CN107324396B - A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material - Google Patents
A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods based on iron oxide doped graphite phase carbon nitride composite material, and steps are as follows: step 1 prepares iron-based ionic liquid；Step 2, carbonitride C3N4Preparation；Step 3, C3N4/Fe2O3The preparation of composite photoelectric material.C prepared by the present invention3N4/Fe2O3Composite photoelectric material is to introduce C3N4P-N junction is constructed, the carrier mobility rate of material is improved, reduces the combined efficiency of electron-hole pair.C prepared by the present invention3N4/Fe2O3Composite photoelectric material has excellent photoelectrochemical behaviour.
Description
Technical field
The present invention relates to field of photovoltaic materials, refer in particular to a kind of preparation side of graphite phase carbon nitride doped ferric oxide composite material
Method.
Background technique
Since photoelectricity occurs, optical electro-chemistry (PEC) research is realizing high efficiency photoelectric conversion, is effectively solving the energy
Crisis mitigates or curbs environmental pollution etc. that contribution is huge, and application prospect is very wide.Photoelectrochemical process realizes photoelectricity
Conversion is substantially optoelectronic pole material after illumination, absorbs a large amount of photons, internal electronics is by valence to conduction band, immediately
Hole is generated in valence band.Electrons and holes efficiently separate, and the electronics on conduction band transfers to electrode surface, through external electrical
Road output light electric current or photovoltage.The separating capacity of electron-hole pair is always to restrict photoelectric material to develop in photoelectric field
An important factor for.Therefore, control synthesis has the novel optoelectronic materials of excellent photoelectrochemical behaviour particularly important.
Its electric conductivity of metal oxide is a kind of very widely used functional material between conductor and insulator
Material.Metal oxide optics, electricity, in terms of there is superior performance, moreover, also have structure abundant,
Pattern, a variety of valence states etc..Fe2O3It is that one kind has narrow band gap, abundance, good environmental stability and exists more
The n-type semiconductor of kind crystal type.The form of being primarily present has bloodstone (α-Fe2O3) and maghemite (γ-Fe2O3).System
Preparation Method has template, hydro-thermal method, sol-gal process, vapor phase method etc..However, pure Fe2O3Active site on surface is less
And it is easy to reunite, the recombination rate of electron-hole pair is high, often limits Fe2O3As a kind of photoelectric material answering in optical electro-chemistry field
With.Accordingly, it is desirable to control the Fe of synthesis different-shape2O3And to Fe2O3It is doped and is improved with constructing P-N junction
Fe2O3Photoelectrochemical behaviour.So far, the Fe of various patterns has been synthesized2O3, such as nano-cluster, nanometer rods, nanotube, receive
Rice band, nano-rings etc. (Nitin K.Chaudhari, and Jong-Sung Yu J.Phys.Chem.C, 2008,112,
19957-19962；C J Jia, L D Sun, Z G Yan, et al.Angew.Chem.Int.Ed.2005,44,4328-
4333；Y M Zhao,Y H Li,RZ Ma,et al.small 2006,2,422-427；S Laurent,D Forge,M
Port,et al.Chem.Rev.2008,108,2064–2110；X Hu,J Yu,J Gong,et al.Adv.Mater.2007,
19,2324-2329).Existing multiple material and Fe2O3Carry out it is compound, such as Au, TiO2, carbon material and other semiconductor materials etc.
Deng (G A Sotiriou, F Starsich, A Dasargyri, et al.Adv.Funct.Mater.2014,24,2818-
2827；H Wang,Y Li,W Liu,et al.RSC Adv.,2014,4,23125–23130；X Zhu,Y Zhu,S
Murali,et al.ACS Nano,2011,5(4)3333–3338；L Xu,J Xia,H Xu,et al.J.Power
Sources,2014,245,866-874).Many documents are also it has been reported that semiconductors coupling is conducive to improve load to construct P-N junction
Flow the separating capacity of sub- migration rate and electron-hole pair.Present invention selection has excellent electronic structure, thermal stability and change
Stability is good, and the carbonitride doping Fe for being easy to modify2O3, it is connected to P-N junction, is then constructed a kind of novel photoelectric
Material is simultaneously applied in optical electro-chemistry field.
Summary of the invention
For the traditional preparation method of iron oxide before, invention introduces environmental-friendly ionic liquids to serve as reaction
Source, template, solvent prepare C3N4/Fe2O3Composite photoelectric material.The method preparation process is easy, and obtained material property is excellent
It is different.
The present invention is achieved through the following technical solutions:
A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material, steps are as follows:
Step 1 prepares iron-based ionic liquid: at room temperature, to T8FeCl is added in Cl (tri-n-octyl methyl ammonium chloride)3·
6H2O is put into oil bath after mixing evenly, is stirred to react for 24 hours；After reaction, reactant filtering 50 DEG C of air blast are placed on to do
It dries in dry case for 24 hours, by iron-based ionic liquid T obtained8Cl/FeCl3It is sealed spare；
Step 2, carbonitride C3N4Preparation: 2.5~5mmol Cyanuric Chloride A is added to polytetrafluoroethyllining lining reaction kettle
In, 20mL acetonitrile is then added, room temperature magnetic agitation to Cyanuric Chloride dissolves；1~2.5mmol melamine B is finally added,
After room temperature magnetic agitation is uniform, solvent thermal reaction 48h is carried out at 160 DEG C；After completion of the reaction, taking-up is cooled to room temperature, and is passed through
Distilled water and dehydrated alcohol, which repeatedly wash to be placed in 60 DEG C of drying boxes, is dried to obtain carbonitride；
Step 3, C3N4/Fe2O3The preparation of composite photoelectric material: by iron-based ionic liquid T8Cl/FeCl3Stirring and dissolving is in 10
In~20mL water, homogeneous phase solution is formed；Then, by CH3COONH4It is added in the homogeneous phase solution, after mixing evenly, 0g is added
~0.5g carbonitride stirs ultrasound 30min after 30min, transfers the solution into the polytetrafluoroethylene liner reaction kettle of 25mL,
Solvent thermal reaction 12h is carried out under the conditions of 180 DEG C, then naturally cools to room temperature, reaction product water and dehydrated alcohol are washed respectively
It washs 3 times, and place the product in 12h, gained sample C dry under the conditions of in baking oven 50 DEG C3N4/Fe2O3Composite photoelectric material room temperature is protected
It deposits spare.
Step 4, C3N4/Fe2O3The preparation of complex light electrode: weighing composite material, disperses in dehydrated alcohol, obtains 1-
The suspension of 2mg/mL takes suitable suspension 40-70 μ L drop coating to pretreated 0.5cm2ITO electro-conductive glass on, in room
It is dried under temperature spare.
In step 1, the tri-n-octyl methyl ammonium chloride and FeCl3·6H2The mass ratio of O is 10~20g:5~15g, described
The temperature of oil bath is 40 DEG C, and the time being stirred to react is for 24 hours.
In step 2, the Cyanuric Chloride A, acetonitrile, melamine B amount ratio be 2.5~5mmol:20mL:1~
2.5mmol, the temperature of the solvent thermal reaction are 160 DEG C, reaction time 48h.
In step 3, the iron-based ionic liquid T8Cl/FeCl3, water, CH3COONH4, carbonitride amount ratio be 0.5~
2g:0.2~0.8g:0.0032~0.032g, the temperature of the solvent thermal reaction are 180 DEG C, reaction time 12h.
The utility model has the advantages that
(1) C prepared by the present invention3N4/Fe2O3Composite photoelectric material is to introduce C3N4P-N junction is constructed, material is improved
Carrier mobility rate reduces the combined efficiency of electron-hole pair.
(2) C prepared by the present invention3N4/Fe2O3Composite photoelectric material has excellent photoelectrochemical behaviour.
Detailed description of the invention
Fig. 1 is C3N4/Fe2O3X-ray diffraction (XRD) figure of material.
Fig. 2 is C3N4/Fe2O3Fourier infrared (FT-IR) spectrogram of material
Fig. 3 is C3N4/Fe2O3The x-ray photoelectron of material can (XPS) analysis
Fig. 4 is C3N4/Fe2O3Transmission electron microscope (TEM) figure of material, wherein (a, b) is C3N4/Fe2O3, (c, d) is Fe2O3
Monomer material
Fig. 5 is C3N4/Fe2O3Uv drs (DRS) figure of material.
Fig. 6 is C3N4/Fe2O3Luminescence generated by light (PL) spectrogram of material
Fig. 7 is C3N4/Fe2O3The transient photocurrents spectrogram of material
Fig. 8 is C3N4/Fe2O3AC impedance (EIS) figure of material.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand
The present invention, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
(1) it prepares iron-based ionic liquid: at room temperature, weighing 20g T8Cl (tri-n-octyl methyl ammonium chloride) is in 50mL round bottom
It is stirred in flask, and 13.376g FeCl is added3·6H2O.Three-necked flask is put into after mixing evenly in 40 DEG C of oil bath, is stirred
Reaction is for 24 hours.After reaction, reactant filtering is placed in 50 DEG C of air dry ovens and is dried for 24 hours.By iron-based ion obtained
Liquid T8Cl/FeCl3It is sealed spare.
(2) Cyanuric Chloride for weighing 5mmol, adds and sets in polytetrafluoroethyllining lining reaction kettle, then measure the second of 20mL again
Nitrile is added in reaction kettle, and room temperature magnetic agitation certain time to Cyanuric Chloride dissolves.The melamine for finally weighing 2.5mmol is slow
It is slow to be added in reaction kettle, after room temperature magnetic agitation 15min, then in 160 DEG C of electric heating constant-temperature blowing drying box high temperature solvent heat
React 48h.It is cooled to room temperature after taking-up, repeatedly washs to be placed in 60 DEG C of drying boxes by distilled water and dehydrated alcohol and be dried to obtain
C3N4Material.
(3)C3N4/Fe2O3The preparation of material is by introducing iron-based ionic liquid and C3N4Polytetrafluoro is packed into after mixing
The control synthesis of ethylene reaction kettle.By Metal Substrate ionic liquid T8Cl/FeCl3(0.5g) is mixed in dissolution 20mL water, and formation mixes
Liquid.Then, by CH3COONH4(0.2006g) is added to above-mentioned dissolved with T8Cl/FeCl3Homogeneous phase solution in.After mixing evenly, add
Enter C3N4(0.0032g) stirs ultrasound 30min after 30min, transfers the solution into the polytetrafluoroethylene liner reaction kettle of 25mL.
Solvent thermal reaction 12h under the conditions of 180 DEG C, then naturally cools to room temperature.Reaction product is respectively washed 3 with water and dehydrated alcohol
It is secondary, and place the product in 12h, gained sample 0.0032-C dry under the conditions of in baking oven 50 DEG C3N4/Fe2O3It is stored at room temperature spare.
(4) preparation of modified electrode: being ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
After being successively cleaned by ultrasonic half an hour in sub- water, ethyl alcohol, repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1M
It in NaOH aqueous solution, is boiled, and is kept for 30 minutes, cleaned with deionized water and dried up and is stand-by.Configure 1mg/mL C3N4/
Fe2O3Suspension.Then, take the 70 suspended drop-coateds of μ L on pretreated ITO electro-conductive glass, room temperature is stand-by after drying up naturally.
Obtained modified electrode is denoted as 0.0032-C3N4/Fe2O3/ITO。
(5) optical electro-chemistry test condition:
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing are smooth with 500W xenon lamp
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filter.Electrochemistry experiment uses CHI
660B electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system: modified electrode is work electricity
Pole, platinum electrode are to electrode, and saturation Ag/AgCl electrode is reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
It is carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment is containing
5mmol/L Fe(CN)6 -3/-40.1mol/L KCl solution in carry out, frequency range is 0.01Hz~10kHz, and initial potential is
0.24V, AC amplitude 5mV.
Embodiment 2:
(1) it prepares iron-based ionic liquid: at room temperature, weighing 15g T8Cl (tri-n-octyl methyl ammonium chloride) is in 50mL round bottom
It is stirred in flask, and 10.032g FeCl is added3·6H2O.Three-necked flask is put into after mixing evenly in 40 DEG C of oil bath, is stirred
Reaction is for 24 hours.After reaction, reactant filtering is placed in 50 DEG C of air dry ovens and is dried for 24 hours.By iron-based ion obtained
Liquid T8Cl/FeCl3It is sealed spare.
(2) Cyanuric Chloride for weighing 3.5mmol, adds and sets in polytetrafluoroethyllining lining reaction kettle, then measure 20mL's again
Acetonitrile is added in reaction kettle, and room temperature magnetic agitation certain time to Cyanuric Chloride dissolves.Finally weigh the melamine of 1.75mmol
Amine is slowly added into reaction kettle, after room temperature magnetic agitation 15min, then it is molten in 160 DEG C of electric heating constant-temperature blowing drying box high temperature
Agent thermal response 48h.It is cooled to room temperature after taking-up, is repeatedly washed by distilled water and dehydrated alcohol and be placed in drying in 60 DEG C of drying boxes
Obtain C3N4Material.
(3)C3N4/Fe2O3The preparation of material is by introducing iron-based ionic liquid and C3N4Polytetrafluoro is packed into after mixing
The control synthesis of ethylene reaction kettle.By Metal Substrate ionic liquid T8Cl/FeCl3In (1.1526g) stirring and dissolving 20mL water, formed equal
Phase solution.Then, by CH3COONH4(0.4625g) is added to above-mentioned dissolved with T8Cl/FeCl3Homogeneous phase solution in.It stirs evenly
Afterwards, C is added3N4(0.016g) stirs ultrasound 30min after 30min, transfers the solution into the polytetrafluoroethylene liner reaction of 25mL
In kettle.Solvent thermal reaction 12h under the conditions of 180 DEG C, then naturally cools to room temperature.Reaction product water and dehydrated alcohol difference
Cleaning 3 times, and place the product in 12h, gained sample 0.016-C dry under the conditions of in baking oven 50 DEG C3N4/Fe2O3It is stored at room temperature standby
With.
(4) preparation of modified electrode: being ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
After being successively cleaned by ultrasonic half an hour in sub- water, ethyl alcohol, repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1M
It in NaOH aqueous solution, is boiled, and is kept for 30 minutes, cleaned with deionized water and dried up and is stand-by.Configure 1mg/mL C3N4/
Fe2O3Suspension.Then, take the 70 suspended drop-coateds of μ L on pretreated ITO electro-conductive glass, room temperature is stand-by after drying up naturally.
Obtained modified electrode is denoted as 0.016-C3N4/Fe2O3/ITO。
(5) optical electro-chemistry test condition:
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing are smooth with 500W xenon lamp
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filter.Electrochemistry experiment uses CHI
660B electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system: modified electrode is work electricity
Pole, platinum electrode are to electrode, and saturation Ag/AgCl electrode is reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
It is carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment is containing
5mmol/L Fe(CN)6 -3/-40.1mol/L KCl solution in carry out, frequency range is 0.01Hz~10kHz, and initial potential is
0.24V, AC amplitude 5mV.
Embodiment 3:
(1) it prepares iron-based ionic liquid: at room temperature, weighing 10g T8Cl (tri-n-octyl methyl ammonium chloride) is in 50mL round bottom
It is stirred in flask, and 6.688g FeCl is added3·6H2O.Three-necked flask is put into after mixing evenly in 40 DEG C of oil bath, is stirred
Reaction is for 24 hours.After reaction, reactant filtering is placed in 50 DEG C of air dry ovens and is dried for 24 hours.By iron-based ion obtained
Liquid T8Cl/FeCl3It is sealed spare.
(2) Cyanuric Chloride for weighing 2.5mmol, adds and sets in polytetrafluoroethyllining lining reaction kettle, then measure 20mL's again
Acetonitrile is added in reaction kettle, and room temperature magnetic agitation certain time to Cyanuric Chloride dissolves.The melamine for finally weighing 1mmol is slow
It is slow to be added in reaction kettle, after room temperature magnetic agitation 15min, then in 160 DEG C of electric heating constant-temperature blowing drying box high temperature solvent heat
React 48h.It is cooled to room temperature after taking-up, repeatedly washs to be placed in 60 DEG C of drying boxes by distilled water and dehydrated alcohol and be dried to obtain
C3N4Material.
(3) by Metal Substrate ionic liquid T8Cl/FeCl3In (2g) stirring and dissolving 10-20mL water, homogeneous phase solution is formed.So
Afterwards, by CH3COONH4(0.8025g) is added to above-mentioned dissolved with T8Cl/FeCl3Homogeneous phase solution in.After mixing evenly, C is added3N4
(0.032g) stirs ultrasound 30min after 30min, transfers the solution into the polytetrafluoroethylene liner reaction kettle of 25mL.180
Solvent thermal reaction 12h under the conditions of DEG C, then naturally cools to room temperature.Reaction product water and dehydrated alcohol are respectively washed 3 times, and
Place the product in 12h, gained sample 0.032-C dry under the conditions of in baking oven 50 DEG C3N4/Fe2O3It is stored at room temperature spare.
(4) preparation of modified electrode: being ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
After being successively cleaned by ultrasonic half an hour in sub- water, ethyl alcohol, repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1M
It in NaOH aqueous solution, is boiled, and is kept for 30 minutes, cleaned with deionized water and dried up and is stand-by.Configure 1mg/mL C3N4/
Fe2O3Suspension.Then, take the 70 suspended drop-coateds of μ L on pretreated ITO electro-conductive glass, room temperature is stand-by after drying up naturally.
Obtained modified electrode is denoted as 0.032-C3N4/Fe2O3/ITO。
(5) optical electro-chemistry test condition:
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing are smooth with 500W xenon lamp
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filter.Electrochemistry experiment uses CHI
660B electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system: modified electrode is work electricity
Pole, platinum electrode are to electrode, and saturation Ag/AgCl electrode is reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
It is carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment is containing
5mmol/LFe(CN)6 -3/-40.1mol/L KCl solution in carry out, frequency range is 0.01Hz~10kHz, and initial potential is
0.24V, AC amplitude 5mV.
Fig. 1 is C3N4/Fe2O3X-ray diffraction (XRD) figure of material.C prepared by the present invention3N4/Fe2O3The XRD of material
Characterize data is as shown in Figure 2.Metal Fe is had found in XRD spectrum in Fig. 12O3Characteristic peak, be not found C3N4's
Characteristic peak.Illustrating prepared material, this may be due to C3N4Amount is fewer and C3N4Disperse relatively uniform.
Fig. 2 is C3N4/Fe2O3Fourier infrared (FT-IR) spectrogram of material.From figure 2 it can be seen that the flexible vibration of Fe-O
Dynamic and C-N heterocycle characteristic absorption peak shows that this composite material is C3N4/Fe2O3.And depositing there is no other miscellaneous peaks in figure
This explanation is washed with alcohol by washing and has cleaned up the ionic liquid of composite material surface.
Fig. 3 is C3N4/Fe2O3X-ray photoelectron energy (XPS) analysis of material, as can be seen from the figure this composite material is
It is made of tetra- kinds of elements of C, N, Fe, O, and Fe is existed in the form of+trivalent.
Fig. 4 is C3N4/Fe2O3Transmission electron microscope (TEM) figure of material, wherein (a, b) is C3N4/Fe2O3, (c, d) is Fe2O3
Monomer material.It can be seen from the figure that with monomer Fe2O3The TEM figure of material compares (Fig. 4 c, d), C3N4/Fe2O3Composite material
Size ratio Fe2O3Material is smaller, about 60nm.Monomer Fe2O3The pattern of material is presented spherical body and is supported on carbonitride C3N4Piece
On layer material.
Fig. 5 is C3N4/Fe2O3Solid uv drs (DRS) figure of material.It can be seen that material is being lower than from Fig. 5
The wave-length coverage of 580nm has stronger light absorption, and with C3N4Addition gradually widen the optical response range of material, more preferably
Promote the separation of light induced electron and hole.
Fig. 6 is C3N4/Fe2O3Luminescence generated by light (PL) spectrogram of material, it can be seen from the figure that C3N4/Fe2O3Composite material
Luminous intensity be lower than monomer Fe2O3, illustrate that composite material has lower photo-generate electron-hole Percentage bound, the introducing of carbonitride
Promote Fe2O3The raising of material photoelectrochemical behaviour.
Fig. 7 is C3N4/Fe2O3The transient photocurrents spectrogram of material, can intuitively compare C from figure3N4/Fe2O3With
Fe2O3The photocurrent response ability of the two.C3N4/Fe2O3The photoelectric current that composite material generates under light illumination is bigger than monomer, and
And carbonitride doping be 0.016g when, C3N4/Fe2O3Composite material photoelectric current maximum can reach 0.25 μ A, be monomer Fe2O3Material
10 times of material.It can be seen that C3N4Introduce really improve composite material photoelectrochemical behaviour.
Fig. 8 is C3N4/Fe2O3AC impedance (EIS) figure of material.C prepared by the present invention3N4/Fe2O3Its resistance value passes through
Nyquist curve further reacts electron transmission ability.C3N4/Fe2O3The resistance value of material is lower, illustrates that it shifts the energy of electronics
Power is stronger, can be effectively by photo-generate electron-hole to separation.From figure 8, it is seen that C3N4/Fe2O3Resistance value be lower than Fe2O3It is single
Body, this illustrates the Fe of carbonitride modification2O3With superior electron transmission ability, the separation in light induced electron and hole is promoted.
Therefore, C3N4/Fe2O3It can be used as a kind of excellent photoelectric material and be applied to optical electro-chemistry every field.
Claims (4)
1. a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material, which is characterized in that steps are as follows:
Step 1 prepares iron-based ionic liquid: at room temperature, FeCl being added into tri-n-octyl methyl ammonium chloride3·6H2O, stirring are equal
It is put into oil bath, is stirred to react after even；After reaction, dry, by iron-based ionic liquid T obtained8Cl/FeCl3It is sealed
It is spare；
Step 2, carbonitride C3N4Preparation: Cyanuric Chloride A is added in polytetrafluoroethyllining lining reaction kettle, second is then added
Nitrile, room temperature magnetic agitation to Cyanuric Chloride A dissolve；Melamine B is finally added, after room temperature magnetic agitation is uniform, is carried out molten
Agent thermal response；After completion of the reaction, taking-up is cooled to room temperature, and is washed, dry, obtains carbonitride；
Step 3, C3N4/Fe2O3The preparation of composite photoelectric material: by iron-based ionic liquid T8Cl/FeCl3Stirring and dissolving Yu Shuizhong,
Form homogeneous phase solution；Then, by CH3COONH4It is added in the homogeneous phase solution, after mixing evenly, carbonitride is added, after stirring
Ultrasound transfers the solution into polytetrafluoroethylene liner reaction kettle, carries out solvent thermal reaction, then naturally cools to room temperature, wash
It washs, dry, gained sample C3N4/Fe2O3Composite photoelectric material is stored at room temperature spare.
2. a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material according to claim 1,
It is characterized in that, in step 1, the tri-n-octyl methyl ammonium chloride and FeCl3·6H2The mass ratio of O is 10~20g:5~15g, institute
The temperature for stating oil bath is 40 DEG C, and the time being stirred to react is for 24 hours.
3. a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material according to claim 1,
Be characterized in that, in step 2, the Cyanuric Chloride A, acetonitrile, melamine B amount ratio be 2.5~5mmol:20mL:1~
2.5mmol, the temperature of the solvent thermal reaction are 160 DEG C, reaction time 48h.
4. a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material according to claim 1,
It is characterized in that, in step 3, the iron-based ionic liquid T8Cl/FeCl3, water, CH3COONH4, carbonitride amount ratio be 0.5~
2g:10~20 mL:0.2~0.8g:0.0032~0.032g, the temperature of the solvent thermal reaction are 180 DEG C, and the reaction time is
12h。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289692A (en) * | 2015-11-19 | 2016-02-03 | 南京工程学院 | g-C3N4/Fe2O3 composite material and its preparation method and use |
| CN106391079A (en) * | 2016-08-22 | 2017-02-15 | 南京航空航天大学 | Preparation method of g-C3N4 film for photoelectrocatalysis hydrolysis |
| CN106596664A (en) * | 2016-12-15 | 2017-04-26 | 江苏大学 | Preparation method and purpose of carbon nitride/bismuth oxide halide optoelectrical composite material |
-
2017
- 2017-06-06 CN CN201710417723.5A patent/CN107324396B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289692A (en) * | 2015-11-19 | 2016-02-03 | 南京工程学院 | g-C3N4/Fe2O3 composite material and its preparation method and use |
| CN106391079A (en) * | 2016-08-22 | 2017-02-15 | 南京航空航天大学 | Preparation method of g-C3N4 film for photoelectrocatalysis hydrolysis |
| CN106596664A (en) * | 2016-12-15 | 2017-04-26 | 江苏大学 | Preparation method and purpose of carbon nitride/bismuth oxide halide optoelectrical composite material |
Non-Patent Citations (3)
| Title |
|---|
| Hematite (α-Fe2O3) with Various Morphologies: Ionic Liquid-Assisted Synthesis, Formation Mechanism, and Properties;Jiabiao Lian, et al.;《ACS NANO》;20091030;第3卷(第11期);3749-3761 |
| Ionic liquid assisted synthesis and photocatalytic properties of α-Fe2O3 hollow microspheres;Li Xu, et al.;《Dalton Transactions》;20130207;第42卷;6468-6477 |
| Reactable ionic liquid assisted solvothermal synthesis of graphite-like C3N4 hybridizeda-Fe2O3 hollow microspheres with enhanced supercapacitive performance;Li Xu, et al.;《Journal of Power Sources》;20130612;第245卷;866-874 |
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