CN106206773B - A kind of preparation method of graphite phase carbon nitride film modified electrod - Google Patents
A kind of preparation method of graphite phase carbon nitride film modified electrod Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 32
- 239000010439 graphite Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 239000000969 carrier Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
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- 238000002309 gasification Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 claims 1
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- 230000005619 thermoelectricity Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 150000007974 melamines Chemical class 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical group C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- -1 cdicynanmide Chemical compound 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Condensed Matter Physics & Semiconductors (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a kind of preparation method of graphite phase carbon nitride film modified electrod.Under protective atmosphere, 450 DEG C first~550 DEG C heating nitridation carbon raw material 1min~6h so that heat-resistant carriers surface is attached to after carbonitride material gasification, and forms carbon nitride precursor；Then 500 DEG C~550 DEG C are heated the heat-resistant carriers 1min~6h for being attached with carbon nitride precursor so that carbon nitride precursor gasifies and the graphite phase carbon nitride film that thickness is 10nm~150nm is formed on conductive substrates surface, obtains the modified electrode.The present invention by using the method for vapour deposition in conductive substrates surface modification graphite phase carbon nitride film, so as to improve the thermoelectricity capability of electrode, and carbon nitride films the uniformity and stability.
Description
Technical field
The invention belongs to film preparing technology and thermoelectricity field, repaiied more particularly, to a kind of graphite phase carbon nitride film
Adorn the preparation method of electrode.
Background technology
Since 2009, professor Wang Xinchen of University of Fuzhou reported graphite phase carbon nitride (g-C first3N4) one can be used as
Since photochemical catalyst is planted for hydrogen production by water decomposition this milestone work, g-C3N4Correlative study by scientific research circle extensive pass
Note, its core and bright spot are that it is organic photochemical catalyst without any metallic element, and the work is that photochemical catalyst family adds
A newcomer, therefore g-C are entered3N4Also star's material that photocatalysis is studied is turned into.Graphite phase carbon nitride is due to low close
The advantages of degree, good chemical inertness, heat endurance, nontoxic, bio-compatibility, being also used as catalyst is used to analyse oxygen, analysis
Hydrogen, decomposition water, contaminant degradation, CO2Reduction, also can be used as luminaire, optical detector, thermoelectricity, light as photoelectric material
In terms of electrochemical cell, and these applications need to prepare graphite phase carbon nitride film.
At present, generally graphite phase carbon nitride powder is prepared in electrode material surface using methods such as drop coating, spin coatings；So as to
The graphite phase carbon nitride powder of the electrode surface of acquisition is uneven, and is easy to come off, and causes the material of electrode unstable.In addition,
Will nitridation toner body solation processing (Angew.Chem.-Int.Edit., 2015,54,6297), or by melamine cyanurate
Mixture is clipped in substrate intermediate heat-treatment (Angew.Chem., 2014,126,3728), or combines vapour deposition and micro- contact print
Brush technology (Adv.Mater., 2015,27,712) prepares film, but it is still uneven that film is made.In addition, prior art is obtained
Carbon nitride films be used in terms of optical electro-chemistry decomposition water, luminescence generated by light, it is undesirable yet with thermoelectricity capability so that not
Thermo-electric generation can be used for.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides graphite phase carbon nitride film modified electrod
Preparation method, its object is to the method using vapour deposition in conductive substrates surface modification graphite phase carbon nitride film, from
And improve the thermoelectricity capability of electrode, and carbon nitride films the uniformity and stability.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of film modified electricity of graphite phase carbon nitride
The preparation method of pole, comprises the following steps：
(1) under protective atmosphere, 450 DEG C~550 DEG C heating nitridation carbon raw material 1min~6h so that carbonitride material gasification
After be attached to heat-resistant carriers surface, and form carbon nitride precursor；
(2) under protective atmosphere, 500 DEG C~550 DEG C are heated the heat-resistant carriers 1min~6h for being attached with carbon nitride precursor,
So that carbon nitride precursor gasification and the graphite phase carbon nitride film for being 10nm~150nm in conductive substrates surface formation thickness,
Obtain the graphite phase carbon nitride film modified electrod.
Preferably, the nitridation carbon raw material in the step (1) is melamine, cdicynanmide, in cyanamide, urea or thiocarbamide
It is one or more.
As it is further preferred that the nitridation carbon raw material in the step (1) is melamine, cyanamide or cdicynanmide.
Preferably, the protective atmosphere is the one or more in nitrogen, helium or argon gas.
As it is further preferred that the protective atmosphere is nitrogen.
Preferably, the heat-resistant carriers in the step (1) are graphite paper, crucible, porcelain boat, quartz boat or carbon cloth.
Preferably, the thickness of the carbon nitride precursor in the step (1) is 0.5mm~1.5mm.
Preferably, the material of the conductive substrates in the step (2) is tin oxide, tin-doped indium oxide, the glass of Fluorin doped
Or metal oxide.
Preferably, the heat time in the step (2) is 2h~4h.
In general, by the contemplated above technical scheme of the present invention compared with prior art, due to being sunk using gas phase
Long-pending method obtains graphite phase carbon nitride film modified electrod, so as to have the advantages that：
1st, the thermoelectricity capability of electrode, empirical tests, the Seebeck coefficient for the carbon nitride films that the inventive method is obtained are improved
Up to -87 μ V/K, so as to have good application potential in fields such as thermo-electric generations；
2nd, the film obtained using the method for vapour deposition is not only more uniform, and can with conductive substrates strong bonded, from
And its mechanical strength is improved, extend service life；
3rd, with melamine, cdicynanmide, cyanamide is directly as nitridation carbon raw material, and preparation method is simple and cheap, energy
Production cost is reduced, production efficiency is improved.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram for the carbon nitride films that embodiment 1 is prepared；
Fig. 2 is embodiment 1, and the Fourier transform infrared spectroscopy picture of film is made in embodiment 2, embodiment 3.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
A kind of preparation method of graphite phase carbon nitride film modified electrod of the present invention, comprises the following steps：
(1) under protective atmosphere, 450 DEG C~550 DEG C (are preferably 500 DEG C~550 DEG C, to ensure carbonitride material gasification
While deamination, it is unlikely to the carbon nitride precursor excessive decomposition for be formed) heating nitridation carbon raw material 1min~6h so that nitrogen
Heat-resistant carriers surface is attached to after changing carbon raw material gasification, and forms carbon nitride precursor；
Wherein, protective atmosphere can be nitrogen, helium, argon gas or its mixed gas；Nitridation carbon raw material is melamine, dicyan
One or more in amine, cyanamide, urea or thiocarbamide, and preferably melamine, cyanamide or cdicynanmide, to ensure to prepare
Carbon nitride films have good thermoelectricity capability.
Heat-resistant carriers can be graphite paper, crucible, porcelain boat, quartz boat or carbon cloth, the thickness for the carbon nitride precursor that surface is formed
Spend for 0.5mm~1.5mm, graphite phase carbon nitride film is obtained to ensure subsequently to be enough modified conducting substrate surface；
(2) under protective atmosphere, 500 DEG C~550 DEG C are heated the heat-resistant carriers 1min~6h for being attached with carbon nitride precursor,
To avoid temperature too high, carbon nitride films attachment is insecure, easily comes off, temperature is too low and the thickness of carbon nitride films is too thin
It can not be formed；So that carbon nitride precursor gasification and the graphite-phase nitrogen for being 10nm~150nm in conductive substrates surface formation thickness
Change C film, obtain the graphite phase carbon nitride film modified electrod；
Wherein, the heat time is generally according to heating-up temperature, the middle nitridation obtained of surface area and step (1) of conductive substrates
Depending on the thickness and area of carbon matrix precursor, it is often preferred that 2h~4h, to ensure that the thickness of carbon nitride films is enough to provide good
Thermoelectricity capability, it is long without regard to the heat time, and make its excessive decomposition so as to being destroyed；Conductive substrates need resistance to gas phase
The high temperature of deposition, can select tin oxide (FTO), tin-doped indium oxide (ITO), glass or the metal oxide of Fluorin doped.
Embodiment 1
S1. 3g melamines are added in crucible, then crucible parcel is placed in tube furnace, lead to 20 minutes pre- places of nitrogen
Reason, in a nitrogen atmosphere, with 2 DEG C/min heating rate, 550 DEG C is increased to by temperature, 4 hours is incubated, is then down to room temperature
Complete to be heat-treated for the first time, obtain the carbon nitride precursor that thickness is about 1.3mm, and be deposited on crucible；
S2. using the tin oxide (FTO) of Fluorin doped as substrate, being placed on deposition after being heat-treated for the first time has the crucible of carbonitride
Under, then parcel is placed in tube furnace, leads to nitrogen pretreatment；In a nitrogen atmosphere, with 2 DEG C/min heating rate, by temperature
550 DEG C are increased to, 4 hours are incubated, room temperature is then down to and completes second of heat treatment；There is the Huang that thickness is about 150 nanometers on FTO
The generation of color film is carbon nitride films.
Embodiment 2
S1. 3g cdicynanmides are added in crucible, then crucible parcel is placed in tube furnace, lead to 20 minutes pre- places of nitrogen
Reason, in a nitrogen atmosphere, with 5 DEG C/min heating rate, 500 DEG C is increased to by temperature, 2 hours is incubated, is then down to room temperature
Complete to be heat-treated for the first time, obtain the carbon nitride precursor that thickness is about 1.4mm, and be deposited on crucible；
S2. using FTO as substrate, being placed on to deposit after being heat-treated for the first time has under the crucible of carbonitride, and then parcel is placed in
In tube furnace, lead to nitrogen pretreatment；In a nitrogen atmosphere, with 5 DEG C/min heating rate, temperature is increased to 500 DEG C, insulation
2 hours, then it is down to room temperature and completes second of heat treatment；It is graphite phase carbon nitride film to have yellow film generation on FTO, thick
Degree is about 150nm.
Embodiment 3
S1. 1g cyanamides are added in crucible, then crucible parcel is placed in tube furnace, leads to nitrogen and pre-processes for 20 minutes,
In a nitrogen atmosphere, with 5 DEG C/min heating rate, temperature is increased to 500 DEG C, 2 hours are incubated, room temperature completion is then down to
It is heat-treated for the first time, obtains the carbon nitride precursor that thickness is about 0.9mm, and be deposited on crucible；
S2. using FTO as substrate, being placed on to deposit after being heat-treated for the first time has under the crucible of carbonitride, and then parcel is placed in
In tube furnace, lead to nitrogen pretreatment；In a nitrogen atmosphere, with 5 DEG C/min heating rate, temperature is increased to 500 DEG C, insulation
2 hours, then it is down to room temperature and completes second of heat treatment；It is graphite phase carbon nitride film to have yellow film generation on FTO, thick
Degree is about 110nm.
Embodiment 4
S1. 3g melamines are added in crucible, then crucible parcel is placed in tube furnace, lead to 20 minutes pre- places of nitrogen
Reason, in a nitrogen atmosphere, with 2 DEG C/min heating rate, 500 DEG C is increased to by temperature, 4 hours is incubated, is then down to room temperature
Complete to be heat-treated for the first time, obtain the carbon nitride precursor that thickness is about 1.3mm, and be deposited on crucible；
S2. using FTO as substrate, being placed on to deposit after being heat-treated for the first time has under the crucible of carbonitride, and then parcel is placed in
In tube furnace, lead to nitrogen pretreatment；In a nitrogen atmosphere, with 2 DEG C/min heating rate, temperature is increased to 500 DEG C, insulation
4 hours, then it is down to room temperature and completes second of heat treatment；It is graphite phase carbon nitride film to have yellow film generation on FTO, thick
Degree is about 90nm.
Embodiment 5
S1. 3g melamines are added in crucible, then crucible parcel is placed in tube furnace, lead to 20 minutes pre- places of nitrogen
Reason, in a nitrogen atmosphere, with 2 DEG C/min heating rate, 550 DEG C is increased to by temperature, 4 hours is incubated, is then down to room temperature
Complete to be heat-treated for the first time, obtain thickness and be 1.3mm carbon nitride precursor, and be deposited on crucible；
S1. by TiO2Film is as substrate, and being placed on to deposit after being heat-treated for the first time has under the crucible of carbonitride, then wraps up
It is placed in tube furnace, leads to nitrogen pretreatment；In a nitrogen atmosphere, with 2 DEG C/min heating rate, temperature is increased to 550 DEG C,
Insulation 4 hours, is then down to room temperature and completes second of heat treatment；TiO2It is graphite-phase nitridation to have yellow film generation on film
C film, thickness is about 100nm.
Embodiment 6
S1. 3g melamines are added in crucible, then crucible parcel is placed in tube furnace, lead to 20 minutes pre- places of nitrogen
Reason, in a nitrogen atmosphere, with 2 DEG C/min heating rate, 550 DEG C is increased to by temperature, 4 hours is incubated, is then down to room temperature
Complete to be heat-treated for the first time, obtain the carbon nitride precursor that thickness is about 1.3mm, and be deposited on crucible；
S2. using tin-doped indium oxide (ITO) as substrate, being placed on to deposit after being heat-treated for the first time has under the crucible of carbonitride,
Then parcel is placed in tube furnace, leads to nitrogen pretreatment；In a nitrogen atmosphere, with 2 DEG C/min heating rate, temperature is raised
To 550 DEG C, 4 hours are incubated, room temperature is then down to and completes second of heat treatment；It is graphite-phase to have yellow film generation on ITO
Carbon nitride films, thickness is about 140nm.
Embodiment 7
S1. 3g melamines are added in crucible, then crucible parcel is placed in tube furnace, lead to 20 minutes pre- places of nitrogen
Reason, in a nitrogen atmosphere, with 2 DEG C/min heating rate, 550 DEG C is increased to by temperature, 4 hours is incubated, is then down to room temperature
Complete to be heat-treated for the first time, obtain the carbon nitride precursor that thickness is about 1.3mm, and be deposited on crucible；
S2. using glass as substrate, being placed on to deposit after being heat-treated for the first time has under the crucible of carbonitride, and then parcel is placed in
In tube furnace, lead to nitrogen pretreatment；In a nitrogen atmosphere, with 2 DEG C/min heating rate, temperature is increased to 550 DEG C, insulation
4 hours, then it is down to room temperature and completes second of heat treatment；It is graphite phase carbon nitride film to have yellow film generation on glass,
Thickness is about 170nm.
Embodiment 8
S1. 3g melamines are added in crucible, then crucible parcel is placed in tube furnace, lead to 20 minutes pre- places of nitrogen
Reason, in a nitrogen atmosphere, 5 DEG C/min are warming up to 550 DEG C, are incubated 4 hours, are down to room temperature and complete to be heat-treated for the first time, obtain thick
Degree is about 1.5mm carbon nitride precursor, and is deposited on crucible；
S2. using FTO as substrate, being placed on to deposit after being heat-treated for the first time has under the crucible of carbonitride, and then parcel is placed in
In tube furnace, lead to nitrogen pretreatment；In a nitrogen atmosphere, 5 DEG C/min is warming up to 550 DEG C, is incubated 4 hours, is down to room temperature completion
Second of heat treatment；It is graphite phase carbon nitride film to have yellow film generation on FTO, and thickness is about 150nm.
Embodiment 9-14 preparation condition is similar with embodiment 1-8, simply heating rate, reaction temperature, soaking time or
Person's substrate and crucible modes of emplacement are different, are specifically shown in Table 1.
The preparation condition of the embodiment 9- embodiments 14 of table 1
Analysis of experimental results
Empirical tests, the thickness of the carbon nitride precursor that embodiment 1- embodiments 14 are obtained in step sl for 0.5mm~
The thickness of the graphite phase carbon nitride film generated in 1.5mm, step S3 is about 10nm~150nm.
The carbon nitride films that embodiment 1 is obtained are observed under scanning electron microscope diagram, it can be seen that the surface of the film
Uniformly.In the case where power is 200W ultrasonic machines, ultrasonic one hour film is not fallen off, and illustrates the carbon nitride films and substrate of electrode surface
Adhesion it is good.
Fig. 2 is the Fourier transform infrared spectroscopy figure of embodiment 1, embodiment 2 and carbon nitride films made from embodiment 3
Piece, it can be seen that wave number be 810cm-1The peak at place is the Typical Vibration peak of 5-triazine units, and wave number is in 1160~1640cm-1It
Between peak be C-N heterocycles stretching vibration, wave number be located at 2160cm-1The peak at place is attributed to the cyano group that pyrolysis is produced, thus
It can learn that carbon nitride films are successfully prepared.
Above-mentioned test is carried out to embodiment 2- embodiments 14, similar result can be also obtained.
One end of the embodiment 1-4 and embodiment 9-10 electrodes obtained is placed at room temperature, the other end is heated, from
And the test of Seebeck coefficient is carried out, and as a result as shown in table 2, mean temperature when wherein abscissa represents electrode temperature.From table 2
Understand, the embodiment of the present invention has preferable thermoelectricity capability；Wherein, embodiment 1~2 is in the interval that temperature is 300K~400K
Interior, Seebeck coefficient is up to -20 μ V/K, and wherein embodiment 2 has been up to -87 μ V/K in 300K, has shown the inventive method
The carbon nitride films prepared have good thermoelectricity capability, with the huge potentiality applied to temperature difference electricity generation device.
The thermoelectric property data of the carbon nitride films of table 2
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of graphite phase carbon nitride film modified electrod, it is characterised in that comprise the following steps：
(1) under protective atmosphere, 450 DEG C~550 DEG C heating nitridation carbon raw material 1min~6h so that attached after carbonitride material gasification
In heat-resistant carriers surface, and form carbon nitride precursor；
(2) under protective atmosphere, 500 DEG C~550 DEG C are heated the heat-resistant carriers 1min~6h for being attached with carbon nitride precursor so that
Carbon nitride precursor gasifies and the graphite phase carbon nitride film that thickness is 10nm~150nm is formed on conductive substrates surface, obtains
The graphite phase carbon nitride film modified electrod.
2. preparation method as claimed in claim 1, it is characterised in that the nitridation carbon raw material in the step (1) is melamine
One or more in amine, cdicynanmide, cyanamide, urea or thiocarbamide.
3. preparation method as claimed in claim 2 described, it is characterised in that the nitridation carbon raw material in the step (1) is
Melamine, cyanamide or cdicynanmide.
4. preparation method as claimed in claim 1, it is characterised in that the protective atmosphere is in nitrogen, helium or argon gas
It is one or more.
5. described preparation method as claimed in claim 4, it is characterised in that the protective atmosphere is nitrogen.
6. preparation method as claimed in claim 1, it is characterised in that the heat-resistant carriers in the step (1) are graphite paper, earthenware
Crucible, porcelain boat, quartz boat or carbon cloth.
7. preparation method as claimed in claim 1, it is characterised in that the thickness of the carbon nitride precursor in the step (1)
For 0.5mm~1.5mm.
8. preparation method as claimed in claim 1, it is characterised in that the material of the conductive substrates in the step (2) is fluorine
Tin oxide, tin-doped indium oxide, glass or the metal oxide of doping.
9. preparation method as claimed in claim 1, it is characterised in that the heat time in the step (2) is 2h~4h.
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| CN110176505A (en) * | 2019-05-14 | 2019-08-27 | 三峡大学 | A kind of preparation method of graphite phase carbon nitride membrane electrode |
| CN110590172B (en) * | 2019-09-29 | 2020-12-25 | 燕山大学 | Graphite phase carbon nitride film and preparation method thereof |
| CN110790515B (en) * | 2019-10-18 | 2020-12-15 | 四川大学 | Transparent super-hydrophilic material with graphite phase carbon nitride and preparation method and application thereof |
| CN113044817B (en) * | 2019-12-27 | 2022-12-02 | 香港城市大学深圳研究院 | Colored carbon nitride-based film and preparation method thereof |
| CN113046724A (en) * | 2021-03-15 | 2021-06-29 | 郑州大学 | Large-area graphite-phase carbon nitride film, preparation method and application |
| CN113667992B (en) * | 2021-07-01 | 2023-11-10 | 昆明理工大学 | Method for preparing graphite phase carbon nitride film electrode by spray thermal polymerization |
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