CN107115885A - It is a kind of to be modified g C with PEG3N4‑Cu2The preparation method and applications of O composite catalysts - Google Patents
It is a kind of to be modified g C with PEG3N4‑Cu2The preparation method and applications of O composite catalysts Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides one kind g C are modified with PEG3N4‑Cu2The preparation method and applications of O composite catalysts, methods described comprises the following steps：One first solution is obtained, first solution includes the Cu of dissolved state2+Ion and PEG 400；The g C of protonation are added in first solution3N4, stirring, ultrasound, acquisition suspension；Xylitol is added into the suspension under stirring, regulation pH value stirs to obtain mixed liquor to 10 12；The mixed liquor is heated to 150 200 DEG C in high-pressure reaction vessel, the 35h of isothermal reaction 25, natural cooling obtains reactant；By the reactant separation of solid and liquid after cooling, clean, 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 are made3N4‑Cu2O composite catalysts.The composite catalyst has stronger visible absorption ability, photocatalysis performance and stability enhancing.
Description
Technical field
The invention belongs to water-treatment technology field, more particularly to one kind g-C is modified with PEG3N4-Cu2O composite catalysts
Preparation method and applications.
Background technology
With developing rapidly for modern industry, the fossil energy such as matchmaker, oil, natural gas is utilized by exhaustive exploitation, is caused tight
The energy crisis and problem of environmental pollution of weight.Therefore, a kind of control technology of the environmental pollution of low energy consumption is sought extremely urgent.Too
Sun can be developed significant as a kind of cleaning, cheap regenerative resource to it.Photocatalysis technology is used as one kind
Effective method, is handled and has produced preferable effect, urged using sunlight catalytic semiconductor light to environmental pollutants with it
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 pollution in catalytic degradation waste water has obtained wide confirmation.Cuprous oxide is after the New Generation Optical after titanium dioxide
Catalyst, is to plant great due to preferable photocatalysis performance, being paid attention in terms of pollution control by researcher
The green photochemical catalyst of DEVELOPMENT PROSPECT.But Cu2O is easily inactivated in degradation of contaminant, and photo-generate electron-hole pair is rapid
It is combined so that Cu2O photocatalysis efficiency has much room for improvement.
The content of the invention
For drawbacks described above of the prior art, it is a primary object of the present invention to provide one kind PEG to be modified g-C3N4-
Cu2The preparation method and applications of O composite catalysts, the catalyst has stronger visible absorption ability, photocatalytic
Energy and stability enhancing.
In order to achieve the above object, the present invention is adopted the following technical scheme that：It is a kind of to be modified g-C with PEG3N4-Cu2O is compound to be urged
The preparation method of agent, methods described comprises the 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, regulation pH value stirs to obtain mixed liquor to 10-12；
The mixed liquor is heated to 150-200 DEG C in high-pressure reaction vessel, isothermal reaction 25-35h is reacted
Thing；
By the reactant separation of solid and liquid after cooling, clean, 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 it is further preferably, in the composite catalyst, the g-C3N4With Cu2O mass ratio is 1:1-1:5.
As further preferably, the rate of heat addition of the solid product is 2-3k/min.
It is used as further preferred, the g-C of the protonation3N4Preparation method include：It is in heating rate by dicyandiamide
It is warming up under conditions of 1-3K/min after 500-600 DEG C, calcines 3-5h, cooling obtains powder, grinds；In powder after grinding
Concentrated sulfuric acid mixing is added, stirring, ultrasound obtains mixture；The mixture and water are mixed, milky is obtained and suspends
Liquid, by milk-white coloured suspension centrifugation, washing and dry, the g-C after being acidified3N4；By the g-C after the acidifying3N4
50-75 DEG C of heat backflow 4-8h, suction filtration, washing and the dry g-C that must be protonated3N4。
As further preferably, the mixing time is 6-10h, the ultrasonic time is 1-3h.
A kind of g-C3N4-Cu2The application of O composite catalysts, the g-C3N4-Cu2O composite catalysts are made in radiation of visible light
With the organic pollution in lower treating wastewater through catalysis of connected.
As further preferably, the processing includes：
G-C is added in waste water3N4-Cu2O composite catalysts, stirring forms mixture；
The mixture is placed in the range of exposures of visible ray；
Visible ray cooperates with g-C3N4-Cu2Organic pollution in O composite catalyst degrading waste waters.
It is used as further preferred, having comprising Anthraquinones, quinone imides, oxa anthracenes and azo in the waste water
One or more in organic pollutants.
As it is further preferably, the organic pollution in the waste water be selected from reactive brilliant bule, methylene blue, rhodamine B,
Reactive brilliant red and methyl orange.
As further preferably, the initial concentration of the Organic Pollutants in Wastewater is 10-30mg/L.
It is used as further preferred, the g-C in the mixture3N4-Cu2The addition of O composite catalysts is 0.3-1g/
L。
The beneficial effects of the invention are as follows：The present invention promotes Cu by the coupling between the semi-conducting material of narrow band gap2O
Photocatalytic activity, g-C has been successfully prepared using solvent-thermal method and with reference to high-temperature calcination3N4-Cu2O composite photo-catalysts, institute
State composite catalyst g-C3N4And Cu2O closely grows together, and two phase compositions coexist and with close contact interface, shape
Into g-C3N4-Cu2The heterojunction structure of O plane-plane contacts.Compared to the g-C of pure phase3N4And Cu2O, g-C3N4-Cu2O composites
With stronger visible absorption ability, specific surface area is bigger, and crystallinity is more preferable.g-C3N4-Cu2O hetero-junctions preferably can band
Distribution 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, it has obvious dispersiveness, can form specific surface area bigger
Flaky nanometer structure, so as to more fully contact Cu2O forms even closer heterojunction structure.In addition, the present invention is in preparation side
PEG-400 is with the addition of in method, PEG-400 is not only to Cu2O particle and pattern has preferable stabilization, and with simple, warp
Ji, with Green Chemistry the characteristics of.
Brief description of the drawings
Fig. 1 is g-C3N4、Cu2G-C in O and the embodiment of the present invention3N4-Cu2The XRD of O composite catalysts.
Fig. 2 a-2b are g-C in the embodiment of the present invention 13N4-Cu2The SEM figures of O composite catalysts.
Fig. 3 is g-C in the embodiment of the present invention 13N4-Cu2The BET test charts of O composite catalysts.
Fig. 4 is in Vis, g-C3N4And Cu2The degraded situation schematic diagram of methyl orange in O various combination reaction system.Fig. 5
For the g-C in the embodiment of the present invention 13N4-Cu2The circulation experiment knot of O composite catalysts under visible light to methyl orange degradation performance
Fruit schematic diagram.
Embodiment
The present invention is a kind of with PEG modifications g-C by providing3N4-Cu2The preparation method and applications of O composite catalysts, solution
Determined existing Cu2The defect that O photocatalyst treatment Organic Pollutants in Wastewater photocatalysis performances are poor, cycle performance is unstable etc.,
G-C prepared by the present invention3N4-Cu2O composite photo-catalysts, with stronger visible absorption ability, photochemical catalyst catalytic performance
With stability enhancing.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is：
The embodiment of the present invention is modified g-C with PEG3N4-Cu2The preparation method of O composite catalysts, methods described 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, regulation pH value stirs to obtain mixed liquor to 10-12；
The mixed liquor is heated to 150-200 DEG C in high-pressure reaction vessel, isothermal reaction 25-35h is reacted
Thing；
By the reactant separation of solid and liquid after cooling, clean, 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 ray can be absorbed.And g-C3N4Taboo
Bandwidth is moderate, can be coupled by good with matching with a variety of semi-conducting materials, and improves light induced electron and point in hole
From efficiency.And p-type semiconductor Cu2O and n-type semiconductor g-C3N4Two kinds of semiconductor combinations can form p-n heterojunction.For p-n junction
For hetero-junctions, p-type semiconductor fermi level is close to valence band, and the fermi level of n-type semiconductor is close to conduction band, two kinds of semiconductors
To reach thermodynamical equilibrium in combination, its fermi level time is gradually close, can be because of photo-generated carrier at the two ends of hetero-junctions
Move and form internal electric field.The presence of internal electric field can promote the separation in light induced electron and hole, thus heterojunction photocatalyst ratio
Single semiconductor catalyst has more preferable photocatalysis performance.Different preparation conditions and method can directly affect the microcosmic of material
Structure, particle size and performance, and influence it to apply.
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 O surfaces
C3N4-Cu2O composite photo-catalysts, have the advantages that mild condition, particle be uniform, pattern is easy to control.Pairing of the embodiment of the present invention
Into photochemical catalyst carried out the sign of structure, pattern and optical property, and have evaluated so that methyl orange etc. is simulating pollution thing
The photocatalytic degradation capability of composite catalyst.Test result indicates that g-C3N4And Cu2The phase compositions of O two coexist and with close
Contact interface, forms g-C3N4-Cu2The heterojunction structure of O plane-plane contacts.In addition g-C3N4-Cu2O hetero-junctions is preferable
The photocatalysis performance of compound can be ensured that with mating structure, than single-phase g-C3N4Or Cu2O is greatly improved, and
And with good photochemical stability.Test and analyze with reference to free radical capture, it is proposed that g-C3N4-Cu2O composite photocatalysts
The possible photocatalytic mechanism of agent.
The overall raising of composite catalyst catalytic performance of the embodiment of the present invention is attributed to p-n junction hetero-junctions and effectively facilitates electric charge
Separation, suppress that electron-hole is compound and absorb the extension of optical wavelength range, compared to homogenous material, it has higher urge
Change activity and stability.
G-C of the embodiment of the present invention3N4-Cu2O composite catalysts effectively can give up in catalytic treatment under radiation of visible light effect
Organic pollution in water.
The embodiment of the present invention have studied catalyst of the embodiment of the present invention by taking methyl orange as an example to be used to have in treating wastewater through catalysis of connected
During organic pollutants, its degradation effect to organic pollution in water environment, but the embodiment of the present invention is not limited to only to first
Base orange works, and other pollutants of degrading can also reach the effect of similar catalytic degradation.
In order to which above and other purpose, feature and the advantage of the present invention can be become apparent, number cited below particularly is implemented
Example, to illustrate g-C of the present invention3N4-Cu2The preparation method and applications of O composite catalysts.
Embodiment 1
Raw material and reagent
Dicyanodiamine (C2H4N4), Salzburg vitriol (CuSO4·5H2O), sodium hydroxide (NaOH), hydrochloric acid (HCl) are
Analyze pure (AR), purchased from Chemical Reagent Co., Ltd., Sinopharm Group；Xylitol (C5H1205), methyl orange (C14H14N3NaO3S)
To analyze pure (AR), purchased from Shanghai Aladdin biochemical technology limited company.
g-C3N4Preparation
G-C is prepared using the method for high temperature pyrolysis dicyandiamide3N4：4g dicyandiamides are weighed to be placed in corundum crucible with cover, and
Crucible is put into Muffle furnace, in air atmosphere with 2k/min heating rate temperature programming to 550 DEG C, and 4h is incubated, treats
The yellow powder of gained is ground into 30min after product natural cooling, grinding gained primary product is standby.The mixing 10ml concentrated sulfuric acids add
Enter in 50ml flasks, 8h, ultrasonic 1h are stirred at room temperature, the mixture after stirring is slowly poured into 100ml deionized waters while stirring
Mix.The milk-white coloured suspension 3000r centrifugation 10min of acquisition are simultaneously washed with deionized.80 DEG C of dryings.Weigh the g- after acidifying
C3N40.4g is poured into equipped with 200ml flasks, 65 DEG C of heat backflow 6h, filtering and washing and 80 DEG C of dry g-C3N4。
g-C3N4-Cu2The preparation of O composite catalysts
First under magnetic stirring by 1.25gCuSO4·5H2O is added in 35mL deionized waters, then add 5mlPEG-400,
When solution is changed into navy blue, continue to add g-C into above-mentioned solution3N4(g-C3N4：Cu2O mass ratio is 1：5), magnetic force is stirred
Mix and be further continued for ultrasonic 1h after 1h uniform suspension is made, and then under conditions of magnetic agitation into above-mentioned suspension plus
Enter 1.5g xylitol, will be upper after the pH for adjusting above-mentioned suspension with 1mol/L NaOH solutions afterwards is 12, magnetic agitation 1h
State mixed liquor and be transferred to the autoclave (pressure is 0.8MPa) of polytetrafluoroethyllining lining and be heated to 180 DEG C of isothermal reaction 30h
Afterwards, natural cooling after reactor is taken out, the sample suction filtration in liner is separated, flushed three times repeatedly with deionized water, in
60 DEG C of dry 8h in vacuum drying chamber.The sample of gained is finally heated to 200 DEG C of holdings under argon gas protection with 2.3k/min
Constant temperature 2h, is made g-C3N4-Cu2O hetero-junctions.
Embodiment 2
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 dicyandiamide3N4：4g dicyandiamides are weighed to be placed in corundum crucible with cover, and
Crucible is put into Muffle furnace, in air atmosphere with 1k/min heating rate temperature programming to 500 DEG C, and 5h is incubated, treats
The yellow powder of gained is ground into 30min after product natural cooling, grinding gained primary product is standby.The mixing 10ml concentrated sulfuric acids add
Enter in 50ml flasks, 6h, ultrasonic 2h are stirred at room temperature, the mixture after stirring is slowly poured into 100ml deionized waters while stirring
Mix.The milk-white coloured suspension 3000r centrifugation 10min of acquisition are simultaneously washed with deionized.80 DEG C of dryings.Weigh the g- after acidifying
C3N40.4g is poured into equipped with 200ml flasks, 50 DEG C of heat backflow 8h, filtering and washing and 80 DEG C of dry g-C3N4。
g-C3N4-Cu2The preparation of O composite catalysts
First under magnetic stirring by 1.25gCuSO4·5H2O is added in 35mL deionized waters, then adds 5ml PEG-
400, when solution is changed into navy blue, continue to add g-C into above-mentioned solution3N4(g-C3N4：Cu2O mass ratio 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
Middle addition 1.5g xylitol, after the pH for adjusting above-mentioned suspension with 1mol/L NaOH solutions afterwards is 10, magnetic agitation 1h,
The autoclave (pressure is 0.6MPa) that above-mentioned mixed liquor is transferred into polytetrafluoroethyllining lining is heated to 150 DEG C of isothermal reactions
After 35h, natural cooling after reactor is taken out, the sample suction filtration in liner is separated, flushed three times repeatedly with deionized water,
60 DEG C of dry 8h in vacuum drying chamber.The sample of gained is finally heated to 150 DEG C of holdings under argon gas protection with 1k/min
Constant temperature 3h, is made g-C3N4-Cu2O hetero-junctions.
Embodiment 3
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 dicyandiamide3N4：4g dicyandiamides are weighed to be placed in corundum crucible with cover, and
Crucible is put into Muffle furnace, in air atmosphere with 3k/min heating rate temperature programming to 600 DEG C, and 3h is incubated, treats
The yellow powder of gained is ground into 30min after product natural cooling, grinding gained primary product is standby.The mixing 10ml concentrated sulfuric acids add
Enter in 50ml flasks, 10h, ultrasonic 3h are stirred at room temperature, the mixture after stirring is slowly poured into 100ml deionized waters while stirring
Mix.The milk-white coloured suspension 3000r centrifugation 10min of acquisition are simultaneously washed with deionized.80 DEG C of dryings.Weigh the g- after acidifying
C3N40.4g is poured into equipped with 200ml flasks, 75 DEG C of heat backflow 4h, filtering and washing and 80 DEG C of dry g-C3N4。
g-C3N4-Cu2The preparation of O composite catalysts
First under magnetic stirring by 1.25gCuSO4·5H2O is added in 35mL deionized waters, then adds 5ml PEG-
400, when solution is changed into navy blue, continue to add g-C into above-mentioned solution3N4(g-C3N4：Cu2O mass ratio 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
Middle addition 1.5g xylitol, after the pH for adjusting above-mentioned suspension with 1mol/L NaOH solutions afterwards is 12, magnetic agitation 1h,
The autoclave (pressure is 0.5MPa) that above-mentioned mixed liquor is transferred into polytetrafluoroethyllining lining is heated to 200 DEG C of isothermal reactions
After 25h, natural cooling after reactor is taken out, the sample suction filtration in liner is separated, flushed three times repeatedly with deionized water,
60 DEG C of dry 8h in vacuum drying chamber.The sample of gained is finally heated to 250 DEG C of holdings under argon gas protection with 3k/min
Constant temperature 1h, is made g-C3N4-Cu2O hetero-junctions.
g-C3N4-Cu2The sign of O composite catalysts
Fig. 1 is g-C3N4、Cu2G-C in O and the embodiment of the present invention3N4-Cu2The XRD of O composite catalysts.Can from figure
See, pure phase g-C3N4Sample has 2 diffraction maximums, corresponds respectively to g-C3N4(JCPDS87-1526) (002) in card and
(100) 12.86 ° of diffraction maximum corresponds to gC in crystal face, its middle position3N4(100) crystal face diffraction, be by graphite phase carbon nitride layer
Interior basic structural unit s-triazine ring periodic arrangement and produce, its 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, is to accumulate what is formed by the interlayer of cyclic aromatic thing, therefore its
Diffracted intensity is stronger.When we are by g-C3N4And Cu2O is carried out after being combined according to different dopings, with Cu2O dopings are not
Disconnected increase, g-C3N4The two feature peak intensities constantly weakening.In g-C3N4-Cu2The θ of the angle of diffraction 2 is in O composite samples:
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 Cu2O crystallinity is preferable.By two kinds
After Material cladding, their diffraction maximum all occurs in composite photo-catalyst, and it is strictly by g- to illustrate composite photo-catalyst
C3N4And Cu2The phase compositions of O two, while each corresponding diffraction peak intensity of phase content ratio is directly proportional.
Fig. 2 a-2b are g-C in the embodiment of the present invention 13N4-Cu2The SEM figures of O composite catalysts.By the embodiment of the present invention
The modified g-C in PEG surfaces3N4-Cu2O, shows obvious dispersiveness, g-C3N4And Cu2O closely grows together, shape
Into close heterojunction structure, so as to promote efficiently separating for electronics and hole, so as to show excellent photocatalysis performance.
Fig. 3 is g-C in the embodiment of the present invention 13N4-Cu2The BET test charts of O composite catalysts.It can be found that compared to not
Plus g-C prepared by PEG3N4-Cu2(i.e. without PEG-400 in the method for the embodiment of the present invention 1, other steps are similar, and make by O
Standby obtained original g-C3N4-Cu2O), the g-C of embodiment 13N4-Cu2O composite catalyst specific surface areas expand more than 3 times, this
It is likely to be the g-C prepared with the embodiment 1 shown in SEM figures3N4-Cu2O formation polymolecularities are relevant.BET analysis results are such as
Shown in table 1 below：
Table 1
In order to obtain visible ray of embodiment of the present invention collaboration g-C3N4-Cu2Organic contamination in O composite catalysts processing waste water
The effect of thing, carrying out following a series of experiments to the composite catalyst prepared by embodiment is proved：
g-C3N4-Cu2The research of O photocatalysis performance
Photocatalytic degradation experiment is using self-designed L ED lamps 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.By 20mg/L of concentration, volume do target degradation product for 50mL methyl orange (MO) solution, catalyst
Dosage is 0.025g.The absorption stirring 30min under first dark unglazed environment before light-catalyzed reaction, to ensure to reach absorption
Balance, is sampled once at regular intervals after turning on light, per sub-sampling 1.2mL, reaction time 30min.With 0.45 μm after sampling
Water system syringe membrane filtration, removes a small amount of catalyst remained in sample, is placed in the centrifuge tube of oiling 0.1mL ethanol, uses purple
Outer visible spectrophotometer detects the absorbance of 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-Cu2Discussions of the O to MO degraded situation, knot
Fruit is as shown in Figure 4, it has been found that in the control experiment of photochemical catalyst is not added with, MO is hardly degraded, and this shows that MO is quite steady
It is fixed, so as to eliminate the possibility that MO occurs from degradation process.As single-phase g-C3N4Or Cu2After O is added, although the degraded to MO
Have certain facilitation, but 30min to MO degraded also less than 20%, and the g-C of the embodiment of the present invention 13N4-Cu2O
After composite catalyst addition system, there is significant facilitation to MO degrading activity, under visible light illumination, 30min just may be used
The MO of degraded 85%.These results show g-C3N4-Cu2Degraded of the O/Vis systems compared to its single-phase photocatalytic system to MO
More efficiently, 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 stabilization
Property and recyclability, each reacted catalyst is collected again to be re-added in circular response next time.Such as
Shown in Fig. 5, reaction 30min is basically unchanged to MO degradation rate after circulating 6 times, and catalyst stability is high.
Technical scheme in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
The present invention promotes Cu by the coupling between the semi-conducting material of narrow band gap2O photocatalytic activities, utilize solvent
Hot method has simultaneously been successfully prepared g-C with reference to high-temperature calcination3N4-Cu2O composite photo-catalysts, the composite catalyst neutral body six
Angle star Cu2O is dispersed into independent angle small one by one, g-C by PEG3N4In Cu2O surfaces quickly grow into surface-to-surface composite construction,
Two phase compositions coexist and with close contact interface, form g-C3N4-Cu2The heterojunction structure of O plane-plane contacts.Compare
In the g-C of pure phase3N4And Cu2O, g-C3N4-Cu2O composites have stronger visible absorption ability, and specific surface area is bigger,
Crystallinity is more preferable.g-C3N4-Cu2O hetero-junctions can preferably ensure that the photocatalysis performance of compound with mating structure, than
Single-phase g-C3N4Or Cu2O is greatly improved.
Wherein, the present invention is using the g-C protonated3N4, it has obvious dispersiveness, can form specific surface area bigger
Flaky nanometer structure, so as to more fully contact Cu2O forms even closer heterojunction structure.In addition, the present invention is in preparation side
PEG-400 is with the addition of in method, PEG-400 is not only to Cu2O particle and pattern has preferable stabilization, and with simple, warp
Ji, with Green Chemistry the characteristics of.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various changes and modification without departing from the spirit and scope of the present invention.So, if these modifications and variations of the present invention
Belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these changes and modification
It is interior.
Claims (10)
1. a kind of be modified g-C with PEG3N4-Cu2The preparation method of O composite catalysts, it is characterised in that：Methods described 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, regulation pH value stirs to obtain mixed liquor to 10-12；
The mixed liquor is heated to 150-200 DEG C in high-pressure reaction vessel, isothermal reaction 25-35h obtains reactant；
By the reactant separation of solid and liquid after cooling, clean, 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 is combined
Catalyst.
2. according to claim 1 be modified g-C with PEG3N4-Cu2The preparation method of O composite catalysts, it is characterised in that：
In the composite catalyst, the g-C3N4With Cu2O mass ratio is 1:1-1:5.
3. according to claim 1 be modified g-C with PEG3N4-Cu2The preparation method of O composite catalysts, it is characterised in that：
The rate of heat addition of the solid product is 2-3k/min.
4. according to claim 1 be modified g-C with PEG3N4-Cu2The preparation method of O composite catalysts, it is characterised in that：
The g-C of the protonation3N4Preparation method include：Dicyandiamide is warming up under conditions of heating rate is 1-3K/min
After 500-600 DEG C, 3-5h is calcined, cooling obtains powder, grinds；Concentrated sulfuric acid mixing is added in powder after grinding, is stirred, is surpassed
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 dry, the g-C after being acidified3N4；By the g-C after the acidifying3N450-75 DEG C heat backflow 4-8h, suction filtration,
Wash and the dry g-C that must be protonated3N4。
5. according to claim 4 be modified g-C with PEG3N4-Cu2The preparation method of O composite catalysts, it is characterised in that：
The mixing time is 6-10h, and the ultrasonic time is 1-3h.
6. g-C made from the preparation method as described in any one of claim 1-5 claim3N4-Cu2O composite catalysts should
With, it is characterised in that：The g-C3N4-Cu2O composite catalysts are under radiation of visible light effect in catalytic treatment organic wastewater
Pollutant.
7. g-C according to claim 63N4-Cu2The application of O composite catalysts, it is characterised in that：The processing includes：
G-C is added in waste water3N4-Cu2O composite catalysts, stirring forms mixture；
The mixture is placed in the range of exposures of visible ray；
Visible ray cooperates with g-C3N4-Cu2Organic pollution in O composite catalyst degrading waste waters.
8. the g-C according to claim 6 or 73N4-Cu2The application of O composite catalysts, it is characterised in that：In the waste water
One or more in organic pollution comprising Anthraquinones, quinone imides, oxa anthracenes and azo.
9. g-C according to claim 83N4-Cu2The application of O composite catalysts, it is characterised in that：Dirt in the waste water
Contaminate thing and be selected from reactive brilliant bule, methylene blue, rhodamine B, reactive brilliant red and methyl orange.
10. g-C according to claim 73N4-Cu2The application of O composite catalysts, it is characterised in that：Have in the waste water
The initial concentration of organic pollutants is 10-30mg/L；G-C in the mixture3N4-Cu2The addition of O composite catalysts is
0.3-1g/L。
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Cited By (4)
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| CN108704655A (en) * | 2018-05-31 | 2018-10-26 | 武汉大学 | A kind of preparation method of cuprous oxide and graphite phase carbon nitride heterojunction photocatalyst |
| CN109908955A (en) * | 2019-04-01 | 2019-06-21 | 山东农业大学 | A kind of floating carbonitride/cellulose acetate flexible light catalytic porous film preparation method certainly |
| CN111036272A (en) * | 2019-12-27 | 2020-04-21 | 江苏大学 | C3N4/LaVO4Composite photocatalyst and preparation 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 |
| CN106223009A (en) * | 2016-07-26 | 2016-12-14 | 东华大学 | A kind of visible light catalyst self-cleaning antibacterial fabric and preparation thereof and application |
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| CN105148968A (en) * | 2015-08-06 | 2015-12-16 | 江苏大学 | Composite photocatalytic material, preparation method and application thereof |
| CN106223009A (en) * | 2016-07-26 | 2016-12-14 | 东华大学 | A kind of visible light catalyst self-cleaning antibacterial fabric and preparation thereof and application |
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| CN108704655A (en) * | 2018-05-31 | 2018-10-26 | 武汉大学 | A kind of preparation method of cuprous oxide and graphite phase carbon nitride heterojunction photocatalyst |
| CN109908955A (en) * | 2019-04-01 | 2019-06-21 | 山东农业大学 | A kind of floating carbonitride/cellulose acetate flexible light catalytic porous film preparation method certainly |
| CN111036272A (en) * | 2019-12-27 | 2020-04-21 | 江苏大学 | C3N4/LaVO4Composite photocatalyst and preparation method thereof |
| CN111036272B (en) * | 2019-12-27 | 2022-05-20 | 江苏大学 | C3N4/LaVO4Composite photocatalyst and preparation method thereof |
| CN115353922A (en) * | 2022-08-29 | 2022-11-18 | 攀枝花学院 | Carbon nitride quantum dot-based polyethylene glycol lubricating additive and preparation method thereof |
| CN115353922B (en) * | 2022-08-29 | 2023-11-14 | 攀枝花学院 | Carbon nitride quantum dot-based polyethylene glycol lubricating additive and preparation method thereof |
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