CN107324396A - A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite - Google Patents
A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite Download PDFInfo
- Publication number
- CN107324396A CN107324396A CN201710417723.5A CN201710417723A CN107324396A CN 107324396 A CN107324396 A CN 107324396A CN 201710417723 A CN201710417723 A CN 201710417723A CN 107324396 A CN107324396 A CN 107324396A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- room temperature
- stirring
- fecl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention provides a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite, step is as follows：Step 1, prepare 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 knots are built, the carrier mobility speed of material is improved, reduces the combined efficiency of electron hole pair.C prepared by the present invention3N4/Fe2O3Composite photoelectric material possesses excellent photoelectrochemical behaviour.
Description
Technical field
The present invention relates to field of photovoltaic materials, a kind of preparation side of graphite phase carbon nitride doped ferric oxide composite is refered in particular to
Method.
Background technology
Since occurring from photoelectricity, optical electro-chemistry (PEC) research is realizing high efficiency opto-electronic conversion, is effectively solving the energy
Crisis, mitigate or contribute huge in terms of curbing environmental pollution, its application prospect is very wide.Photoelectrochemical process realizes photoelectricity
Conversion be substantially optoelectronic pole material after illumination, absorb a large amount of photons, its internal electronics is by valence to conduction band, immediately
Hole is produced in valence band.Electronics and hole are efficiently separated, 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 that restriction photoelectric material develops in photoelectric field
Key factor.Therefore, novel optoelectronic materials of the control synthesis with excellent photoelectrochemical behaviour are particularly important.
Its electric conductivity of metal oxide is the feature material of class application widely between conductor and insulator
Material.Metal oxide in terms of optics, electricity, magnetics have superior performance, moreover, also have abundant structure,
Pattern, a variety of valence states etc..Fe2O3Be it is a kind of have narrow band gap, abundance, good environmental stability and exist it is many
Plant the n-type semiconductor of 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 Fe2O3Avtive spot on surface is less
And easily reunite, the recombination rate of electron-hole pair is high, often limits Fe2O3It is used as a class photoelectric material answering in optical electro-chemistry field
With.Accordingly, it is desirable to control to synthesize the Fe of different-shape2O3And to Fe2O3It is doped to build P-N junction to improve
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 Fe2O3It is combined, such as Au, TiO2, carbon material and other semi-conducting 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 improving load to build P-N junction
Flow sub- migration rate and the separating capacity of electron-hole pair.Present invention selection has excellent electronic structure, heat endurance and change
Stability is good, and is easy to the nitridation carbon doping Fe of modification2O3, P-N junction is connected to, a class novel photoelectric is then built
Material is simultaneously applied in optical electro-chemistry field.
The content of the invention
For the traditional preparation method of iron oxide before, reaction is served as invention introduces environment-friendly ionic liquid
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, step is as follows：
Step 1, prepare 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 stirring, stirring reaction 24h；After reaction terminates, 50 DEG C of air blast are placed in after reactant is filtered and are done
24h is dried in dry case, by obtained iron-based ionic liquid T8Cl/FeCl3Sealing preserve is standby；
Step 2, carbonitride C3N4Preparation：2.5~5mmol Cyanuric Chlorides A is added to polytetrafluoroethyllining lining reactor
In, 20mL acetonitriles are then added, room temperature magnetic agitation to Cyanuric Chloride dissolves；1~2.5mmol melamine B are 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, take out and be cooled to room temperature, pass through
Distilled water and absolute ethyl 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 stirring, adds 0g
In ultrasound 30min after~0.5g carbonitrides, stirring 30min, the polytetrafluoroethylene liner reactor for transferring the solution into 25mL,
Solvent thermal reaction 12h is carried out under the conditions of 180 DEG C, room temperature is then naturally cooled to, reaction product is washed respectively with water and absolute ethyl alcohol
Wash 3 times, and product is placed in baking oven under the conditions of 50 DEG C dry 12h, gained sample C3N4/Fe2O3Composite photoelectric material normal temperature is protected
Deposit standby.
Step 4, C3N4/Fe2O3The preparation of complex light electrode：Composite is weighed, disperses in absolute ethyl alcohol, obtains 1-
2mg/mL suspension, takes appropriate suspension 40-70 μ L drop coatings to the 0.5cm pre-processed2ITO electro-conductive glass on, in room
Dried under temperature standby.
In step 1, the tri-n-octyl methyl ammonium chloride and FeCl3·6H2O mass ratio is 10~20g：5~15g, it is described
The temperature of oil bath is 40 DEG C, and the time of the stirring reaction is 24h.
In step 2, the Cyanuric Chloride A, acetonitrile, melamine B amount ratio are 2.5~5mmol：20mL：1~
2.5mmol, the temperature of the solvent thermal reaction is 160 DEG C, and the reaction time is 48h.
In step 3, the iron-based ionic liquid T8Cl/FeCl3, water, CH3COONH4, carbonitride amount ratio for 0.5~
2g:0.2~0.8g:0.0032~0.032g, the temperature of the solvent thermal reaction is 180 DEG C, and the reaction time is 12h.
Beneficial effect：
(1) C prepared by the present invention3N4/Fe2O3Composite photoelectric material is to introduce C3N4P-N junction is built, material is improved
Carrier mobility speed, reduces the combined efficiency of electron-hole pair.
(2) C prepared by the present invention3N4/Fe2O3Composite photoelectric material possesses excellent photoelectrochemical behaviour.
Brief description of the drawings
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 drses (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.
Embodiment
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 examples.
Embodiment 1：
(1) iron-based ionic liquid is prepared：At room temperature, 20g T are weighed8Cl (tri-n-octyl methyl ammonium chloride) is in 50mL round bottoms
Stirred in flask, and add 13.376g FeCl3·6H2O.Three-necked flask is put into 40 DEG C of oil bath after stirring, stirred
React 24h.After reaction terminates, it is placed in after reactant is filtered in 50 DEG C of air dry ovens and dries 24h.By obtained iron-based ion
Liquid T8Cl/FeCl3Sealing preserve is standby.
(2) 5mmol Cyanuric Chloride is weighed, plus is put in polytetrafluoroethyllining lining reactor, 20mL second is then measured again
Nitrile is added in reactor, and room temperature magnetic agitation certain time to Cyanuric Chloride dissolves.The melamine for finally weighing 2.5mmol is slow
It is slow to add in reactor, 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.Room temperature is cooled to after taking-up, is placed in 60 DEG C of drying boxes and is dried to obtain by distilled water and the multiple washing of absolute ethyl alcohol
C3N4Material.
(3)C3N4/Fe2O3The preparation of material is by introducing iron-based ionic liquid and C3N4Load polytetrafluoro after mixing
The control synthesis of ethylene reaction kettle.By Metal Substrate ionic liquid T8Cl/FeCl3(0.5g) is mixed in dissolving 20mL water, and formation mixes
Liquid.Then, by CH3COONH4(0.2006g) is added to above-mentioned dissolved with T8Cl/FeCl3Homogeneous phase solution in.After stirring, plus
Enter C3N4In ultrasound 30min after (0.0032g), stirring 30min, the polytetrafluoroethylene liner reactor for transferring the solution into 25mL.
Solvent thermal reaction 12h, then naturally cools to room temperature under the conditions of 180 DEG C.Reaction product is respectively washed 3 with water and absolute ethyl alcohol
It is secondary, and product is placed in baking oven under the conditions of 50 DEG C dry 12h, gained sample 0.0032-C3N4/Fe2O3Normal temperature is saved backup.
(4) preparation of modified electrode：ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
It is cleaned by ultrasonic successively after half an hour in sub- water, ethanol, is repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1M
In the NaOH aqueous solution, boiled, and kept for 30 minutes, cleaned and dried up stand-by with deionized water.Configure 1mg/mL C3N4/
Fe2O3Suspension.Then, take the 70 suspended drop-coateds of μ L on the ITO electro-conductive glass of pretreatment, 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 is smooth with 500W xenon lamps
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filters.Electrochemistry experiment uses CHI
660B electrochemical workstations (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system：Modified electrode is work electricity
Pole, platinum electrode is that, to electrode, saturation Ag/AgCl electrodes are reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
Carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment 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 is 5mV.
Embodiment 2：
(1) iron-based ionic liquid is prepared：At room temperature, 15g T are weighed8Cl (tri-n-octyl methyl ammonium chloride) is in 50mL round bottoms
Stirred in flask, and add 10.032g FeCl3·6H2O.Three-necked flask is put into 40 DEG C of oil bath after stirring, stirred
React 24h.After reaction terminates, it is placed in after reactant is filtered in 50 DEG C of air dry ovens and dries 24h.By obtained iron-based ion
Liquid T8Cl/FeCl3Sealing preserve is standby.
(2) 3.5mmol Cyanuric Chloride is weighed, plus is put in polytetrafluoroethyllining lining reactor, then measures 20mL's again
Acetonitrile is added in reactor, and room temperature magnetic agitation certain time to Cyanuric Chloride dissolves.Finally weigh 1.75mmol melamine
Amine is slowly added into reactor, after room temperature magnetic agitation 15min, then molten in 160 DEG C of electric heating constant-temperature blowing drying box high temperature
Agent thermal response 48h.Room temperature is cooled to after taking-up, repeatedly washs to be placed in 60 DEG C of drying boxes by distilled water and absolute ethyl alcohol and dries
Obtain C3N4Material.
(3)C3N4/Fe2O3The preparation of material is by introducing iron-based ionic liquid and C3N4Load polytetrafluoro after mixing
The control synthesis of ethylene reaction kettle.By Metal Substrate ionic liquid T8Cl/FeCl3In (1.1526g) stirring and dissolving 20mL water, form equal
Phase solution.Then, by CH3COONH4(0.4625g) is added to above-mentioned dissolved with T8Cl/FeCl3Homogeneous phase solution in.Stir
Afterwards, C is added3N4Ultrasound 30min after (0.016g), stirring 30min, transfers the solution into 25mL polytetrafluoroethylene liner reaction
In kettle.Solvent thermal reaction 12h, then naturally cools to room temperature under the conditions of 180 DEG C.Reaction product water and absolute ethyl alcohol difference
Cleaning 3 times, and product is placed in baking oven under the conditions of 50 DEG C dry 12h, gained sample 0.016-C3N4/Fe2O3Normal temperature preserves standby
With.
(4) preparation of modified electrode：ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
It is cleaned by ultrasonic successively after half an hour in sub- water, ethanol, is repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1M
In the NaOH aqueous solution, boiled, and kept for 30 minutes, cleaned and dried up stand-by with deionized water.Configure 1mg/mL C3N4/
Fe2O3Suspension.Then, take the 70 suspended drop-coateds of μ L on the ITO electro-conductive glass of pretreatment, 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 is smooth with 500W xenon lamps
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filters.Electrochemistry experiment uses CHI
660B electrochemical workstations (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system：Modified electrode is work electricity
Pole, platinum electrode is that, to electrode, saturation Ag/AgCl electrodes are reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
Carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment 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 is 5mV.
Embodiment 3：
(1) iron-based ionic liquid is prepared：At room temperature, 10g T are weighed8Cl (tri-n-octyl methyl ammonium chloride) is in 50mL round bottoms
Stirred in flask, and add 6.688g FeCl3·6H2O.Three-necked flask is put into 40 DEG C of oil bath after stirring, stirred
React 24h.After reaction terminates, it is placed in after reactant is filtered in 50 DEG C of air dry ovens and dries 24h.By obtained iron-based ion
Liquid T8Cl/FeCl3Sealing preserve is standby.
(2) 2.5mmol Cyanuric Chloride is weighed, plus is put in polytetrafluoroethyllining lining reactor, then measures 20mL's again
Acetonitrile is added in reactor, and room temperature magnetic agitation certain time to Cyanuric Chloride dissolves.The melamine for finally weighing 1mmol is slow
It is slow to add in reactor, 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.Room temperature is cooled to after taking-up, is placed in 60 DEG C of drying boxes and is dried to obtain by distilled water and the multiple washing of absolute ethyl alcohol
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 stirring, C is added3N4
In ultrasound 30min after (0.032g), stirring 30min, the polytetrafluoroethylene liner reactor for transferring the solution into 25mL.180
Solvent thermal reaction 12h under the conditions of DEG C, then naturally cools to room temperature.Reaction product is respectively washed 3 times with water and absolute ethyl alcohol, and
Product is placed in baking oven under the conditions of 50 DEG C and dries 12h, gained sample 0.032-C3N4/Fe2O3Normal temperature is saved backup.
(4) preparation of modified electrode：ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
It is cleaned by ultrasonic successively after half an hour in sub- water, ethanol, is repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1M
In the NaOH aqueous solution, boiled, and kept for 30 minutes, cleaned and dried up stand-by with deionized water.Configure 1mg/mL C3N4/
Fe2O3Suspension.Then, take the 70 suspended drop-coateds of μ L on the ITO electro-conductive glass of pretreatment, 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 is smooth with 500W xenon lamps
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filters.Electrochemistry experiment uses CHI
660B electrochemical workstations (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system：Modified electrode is work electricity
Pole, platinum electrode is that, to electrode, saturation Ag/AgCl electrodes are reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
Carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment 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 is 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 found that in XRD spectrum in Fig. 12O3Characteristic peak, C is not found3N4's
Characteristic peak.Illustrating prepared material, this is probably due to C3N4Amount it is fewer, and C3N4Dispersion ratio is more uniform.
Fig. 2 is C3N4/Fe2O3Fourier infrared (FT-IR) spectrogram of material.Shaken from figure 2 it can be seen that Fe-O is flexible
The characteristic absorption peak of dynamic and C-N heterocycles, it is C to show this composite3N4/Fe2O3.And do not have depositing for other miscellaneous peaks in figure
This explanation is washed by washing and alcohol and has been 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 is
It is made up of tetra- kinds of elements of C, N, Fe, O, and Fe is present 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 that with monomer Fe2O3The TEM figures of material compare (Fig. 4 c, d), C3N4/Fe2O3Composite
Size compares 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 drses (DRS) figure of material.From Fig. 5 it can be seen that material less than
580nm wave-length coverage has stronger light absorbs, and with C3N4Addition gradually widen the photoresponse scope of material, more preferably
Promote the separation in light induced electron and hole.
Fig. 6 is C3N4/Fe2O3Luminescence generated by light (PL) spectrogram of material, it can be seen that C3N4/Fe2O3Composite
Luminous intensity be less than monomer Fe2O3, illustrate that composite 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 contrast C from figure3N4/Fe2O3With
Fe2O3The photocurrent response ability of the two.C3N4/Fe2O3The photoelectric current that composite is produced under light illumination is bigger than monomer, and
And carbonitride doping be 0.016g when, C3N4/Fe2O3Composite 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 photoelectrochemical behaviour.
Fig. 8 is C3N4/Fe2O3AC impedance (EIS) figure of material.C prepared by the present invention3N4/Fe2O3Its resistance passes through
Nyquist curves further react electron transmission ability.C3N4/Fe2O3The resistance of material is lower, illustrates its energy for shifting electronics
Power is stronger, can be effectively by photo-generate electron-hole to separation.From figure 8, it is seen that C3N4/Fe2O3Resistance be less than Fe2O3It is single
Body, the Fe of this explanation carbonitride modification2O3With more excellent electron transmission ability, the separation in light induced electron and hole is promoted.
Therefore, C3N4/Fe2O3Optical electro-chemistry every field can be applied to as the excellent photoelectric material of a class.
Claims (4)
1. a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite, it is characterised in that step is as follows：
Step 1, prepare iron-based ionic liquid：At room temperature, FeCl is added into tri-n-octyl methyl ammonium chloride3·6H2O, stirring is equal
It is put into after even in oil bath, stirring reaction；After reaction terminates, dry, by obtained iron-based ionic liquid T8Cl/FeCl3Sealing preserve
It is standby；
Step 2, carbonitride C3N4Preparation：Cyanuric Chloride A is added in polytetrafluoroethyllining lining reactor, second is then added
Nitrile, room temperature magnetic agitation to Cyanuric Chloride dissolves；Melamine B is finally added, after room temperature magnetic agitation is uniform, solvent is carried out
Thermal response；After completion of the reaction, take out and be cooled to room temperature, wash, dry, obtain carbonitride；
Step 3, C3N4/Fe2O3The preparation of composite photoelectric material：By iron-based ionic liquid T8Cl/FeCl3Stirring and dissolving in water,
Form homogeneous phase solution；Then, by CH3COONH4It is added in the homogeneous phase solution, after stirring, carbonitride is added, after stirring
Ultrasound, is transferred the solution into polytetrafluoroethylene liner reactor, is carried out solvent thermal reaction, is then naturally cooled to room temperature, wash
Wash, dry, gained sample C3N4/Fe2O3Composite photoelectric material normal temperature is saved backup.
2. a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite according to claim 1, its
It is characterised by, in step 1, the tri-n-octyl methyl ammonium chloride and FeCl3·6H2O mass ratio is 10~20g：5~15g, institute
The temperature for stating oil bath is 40 DEG C, and the time of the stirring reaction is 24h.
3. a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite according to claim 1, its
It is characterised by, in step 2, the Cyanuric Chloride A, acetonitrile, melamine B amount ratio are 2.5~5mmol：20mL：1~
2.5mmol, the temperature of the solvent thermal reaction is 160 DEG C, and the reaction time is 48h.
4. a kind of preparation method based on iron oxide doped graphite phase carbon nitride composite according to claim 1, its
It is characterised by, in step 3, the iron-based ionic liquid T8Cl/FeCl3, water, CH3COONH4, carbonitride amount ratio for 0.5~
2g:0.2~0.8g:0.0032~0.032g, the temperature of the solvent thermal reaction is 180 DEG C, and the reaction time is 12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710417723.5A CN107324396B (en) | 2017-06-06 | 2017-06-06 | A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710417723.5A CN107324396B (en) | 2017-06-06 | 2017-06-06 | A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107324396A true CN107324396A (en) | 2017-11-07 |
| CN107324396B CN107324396B (en) | 2019-05-31 |
Family
ID=60194218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710417723.5A Active CN107324396B (en) | 2017-06-06 | 2017-06-06 | A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107324396B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108063249A (en) * | 2017-12-06 | 2018-05-22 | 江汉大学 | A kind of preparation method of high-purity copper nitride nano crystalline |
| CN108339562A (en) * | 2018-02-11 | 2018-07-31 | 济南大学 | A kind of preparation method and products obtained therefrom of the azotized carbon nano pipe of iron ion doping |
| CN109142493A (en) * | 2018-07-17 | 2019-01-04 | 江苏大学 | A kind of construction method of the optical electro-chemistry sensor for label-free detection 4- chlorophenol |
| CN110124711A (en) * | 2019-04-04 | 2019-08-16 | 江苏大学 | The preparation method and its desulfurization application of few layer carbonitride loaded tungsten trioxide nanoparticle catalyst |
| CN110548533A (en) * | 2019-09-11 | 2019-12-10 | 王杰 | Preparation method and application of metal and nonmetal co-doped carbon nitride nano material |
| CN110548532A (en) * | 2019-09-10 | 2019-12-10 | 重庆工商大学 | Preparation method of recyclable efficient carbon nitride-based composite photocatalyst |
| CN110961135A (en) * | 2019-12-12 | 2020-04-07 | 南京理工大学 | Preparation method of graphite-like phase carbon nitride-based composite nano semiconductor material |
| CN113735178A (en) * | 2021-09-06 | 2021-12-03 | 派尔森环保科技有限公司 | Preparation method of lithium ion battery cathode material with iron oxide particles embedded in carbon nitride sheet |
| CN114682284A (en) * | 2020-12-30 | 2022-07-01 | Tcl科技集团股份有限公司 | Composite photocatalyst and preparation method and application thereof |
| CN115475632A (en) * | 2022-09-13 | 2022-12-16 | 东南大学 | CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, product and application thereof |
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 |
|---|
| JIABIAO LIAN, ET AL.: "Hematite (α-Fe2O3) with Various Morphologies: Ionic Liquid-Assisted Synthesis, Formation Mechanism, and Properties", 《ACS NANO》 * |
| LI XU, ET AL.: "Ionic liquid assisted synthesis and photocatalytic properties of α-Fe2O3 hollow microspheres", 《DALTON TRANSACTIONS》 * |
| LI XU, ET AL.: "Reactable ionic liquid assisted solvothermal synthesis of graphite-like C3N4 hybridizeda-Fe2O3 hollow microspheres with enhanced supercapacitive performance", 《JOURNAL OF POWER SOURCES》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108063249A (en) * | 2017-12-06 | 2018-05-22 | 江汉大学 | A kind of preparation method of high-purity copper nitride nano crystalline |
| CN108339562A (en) * | 2018-02-11 | 2018-07-31 | 济南大学 | A kind of preparation method and products obtained therefrom of the azotized carbon nano pipe of iron ion doping |
| CN108339562B (en) * | 2018-02-11 | 2020-07-07 | 济南大学 | Preparation method of iron ion doped carbon nitride nanotube and obtained product |
| CN109142493A (en) * | 2018-07-17 | 2019-01-04 | 江苏大学 | A kind of construction method of the optical electro-chemistry sensor for label-free detection 4- chlorophenol |
| CN109142493B (en) * | 2018-07-17 | 2020-06-26 | 江苏大学 | Construction method of photoelectrochemical sensor for non-labeled detection of 4-chlorophenol |
| CN110124711B (en) * | 2019-04-04 | 2021-12-21 | 江苏大学 | Preparation method and desulfurization application of few-layer carbon nitride loaded tungsten trioxide nanoparticle catalyst |
| CN110124711A (en) * | 2019-04-04 | 2019-08-16 | 江苏大学 | The preparation method and its desulfurization application of few layer carbonitride loaded tungsten trioxide nanoparticle catalyst |
| CN110548532A (en) * | 2019-09-10 | 2019-12-10 | 重庆工商大学 | Preparation method of recyclable efficient carbon nitride-based composite photocatalyst |
| CN110548533A (en) * | 2019-09-11 | 2019-12-10 | 王杰 | Preparation method and application of metal and nonmetal co-doped carbon nitride nano material |
| CN110961135A (en) * | 2019-12-12 | 2020-04-07 | 南京理工大学 | Preparation method of graphite-like phase carbon nitride-based composite nano semiconductor material |
| CN114682284A (en) * | 2020-12-30 | 2022-07-01 | Tcl科技集团股份有限公司 | Composite photocatalyst and preparation method and application thereof |
| CN113735178A (en) * | 2021-09-06 | 2021-12-03 | 派尔森环保科技有限公司 | Preparation method of lithium ion battery cathode material with iron oxide particles embedded in carbon nitride sheet |
| CN115475632A (en) * | 2022-09-13 | 2022-12-16 | 东南大学 | CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, product and application thereof |
| CN115475632B (en) * | 2022-09-13 | 2024-04-05 | 东南大学 | CN/Mn 2 O 3 Preparation method of/FTOp-n heterojunction material, and product and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107324396B (en) | 2019-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107324396B (en) | A kind of preparation method based on iron oxide doped graphite phase carbon nitride composite material | |
| Yang et al. | 1D/2D carbon-doped nanowire/ultra-thin nanosheet g-C3N4 isotype heterojunction for effective and durable photocatalytic H2 evolution | |
| CN104733716B (en) | Molybdenum oxide/nitrogen-doped carbon composite electrode material and preparation method thereof | |
| CN103903861B (en) | Counter electrode made of metal sulfide and graphene composite materials and preparation method and application of counter electrode | |
| Xu et al. | Fabrication of an innovative designed TiO2 nanosheets/CdSe/polyaniline/graphene quaternary composite and its application as in-situ photocathodic protection coatings on 304SS | |
| Li et al. | Insights into the Operation of Noble‐Metal‐Free Cocatalyst 1T‐WS2‐Decorated Zn0. 5Cd0. 5S for Enhanced Photocatalytic Hydrogen Evolution | |
| Huo et al. | A transparent cobalt sulfide/reduced graphene oxide nanostructure counter electrode for high efficient dye-sensitized solar cells | |
| CN107833752B (en) | It is a kind of for dye-sensitized solar cells to the material and preparation method thereof of electrode | |
| CN103560014B (en) | Dye-sensitized cell is with to electrode, its preparation method and dye-sensitized cell | |
| CN106000431A (en) | Flaky CdS/BiOCl composite nanometer material and preparation method thereof | |
| Xu et al. | A new in-situ preparation method to CuS electrodes for CdS/CdSe co-sensitized solar cells | |
| CN106207196B (en) | A kind of preparation method of flower-shaped titanium nitride/carbonitride/graphene composite nano material | |
| CN106206043B (en) | A kind of FeS2Nanometer rods/graphene is to electrode material and the preparation method and application thereof | |
| CN107313064B (en) | Metal boron or the α-Fe of phosphide modification2O3The preparation method and application of optical anode material | |
| CN108565122A (en) | For dye-sensitized solar cells to the Fe of electrode2O3-C3N4- CQDs composite materials and preparation method | |
| Ma et al. | Decorating Phosphorus‐Doped g‐C3N4 with Zinc Porphyrin Metal–Organic Framework via an Electrostatic Self‐Assembly Process: An Efficient Strategy to Boost Photocatalytic Hydrogen Evolution Performance | |
| CN109731583A (en) | A kind of two-step method preparation Zn0.2Cd0.8The method of S/rGO composite material | |
| Gadisa et al. | ZnO@ Ni foam photoelectrode modified with heteroatom doped graphitic carbon for enhanced photoelectrochemical water splitting under solar light | |
| Fan et al. | Construction of 0D/2D Ni2P/Ni2P homophase Schottky junction by molten salt-assisted strategy for enhanced photocatalytic H2 evolution | |
| CN105778088B (en) | A kind of graphene/polyaniline nanometer stick array composite and preparation method and application | |
| CN107188178B (en) | A kind of g-C3N4The preparation method of surface photovoltage signal enhancing | |
| Zhang et al. | Enhanced photoelectrochemical cathodic protection performance of gC 3 N 4 caused by the co-modification with N defects and C deposition | |
| CN108376613A (en) | It is a kind of to be used for zno-based composite material and preparation method of the dye-sensitized solar cells to electrode | |
| CN107342364A (en) | A kind of UV photodetector of zinc oxide polyaniline sandwich structure and preparation method thereof | |
| Kong et al. | Improved photoelectrochemical cathodic protection properties of a flower-like SrTiO3 photoanode decorated With g-C3N4 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201211 Address after: No. 159, Chengjiang Middle Road, Jiangyin City, Wuxi City, Jiangsu Province Patentee after: Jiangyin Intellectual Property Operation Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: JIANGSU University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220916 Address after: No. 118, Xiji Avenue, Nanyue Village, Xinjie Street, Yixing City, Wuxi City, Jiangsu Province, 214200 Patentee after: Wuxi Wisdom Xingyi Information Technology Co.,Ltd. Address before: No. 159, Chengjiang Middle Road, Jiangyin City, Wuxi City, Jiangsu Province Patentee before: Jiangyin Intellectual Property Operation Co.,Ltd. |
|
| TR01 | Transfer of patent right |