more
Greatly, crystallinity is more preferable. g-C3N4-Cu2The preferable energy band mating structure of O hetero-junctions ensures that the photocatalytic of compound
Can, than single-phase g-C3N4Or Cu2O is greatly improved.
Wherein, the present invention is using the g-C protonated3N4, there is apparent dispersibility, it is bigger specific surface area to be formed
Flaky nanometer structure, to more fully contact Cu2O forms even closer heterojunction structure.In addition, the present invention is in preparation side
PEG-400 is added in method, PEG-400 is not only to Cu2The particle and pattern of O has preferable stabilization, and has simple, warp
Ji has the characteristics that Green Chemistry.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to encompass these modification and variations and exists
It is interior.
Claims (9)
1. a kind of modified g-C of PEG3N4-Cu2The preparation method of O composite catalyst, it is characterised in that: the method includes as follows
Step:
The first solution is obtained, first solution includes the Cu of dissolved state2+And PEG-400；
The g-C of protonation is added in first solution3N4, stirring, ultrasound, acquisition suspension；
Xylitol is added into the suspension under stirring, adjusts pH value to 10-12, stirs to obtain mixed liquor；
The mixed liquor is heated to 150-200 DEG C, isothermal reaction 25-35h in high-pressure reaction vessel, obtains reactant；
The reactant after cooling is separated by solid-liquid separation, is cleaned, vacuum drying obtains solid product；
The solid product is heated to 150-250 DEG C of holding constant temperature 1h-3h under atmosphere protection, the modified g-C of PEG is made3N4-
Cu2O composite catalyst；
In the composite catalyst, the g-C3N4With Cu2The mass ratio of O is 1: 1-1: 5；The PEG-400 and Cu2+Volume
Mass ratio is 125: 8mL/g.
2. the modified g-C of PEG according to claim 13N4-Cu2The preparation method of O composite catalyst, it is characterised in that:
The rate of heat addition of the solid product is 2-3k/min.
3. the modified g-C of PEG according to claim 13N4-Cu2The preparation method of O composite catalyst, it is characterised in that:
The g-C of the protonation3N4Preparation method include: by dicyandiamide heating rate be 1-3K/min under conditions of be warming up to
After 500-600 DEG C, 3-5h is calcined, cooling obtains powder, grinds；Concentrated sulfuric acid mixing is added in powder after grinding, stirs, surpasses
Sound obtains mixture；The mixture and water are mixed, milk-white coloured suspension is obtained, by the milk-white coloured suspension from
The heart, washing and drying, the g-C after being acidified3N4；By the g-C after the acidification3N4In 50-75 DEG C of heat reflux 4-8h, filter,
It washs and the g-C of dry protonation3N4。
4. the modified g-C of PEG according to claim 33N4-Cu2The preparation method of O composite catalyst, it is characterised in that:
The mixing time is 6-10h, and the ultrasonic time is 1-3h.
5. PEG made from the preparation method as described in any one of claim 1-4 claim is modified g-C3N4-Cu2O is compound to be urged
The application of agent, it is characterised in that: the modified g-C of the PEG3N4-Cu2O composite catalyst is under radiation of visible light effect at catalysis
Manage the pollutant in organic wastewater.
6. the modified g-C of PEG according to claim 53N4-Cu2The application of O composite catalyst, it is characterised in that: the place
Reason includes:
The modified g-C of PEG is added in waste water3N4-Cu2O composite catalyst, stirring form mixture；
The mixture is placed in the range of exposures of visible light；
Visible light cooperates with the modified g-C of PEG3N4-Cu2Organic pollutant in O composite catalyst degrading waste water.
7. the modified g-C of PEG according to claim 5 or 63N4-Cu2The application of O composite catalyst, it is characterised in that: described
One of organic pollutant comprising Anthraquinones, quinone imides, oxa anthracenes and azo in waste water is a variety of.
8. the modified g-C of PEG according to claim 73N4-Cu2The application of O composite catalyst, it is characterised in that: described useless
Pollutant in water is selected from reactive brilliant bule, methylene blue, rhodamine B, reactive brilliant red and methyl orange.
9. the modified g-C of PEG according to claim 63N4-Cu2The application of O composite catalyst, it is characterised in that: described useless
The initial concentration of organic pollutants is 10-30mg/L；The modified g-C of PEG in the mixture3N4-Cu2O composite catalyst
Additional amount be 0.3-1g/L.
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| CN105032468A (en) * | 2015-08-03 | 2015-11-11 | 中南大学 | Cu2O-TiO2/g-C3N4 ternary complex and preparation and application method thereof |
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| CN105148968A (en) * | 2015-08-06 | 2015-12-16 | 江苏大学 | Composite photocatalytic material, preparation method and application thereof |
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