CN106978595A - A kind of graphite type carbon nitride nanotube array photoelectrode, preparation method and the usage - Google Patents
A kind of graphite type carbon nitride nanotube array photoelectrode, preparation method and the usage Download PDFInfo
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- CN106978595A CN106978595A CN201710220962.1A CN201710220962A CN106978595A CN 106978595 A CN106978595 A CN 106978595A CN 201710220962 A CN201710220962 A CN 201710220962A CN 106978595 A CN106978595 A CN 106978595A
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- carbon nitride
- type carbon
- cyanamide
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- 239000002071 nanotube Substances 0.000 title claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000010439 graphite Substances 0.000 title claims abstract description 69
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 69
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 69
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 239000004411 aluminium Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 115
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 75
- 230000003647 oxidation Effects 0.000 claims description 64
- 238000007254 oxidation reaction Methods 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000000137 annealing Methods 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000741 silica gel Substances 0.000 claims description 26
- 229910002027 silica gel Inorganic materials 0.000 claims description 26
- 235000006408 oxalic acid Nutrition 0.000 claims description 25
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 21
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- 230000001476 alcoholic effect Effects 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 19
- 238000002604 ultrasonography Methods 0.000 claims description 19
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000009415 formwork Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005538 encapsulation Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 230000005693 optoelectronics Effects 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 6
- 235000005979 Citrus limon Nutrition 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 244000248349 Citrus limon Species 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000011260 aqueous acid Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000004806 packaging method and process Methods 0.000 description 8
- 239000005357 flat glass Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- -1 after taking-up Substances 0.000 description 4
- 238000003491 array Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000813 microcontact printing Methods 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
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/14—Metallic material, boron or silicon
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- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a kind of graphite type carbon nitride nanotube array photoelectrode, its preparation method and as light anode solar energy electrochemical decomposition aquatic products oxygen purposes, the diameter and adjustable length of graphite type carbon nitride nanotube in the graphite type carbon nitride nanotube array photoelectrode of the present invention, diameter range is 20nm 170nm, and length range is 400nm 2500nm.The present invention graphite type carbon nitride nanotube array photoelectrode be the anodised aluminium supported using conductive substrates as template, the cyanamide solution using concentration is presoma, and high-temperature polycondensation is obtained in an inert atmosphere.The graphite type carbon nitride nanotube array photoelectrode of the present invention possesses big specific surface area, more surface-active site, and solar energy electrochemical decomposition aquatic products oxygen excellent performance is applied to as light anode.
Description
Technical field
The invention belongs to organic semiconducting materials and field of nanometer technology, it is related to a kind of graphite type carbon nitride nano-tube array
Optoelectronic pole, preparation method and the usage, and in particular to a kind of graphite type carbon nitride nanotube array photoelectrode, its preparation method and
As light anode solar energy electrochemical decomposition aquatic products oxygen purposes.
Background technology
Graphite type carbon nitride (referred to as g-CN) is that a kind of polymer being only made up of two kinds of nonmetalloids of C and N is partly led
Body, because it has visible light-responded, rich and easy to get, non-toxic stable, is widely used in light degradation pollutant, photocatalysis point
Solve aquatic products hydrogen field.So far, comprising a variety of nanostructureds including mesoporous g-CN, g-CN nanometer rods, g-CN nanotubes
G-CN photochemical catalysts are seen in report.They generally possess larger specific surface area and more surface-active site, thus display
Go out very excellent photocatalysis performance.
Correlative study exploration work using g-CN as optoelectronic pole applied to optical electro-chemistry decomposition water is still at an early stage,
The efficiency of optical electro-chemistry decomposition water is generally relatively low.Recently, Liu and Bian et al. are utilized respectively " micro-contact printing " and " gas phase is cold
Solidifying method " success grown g-CN films in conductive substrates, and still, the optoelectronic pole of gained is in 0.1M Na2SO4In solution, 1.23V
During vs RHE, photoelectric current is below 40 μ A/cm2(Liu J,Wang H,Chen Z P,et al.Advanced Materials,
2015,27(4):712-718；Bian J,Li Q,Huang C,et al.Nano Energy,2015,15:353-361.).It is former
Because being, the optoelectronic pole that both approaches are obtained is without special nanostructured, and specific surface area is less than normal, causes electron hole can not
Efficiently separate, and then photoelectric properties are very low.
So, the g-CN optoelectronic poles with special nanostructured are prepared, to increase the specific surface area of optoelectronic pole, shorten a small number of
The collection distance of carrier, so that the utilization ratio for lifting electrode interior photo-generated carrier is significant.
The content of the invention
For the above-mentioned problems in the prior art, present invention aims at provide a kind of graphite type carbon nitride nanotube
Array photoelectric pole, preparation method and the usage.Graphite mould nitrogen in the graphite type carbon nitride nanotube array photoelectrode of the present invention
Carbon nano tube length and caliber are adjustable, and the nanotube array photoelectrode possesses larger specific surface area, more active sites
Point, while the hollow one-dimentional structure of nanotube is also conducive to the separation of electron hole.The graphite type carbon nitride nanotube of the present invention
Array photoelectric pole as light anode be applied to solar energy electrochemical decomposition is aqueous can be very excellent, in 1.23V vsRHE,
0.1M Na2SO4In solution, graphite type carbon nitride nanotube array photoelectrode photoelectric current prepared by the present invention can reach 94 μ A/
cm2。
For up to above-mentioned purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of graphite type carbon nitride nanotube array photoelectrode, the graphite type carbon nitride
Graphite type carbon nitride nano-tube array of the nanotube array photoelectrode by substrate and in the substrate is constituted, the graphite mould
Azotized carbon nano pipe array is formed by graphite type carbon nitride Nanotube alignment.
In the present invention, the axial direction of graphite type carbon nitride nanotube and the surface of substrate are substantially vertical.
In the graphite type carbon nitride nanotube array photoelectrode of the present invention, each graphite type carbon nitride Nanotube alignment is regular,
And orientation is consistent, the length direction of each graphite type carbon nitride nanotube is on same group of parallel lines.
The pattern of the graphite type carbon nitride nanotube of the present invention is nanotube-shaped, and chemical composition is graphite mould C3N4。
Preferably, a diameter of 20nm-170nm of the graphite type carbon nitride nanotube, for example, 20nm, 30nm, 40nm,
50nm、55nm、60nm、65nm、70nm、80nm、85nm、90nm、100nm、105nm、110nm、120nm、130nm、140nm、
150nm or 170nm etc., preferably 70nm-150nm.
Preferably, the length of the graphite type carbon nitride nanotube be 400nm-2500nm, for example, 400nm, 420nm,
450nm、500nm、550nm、575nm、600nm、650nm、700nm、750nm、800nm、850nm、900nm、1000nm、
1100nm、1150nm、1200nm、1300nm、1400nm、1500nm、1600nm、1700nm、1850nm、2000nm、2100nm、
2250nm, 2350nm or 2500nm etc., preferably 400nm-1600nm.
Preferably, the substrate is conductive substrates, preferably any one in ito glass, FTO glass or Si pieces.
Second aspect, the present invention provides the preparation of graphite type carbon nitride nanotube array photoelectrode as described in relation to the first aspect
Method, the described method comprises the following steps：
(1) adhesion layer is sputtered in substrate；
(2) continue to sputter Al films, encapsulation on adhesion layer；
(3) step (2) is encapsulated to obtained electrode to be placed in electrolyte, anodic oxidation is carried out；
(4) electrode for obtaining step (3) anodic oxidation is placed in H3PO4Reaming in solution, obtains the anodic oxygen of substrate support
Change aluminum alloy pattern plate；
(5) remove in encapsulation, the anodic oxidation aluminium formwork of the substrate support obtained to step (4) and pour into cyanamide, obtain base
The template for pouring into cyanamide of bottom support；
(6) encapsulation process is carried out, is then annealed under inert gas shielding；
(7) removing template is removed, graphite type carbon nitride nanotube array photoelectrode is obtained.
In the present invention, after step (3) anodic oxidation, Woelm Alumina and fine and close alumina flake, aluminum oxide are obtained
Thin layer is located between Woelm Alumina and adhesion layer, as barrier layer.
In the present invention, step (4) uses H3PO4Solution carries out reaming, the porous oxygen that on the one hand can be formed to step (3)
Change aluminium and carry out reaming, on the other hand can also get rid of the alumina barrier layer of densification.
Preferably, step (1) described substrate is conductive substrates, preferably any in ito glass, FTO glass or Si pieces
It is a kind of.
Preferably, the step of step (1) described substrate is first cleaned by ultrasonic and dried up before the use.
Preferably, the thickness of step (1) described adhesion layer be 5nm-70nm, for example, 5nm, 10nm, 20nm, 25nm,
30nm, 35nm, 40nm, 45nm, 50nm, 60nm or 70nm etc..
Preferably, step (1) described adhesion layer is TiO2Layer, or for by the Ti layers and W layers combination layer constituted.
Preferably, step (1) described adhesion layer is TiO2Layer, and the TiO2The thickness of layer is 20nm-50nm.
Preferably, step (1) described adhesion layer is the thick TiO of 30nm2Layer.
Preferably, step (1) described adhesion layer is by the Ti layers and W layers combination layer constituted, and the Ti in the combination layer
The thickness of layer is 5nm-10nm, and described W layers thickness is 40nm-70nm.
Preferably, step (1) described adhesion layer is the combination layer being made up of the thick W layers of thick 10nm Ti layers and 60nm.
Preferably, when step (1) described adhesion layer is TiO2During layer, TiO has been sputtered in step (1)2After layer, step (2)
Sputter before Al films, proceed as follows：To having sputtered TiO2The substrate of layer is made annealing treatment.
Preferably, to having sputtered TiO2During the substrate of layer is made annealing treatment, annealing temperature is 450 DEG C -550
DEG C, for example, 450 DEG C, 455 DEG C, 460 DEG C, 465 DEG C, 470 DEG C, 480 DEG C, 485 DEG C, 490 DEG C, 500 DEG C, 515 DEG C, 530 DEG C or
550 DEG C etc., preferably 500 DEG C.
Preferably, to having sputtered TiO2During the substrate of layer is made annealing treatment, annealing time is 30min-4h, example
Such as it is 30min, 1h, 2h, 2.5h, 3h or 4h, preferably 2h.
Preferably, to having sputtered TiO2During the substrate of layer is made annealing treatment, the heating of annealing temperature is warming up to
Speed be 10 DEG C/min-20 DEG C/min, for example, 10 DEG C/min, 13 DEG C/min, 15 DEG C/min, 16 DEG C/min, 18 DEG C/min or
20 DEG C/min etc., preferably 16 DEG C/min.
Preferably, the thickness of step (2) the Al films be 400nm-2500nm, for example, 400nm, 500nm, 550nm,
600nm、625nm、650nm、700nm、800nm、850nm、900nm、930nm、960nm、1000nm、1100nm、1150nm、
1200nm、1300nm、1350nm、1400nm、1500nm、1600nm、1700nm、1850nm、2000nm、2200nm、2300nm
Or 2500nm etc., preferably 400nm-1600nm.
Preferably, step (2) is described is encapsulated as：The electrode after sputtering Al films is packaged and solidified using silica gel.
Preferably, step (3) described electrolyte is in oxalic acid solution, phosphoric acid solution, sulfuric acid solution or citric acid solution
Any one or at least two combination, preferably oxalic acid aqueous solution, phosphate aqueous solution, sulfuric acid water-alcohol solution, or citric acid water
The oxalic acid aqueous solution of the mixed solution of alcoholic solution and oxalic acid aqueous solution, preferably 0.2M-0.4M, 5wt%-10wt% phosphoric acid water
Solution, 0.5M-1M sulfuric acid water-alcohol solution, or it is any one in the mixed solution of citric acid water alcoholic solution and oxalic acid aqueous solution
Kind.
Preferably, the sulfuric acid water-alcohol solution of the 0.5M-1M is prepared via a method which to obtain：By 98wt% sulfuric acid with
Water and alcohol mixing, the molar concentration for making sulfuric acid water-alcohol solution is 0.5M-1M.
Preferably, during the sulfuric acid water-alcohol solution for preparing 0.5M-1M, the volume ratio of water and alcohol is 1:1.
Preferably, the mixed solution of the citric acid water alcoholic solution and oxalic acid aqueous solution is prepared via a method which to obtain：
Citric acid is mixed with water and alcohol, 0.15M citric acid water alcoholic solution is obtained, then by 0.15M citric acid water alcoholic solution and
0.3M oxalic acid aqueous solution is according to volume ratio 10:1-60:1 mixing.
Preferably, during the mixed solution for preparing citric acid water alcoholic solution and oxalic acid aqueous solution, the volume of water and alcohol
Than for 1:1.
" 5wt%-10wt% phosphate aqueous solution " refers in the aqueous solution in the present invention, and the mass fraction of phosphoric acid is 5wt%-
10wt%.
Preferably, step (3) carry out anodic oxidation during, voltage is 10V-120V, for example, 10V, 20V, 30V,
40V, 45V, 48V, 50V, 53V, 55V, 60V, 65V, 70V, 72V, 75V, 80V, 85V, 90V, 100V, 115V or 120V etc..
In the present invention, by the species and the voltage of anode oxidation process of suitably selected electrolyte, and coordinate adjustment
Other technological parameters of the invention, can control the diameter and length of graphite type carbon nitride nanotube.It is presented below several preferred
Technical scheme is illustrated：
One of optimal technical scheme as the method for the invention, when the electrolyte that step (3) is used is 0.2M-0.4M
Oxalic acid when, during carrying out anodic oxidation, voltage is 30V-60V, coordinates other of the invention technological parameters of adjustment, can make this
The length of graphite type carbon nitride nanotube in the graphite type carbon nitride nanotube array photoelectrode of invention in 400nm-1600nm,
Diameter is in 60nm-90nm.
Preferably, when the electrolyte that step (3) is used is 0.3M oxalic acid, during carrying out anodic oxidation, voltage
For 40V, coordinate in adjustment other technological parameters of the invention, the graphite type carbon nitride nanotube array photoelectrode that the present invention can be made
The length of graphite type carbon nitride nanotube is in 400nm-1600nm, and diameter is in 70nm.
Preferably, when the electrolyte that step (3) is used is 5wt%-10wt% phosphoric acid solution, anodic oxidation is carried out
During, voltage is 70V-100V, coordinates adjustment other technological parameters of the invention, can make the graphite type carbon nitride nanometer of the present invention
Pipe array photoelectric extremely in graphite type carbon nitride nanotube length in 400nm-1600nm, diameter is in 130nm-160nm.
Preferably, when the electrolyte that step (3) is used is 5wt% phosphoric acid solution, during carrying out anodic oxidation,
Voltage is 86V, coordinates adjustment other technological parameters of the invention, can make the graphite type carbon nitride nanotube array photoelectrode of the present invention
In graphite type carbon nitride nanotube length in 400nm-1600nm, diameter is in 150nm.
Preferably, when the electrolyte that step (3) is used is 0.5M-1M sulfuric acid water-alcohol solution, anodic oxidation is carried out
During, voltage is 10V-25V, coordinates adjustment other technological parameters of the invention, can make the graphite type carbon nitride nanometer of the present invention
Pipe array photoelectric extremely in graphite type carbon nitride nanotube length in 400nm-1600nm, diameter is in 20nm-35nm.
Preferably, when the electrolyte that step (3) is used is 0.55M sulfuric acid water-alcohol solution, the mistake of anodic oxidation is carried out
Cheng Zhong, voltage is 20V, coordinates adjustment other technological parameters of the invention, can make the graphite type carbon nitride nano-tube array of the present invention
The length of graphite type carbon nitride nanotube in optoelectronic pole is in 400nm-1600nm, and diameter is in 30nm.
Preferably, when the electrolyte that step (3) is used is the mixed solution of citric acid water alcoholic solution and oxalic acid aqueous solution,
During carrying out anodic oxidation, voltage is 90V-120V, coordinates adjustment other technological parameters of the invention, can make the stone of the present invention
Black type azotized carbon nano pipe array photoelectric extremely in graphite type carbon nitride nanotube length in 400nm-2500nm, diameter exists
120nm-170nm。
Preferably, when the electrolyte that step (3) is used is the mixed solution of citric acid water alcoholic solution and oxalic acid aqueous solution,
During carrying out anodic oxidation, voltage is 120V, coordinates adjustment other technological parameters of the invention, can make the graphite mould of the present invention
Azotized carbon nano pipe array photoelectric extremely in graphite type carbon nitride nanotube length in 400nm-2500nm, diameter is in 170nm.
Preferably, step (4) H3PO4The mass fraction of solution is 5wt%.
Preferably, the time of step (4) described reaming be 40min-300min, for example, 40min, 50min, 60min,
70min、80min、90min、95min、100min、110min、115min、120min、125min、130min、135min、
140min, 160min, 180min, 200min, 215min, 230min, 245min, 270min or 300min etc., be preferably
80min-140min。
Preferably, cyanamide is poured into the anodic oxidation aluminium formwork of step (5) substrate support obtained to step (4)
Process is：By in the anodic oxidation aluminium formwork of substrate support immersion cyanamide solution, ultrasound obtains the cyanamide that pours into of substrate support
Template.
Preferably, the cyanamide solution is the cyanamide solution of concentration, and the concentration of the cyanamide solution of the concentration is 75wt%-
95wt%, for example, 75wt%, 78wt%, 80wt%, 82wt%, 85wt%, 90wt% or 95wt% etc..
Preferably, the cyanamide solution of the concentration is obtained by the following method：By the cyanamide water that mass fraction is 50wt%
Solution is placed 3 days in 50 DEG C of vacuum drying ovens, the cyanamide solution concentrated.
Preferably, the ultrasonic time be 5min-10min, for example, 5min, 6min, 7min, 8min, 9min or
10min etc..
Preferably, the process of step (6) described encapsulation process is：In the template upper cover one for pouring into cyanamide of substrate support
The glass of the sizes such as block, is encased with tinfoil, is then placed in crucible, then with tinfoil by sealed crucible.
The crucible that the present invention is used preferably ceramic crucible.
Preferably, step (6) described inert gas be helium, neon, argon gas, Krypton or xenon in any one or extremely
Few two kinds gaseous mixture, preferably argon gas.
Preferably, step (6) described inert gas is passed through speed for 50sccm-200sccm, for example, 50sccm,
60sccm、70sccm、80sccm、90sccm、100sccm、110sccm、120sccm、125sccm、135sccm、140sccm、
150sccm, 160sccm, 170sccm, 180sccm or 200sccm etc., preferably 100sccm.
Preferably, during step (6) described annealing, annealing temperature is 480 DEG C -550 DEG C, for example, 480 DEG C, 490
DEG C, 500 DEG C, 515 DEG C, 520 DEG C, 530 DEG C, 540 DEG C or 550 DEG C etc., preferably 550 DEG C.
Preferably, during step (6) described annealing, annealing time is 3h-6h, for example 3h, 3.5h, 4h, 4.5h, 5h
Or 6h etc., preferably 4h.
Preferably, the heating rate that step (6) is warming up to the annealing temperature is 2 DEG C/min-3 DEG C/min, for example, 2
DEG C/min, 2.2 DEG C/min, 2.5 DEG C/min or 3 DEG C/min etc., preferably 2.5 DEG C/min.
Preferably, step (7) it is described remove removing template process be：Electrode after step (7) is made annealing treatment immerses NaOH
In solution.
Preferably, during removing removing template described in step (7), the concentration of NaOH solution is 0.12M.
Preferably, step (7) is described remove removing template during, time of immersion is 3h-12h, for example, 3h, 4h, 5h,
6h, 7.5h, 8h, 9h, 10h, 10.5h, 11h or 12h etc..
As the optimal technical scheme of the method for the invention, methods described be additionally included in after step (5) step (6) it
Preceding progress step (5) '：Remove the cyanamide solution of the template surface for pouring into cyanamide of substrate support.
Preferably, step (7) carries out step (6) ' before after methods described is additionally included in step (6)：Cool and close
It is passed through inert gas.
As the optimal technical scheme of the method for the invention, (preparation flow schematic diagram the described method comprises the following steps
Referring to Fig. 1)：
(1) adhesion layer is sputtered in conductive substrates；
(2) conductive substrates for having sputtered adhesion layer are annealed；
(3) continue to sputter Al films on adhesion layer, obtain Al/ adhesion layers/conductive substrates, encapsulate；
(4) step (3) is encapsulated to obtained electrode to be placed in electrolyte, anode is carried out under 20V-120V voltage conditions
Oxidation；
(5) electrode for obtaining step (4) anodic oxidation is placed in H3PO4Reaming 40min-300min in solution, obtains substrate
The anodic oxidation aluminium formwork of support, is named as through hole AAO templates/adhesion layer/conductive substrates；
(6) remove in the silica gel of encapsulated electrode, immersion cyanamide solution, ultrasound obtains the mould for pouring into cyanamide of substrate support
Plate, is named as cyanamide-AAO/ adhesion layers/conductive substrates；
(7) in the glass of the sizes such as one piece of the template upper cover for pouring into cyanamide of substrate support, sealed with tinfoil, in argon gas
Anneal 4h under protection in 550 DEG C, is cooled to room temperature, and closing is passed through argon gas；
(8) removing template, obtains graphite type carbon nitride nanotube array photoelectrode.
As the another optimal technical scheme of the method for the invention, it the described method comprises the following steps：
(1) conductive substrates are placed into alcoholic solution, ultrasound obtains clean conductive substrates；
(2) adhesion layer is sputtered in clean conductive substrates；
(3) continue to sputter Al films on adhesion layer, use silica gel packaging, solidification；
(4) step (3) is encapsulated to obtained electrode to be placed in electrolyte, anode is carried out under 20V-120V voltage conditions
Oxidation；
(5) electrode for obtaining step (4) anodic oxidation is placed in H3PO4Reaming 40min-300min in solution, obtains substrate
The anodic oxidation aluminium formwork of support；
(6) mass fraction is placed 3 days for the 50wt% cyanamide aqueous solution in 50 DEG C of vacuum drying ovens, the ammonia concentrated
Nitrile solution；
(7) remove in the silica gel of encapsulated electrode, the cyanamide solution for immersing above-mentioned concentration, ultrasound obtains substrate support
Pour into the template of cyanamide；
(8) the cyanamide solution of the template surface for pouring into cyanamide of substrate support is removed, then, ammonia is poured into substrate support
The glass of the sizes such as one piece of the template upper cover of nitrile, is encased with tinfoil, is then placed in ceramic crucible, then with tinfoil that crucible is close
Envelope, anneal 4h under argon gas protection in 550 DEG C, is cooled to room temperature, and closing is passed through argon gas；
(9) 3h-12h obtains so as to remove removing template in the NaOH of the electrode immersion 0.12M after step (8) is made annealing treatment
Graphite type carbon nitride nanotube array photoelectrode.
The third aspect, the graphite type carbon nitride nanotube array photoelectrode that the present invention provides as described in relation to the first aspect is used as light
Purposes of the anode in solar energy electrochemical decomposition aquatic products oxygen.
Compared with the prior art, the present invention has the advantages that：
(1) anodised aluminium that method of the invention is supported using conductive substrates is template, and the cyanamide solution using concentration is before
Body is driven, high-temperature polycondensation is obtained in an inert atmosphere, by adjusting the voltage in Arrays Aluminum Films in Acid Solution, anode oxidation process, Yi Jiyu
The cooperation of other specification, has been obtained by diameter, adjustable length graphite type carbon nitride nanotube is regular is arranged in shape in conductive substrates
Into graphite type carbon nitride nanotube array photoelectrode, the diameter range of graphite type carbon nitride nanotube is 20nm-170nm, long
Degree scope is 400nm-2500nm.
(2) graphite type carbon nitride nanotube array photoelectrode prepared by the present invention has big specific surface area, more table
Face avtive spot, and the hollow one-dimentional structure of the graphite type carbon nitride nanotube of regular arrangement is conducive to dividing for electron hole
From graphite type carbon nitride nanotube array photoelectrode of the invention is applied to solar energy electrochemical decomposition aquatic products as light anode
Oxygen excellent performance, in 1.23V vsRHE, in 0.1M Na2SO4In solution, graphite type carbon nitride nanotube prepared by the present invention
Array photoelectric aurora electric current can reach 94 μ A/cm2。
(3) graphite type carbon nitride nano-tube array cheap, the material growth method letter for preparing device therefor in the present invention
List and technological parameter are easy to regulation and control.
Brief description of the drawings
Fig. 1 is the preparation flow schematic diagram that the present invention prepares g-CN nanotube array photoelectrodes；
Fig. 2 is the SEM sectional views of g-CN nanotube array photoelectrodes prepared by embodiment 2；
Fig. 3 is the SEM plans of g-CN nanotube array photoelectrodes prepared by embodiment 3；
Fig. 4 is the SEM sectional views of g-CN nanotube array photoelectrodes prepared by embodiment 3；
Fig. 5 is the photoelectric properties figure of g-CN nanotube array photoelectrodes prepared by embodiment 3；
Fig. 6 is the SEM sectional views of g-CN nanotube array photoelectrodes prepared by embodiment 4.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1
(1) FTO is cut into 2cm*2.5cm sizes, successively each ultrasonic 15min in isopropanol, acetone and ethanol,
Then dried up with nitrogen.
(2) clean FTO one end is stained with high temperature gummed tape, the thick TiO of 30nm is then sputtered on FTO2, sputtering terminates
Afterwards, tear high temperature gummed tape, be placed in Muffle furnace, anneal 2h at 500 DEG C, heating rate is 16 DEG C/min.
(3) TiO will not be sputtered2FTO part be stained with high temperature gummed tape, then have TiO in sputtering2Part continue sputter
1600nm aluminium, after taking-up, adhesive tape of tearing, labeled as Al/TiO2/FTO。
(4) silica gel packaging Al/TiO is used2/ FTO electrodes, are then stood 2-5 days, allow silica gel fully to solidify.
(5) electrode for preparing step (4) is placed in 0.3M H2C2O4In solution, anodic oxidation is carried out, oxidation voltage is
40V, anodic oxidation to electrode it is transparent when, terminate oxidation, be then immersed in 5wt%H3PO4In solution, reaming 120min is obtained
The anodic oxidation aluminium formwork of substrate support, labeled as AAO-O/TiO2/ FTO, wherein, the aperture of anodic oxidation aluminium formwork is about
70nm。
(6) silica gel of encapsulated electrode is removed, is put into the cyanamide solution of concentration that (the 50wt% cyanamide aqueous solution is at 50 DEG C
Placed 3 days in vacuum drying oven), the ultrasound 10min in ultrasonic cleaner, power is 100w.After ultrasound terminates, take out, remove
The cyanamide solution of excess surface, then the sizes such as its surface cover lastblock sheet glass and encase with tinfoil sealing, then will
It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible of the good seal in step (6) is placed in tube furnace, under the protection of argon gas, 550 DEG C of annealing 4h,
Heating rate is 2.5 DEG C/min, and the flow velocity of argon gas is 100sccm.
(8) reaction terminates, after temperature is down to room temperature, closes gas, takes out sample.The sample that reaction is obtained is placed in
Soak 7h in 0.12M NaOH solutions, remove template, obtain g-CN nanometer pipe array electrodes, wherein, g-CN nanotubes are averaged
Caliber about 70nm, length is 1600nm.
Embodiment 2
(1) FTO is cut into 2cm*2.5cm sizes, successively each ultrasonic 15min in isopropanol, acetone and ethanol,
Then dried up with nitrogen.
(2) clean FTO one end is stained with high temperature gummed tape, the thick TiO of 30nm is then sputtered on FTO2It is used as adhesion
Layer, after sputtering terminates, high temperature gummed tape of tearing is placed in Muffle furnace, and anneal 2h at 500 DEG C, and heating rate is 16 DEG C/min.
(3) TiO will not be sputtered2FTO part be stained with high temperature gummed tape, then have TiO in sputtering2Part continue sputter
800nm aluminium, after taking-up, adhesive tape of tearing, labeled as Al/TiO2/FTO。
(4) silica gel packaging Al/TiO is used2/ FTO electrodes, are then stood 2-5 days, allow silica gel fully to solidify.
(5) electrode for preparing step (4) is placed in 5wt%H3PO4In solution, oxidation voltage is 86V, anodic oxidation to electricity
When extremely transparent, terminate oxidation, be then immersed in 5wt%H3PO4In solution, reaming 120min obtains the anodic oxygen of substrate support
Change aluminum alloy pattern plate, labeled as AAO-p/TiO2/ FTO, wherein, the aperture of anodic oxidation aluminium formwork is about 150nm.
(6) silica gel of encapsulated electrode is removed, is put into the cyanamide solution of concentration that (the 50wt% cyanamide aqueous solution is at 50 DEG C
Placed 3 days in vacuum drying oven), the ultrasound 10min in ultrasonic cleaner, power is 100w.After ultrasound terminates, take out, remove
The cyanamide solution of excess surface, then the sizes such as its surface cover lastblock sheet glass and encase with tinfoil sealing, then will
It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible of the good seal in step (6) is placed in tube furnace, under the protection of argon gas, 550 DEG C of annealing 4h,
Heating rate is 2.5 DEG C/min, and the flow velocity of argon gas is 100sccm.
(8) reaction terminates, after temperature is down to room temperature, closes gas, takes out sample.The sample that reaction is obtained is placed in
Soak 6h in 0.12M NaOH solutions, remove template, obtain g-CN nanometer pipe array electrodes, wherein, g-CN nanotubes are averaged
Caliber about 150nm.
Fig. 2 is the SEM sectional views of g-CN nanotube array photoelectrodes prepared by this example, as seen from the figure, average straight
Footpath is 150nm, and length is basically perpendicular to substrate for 800nm g-CN nano-tube arrays.
Embodiment 3
(1) FTO is cut into 2cm*2.5cm sizes, successively each ultrasonic 15min in isopropanol, acetone and ethanol,
Then dried up with nitrogen.
(2) clean FTO one end is stained with high temperature gummed tape, the thick TiO of 30nm is then sputtered on FTO2, sputtering terminates
Afterwards, tear high temperature gummed tape, be placed in Muffle furnace, anneal 2h at 500 DEG C, heating rate is 16 DEG C/min.
(3) TiO will not be sputtered2FTO part be stained with high temperature gummed tape, then have TiO in sputtering2Part continue sputter
1600nm aluminium, after taking-up, adhesive tape of tearing, labeled as Al/TiO2/FTO。
(4) silica gel packaging Al/TiO is used2/ FTO electrodes, are then stood 2-5 days, allow silica gel fully to solidify.
(5) electrode for preparing step (4) is placed in 5wt%H3PO4In solution, oxidation voltage is 86V, anodic oxidation to electricity
When extremely transparent, terminate oxidation, be then immersed in 5wt%H3PO4In solution, reaming 140min obtains the anodic oxygen of substrate support
Change aluminum alloy pattern plate, labeled as AAO-p/TiO2/ FTO, wherein, the aperture of anodic oxidation aluminium formwork is about 150nm.
(6) silica gel of encapsulated electrode is removed, is put into the cyanamide solution of concentration that (the 50wt% cyanamide aqueous solution is at 50 DEG C
Placed 3 days in vacuum drying oven), the ultrasound 10min in ultrasonic cleaner, power is 100w.After ultrasound terminates, take out, remove
The cyanamide solution of excess surface, then the sizes such as its surface cover lastblock sheet glass and encase with tinfoil sealing, then will
It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible of the good seal in step (6) is placed in tube furnace, under the protection of argon gas, 550 DEG C of annealing 4h,
Heating rate is 2.5 DEG C/min, and the flow velocity of argon gas is 100sccm.
(8) reaction terminates, after temperature is down to room temperature, closes gas, takes out sample.The sample that reaction is obtained is placed in
Soak 12h in 0.12M NaOH solutions, remove template, obtain g-CN nanometer pipe array electrodes, wherein, g-CN nanotubes are averaged
Caliber about 150nm.
Fig. 3 is the SEM plans of g-CN nanotube array photoelectrodes prepared by this example, as seen from the figure, nanotube
Top it is opening-like.
Fig. 4 is the SEM sectional views of g-CN nanotube array photoelectrodes prepared by this example, as seen from the figure, average straight
Footpath is 150nm, and length is basically perpendicular to substrate for 1600nm g-CN nano-tube arrays.
Fig. 5 is the photoelectric properties figure of g-CN nanotube array photoelectrodes prepared by this example, as seen from the figure,
During 1.23V vsRHE, in 0.1M Na2SO4In solution, g-CN nanotube array photoelectrodes photoelectric current manufactured in the present embodiment is reachable
To 94 μ A/cm2。
Embodiment 4
(1) ITO is cut into 2cm*2.5cm sizes, successively each ultrasonic 15min in isopropanol, acetone and ethanol,
Then dried up with nitrogen.
(2) clean ITO one end is stained with high temperature gummed tape, then sputters 10nm thick Ti, 60nm successively on ITO thick
The thick Al of W, 400nm, labeled as Al/W/Ti/ITO.
(3) silica gel packaging Al/W/Ti/ITO electrodes are used, 2-5 days is then stood, allows silica gel fully to solidify.
(4) electrode for preparing step (3) is placed in 5wt%H3PO4In solution, oxidation voltage is 86V, anodic oxidation to electricity
When extremely transparent, terminate oxidation, be then immersed in 5wt%H3PO4In solution, reaming 90min obtains the anodic oxygen of substrate support
Change aluminum alloy pattern plate, labeled as AAO-P/W/Ti/ITO, wherein, the aperture of anodic oxidation aluminium formwork is about 150nm.
(5) silica gel of encapsulated electrode is removed, is put into the cyanamide solution of concentration that (the 50wt% cyanamide aqueous solution is at 50 DEG C
Placed 3 days in vacuum drying oven), the ultrasound 5min in ultrasonic cleaner, power is 100w.After ultrasound terminates, take out, remove table
The unnecessary cyanamide solution in face, then the sizes such as its surface cover lastblock sheet glass and encase sealing with tinfoil, then by it
It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(6) crucible of the good seal in step (5) is placed in tube furnace, under the protection of argon gas, 550 DEG C of annealing 4h,
Heating rate is 2.5 DEG C/min, and the flow velocity of argon gas is 100sccm.
(7) reaction terminates, after temperature is down to room temperature, closes gas, takes out sample.The sample that reaction is obtained is placed in
Soak 3h in 0.12M NaOH solutions, remove template, obtain g-CN nanometer pipe array electrodes, wherein, g-CN nanotubes are averaged
Caliber about 150nm.
Fig. 6 is the SEM sectional views of g-CN nanotube array photoelectrodes prepared by this example, as seen from the figure, average straight
Footpath is 150nm, and length is 400nm g-CN nano-tube arrays perpendicular to substrate.
Embodiment 5
(1) FTO is cut into 2cm*2.5cm sizes, successively each ultrasonic 10min in isopropanol, acetone and ethanol,
Then dried up with nitrogen.
(2) clean FTO one end is stained with high temperature gummed tape, 25nm TiO is then sputtered on FTO2, sputtering terminates
Afterwards, tear high temperature gummed tape, be placed in Muffle furnace, anneal 2h at 500 DEG C, heating rate is 15 DEG C/min.
(3) TiO will not be sputtered2FTO part be stained with high temperature gummed tape, then have TiO in sputtering2Part continue sputter
600nm aluminium, after taking-up, adhesive tape of tearing, labeled as Al/TiO2/FTO。
(4) silica gel packaging Al/TiO is used2/ FTO electrodes, are then stood 2-5 days, allow silica gel fully to solidify.
(5) electrode for preparing step (4) is placed in 0.3M H2C2O4In solution, anodic oxidation is carried out, oxidation voltage is
50V, anodic oxidation to electrode it is transparent when, terminate oxidation, be then immersed in 5wt%H3PO4In solution, reaming 90min is obtained
The anodic oxidation aluminium formwork of substrate support, labeled as AAO-O/TiO2/ FTO, wherein, the aperture of anodic oxidation aluminium formwork is about
80nm。
(6) silica gel of encapsulated electrode is removed, is put into the cyanamide solution of concentration that (the 50wt% cyanamide aqueous solution is at 50 DEG C
Placed 3 days in vacuum drying oven), the ultrasound 8min in ultrasonic cleaner, power is 100w.After ultrasound terminates, take out, remove table
The unnecessary cyanamide solution in face, then the sizes such as its surface cover lastblock sheet glass and encase sealing with tinfoil, then by it
It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible of the good seal in step (6) is placed in tube furnace, under the protection of argon gas, 550 DEG C of annealing 4h,
Heating rate is 2.5 DEG C/min, and the flow velocity of argon gas is 75sccm.
(8) reaction terminates, after temperature is down to room temperature, closes gas, takes out sample.The sample that reaction is obtained is placed in
Soak 5h in 0.12M NaOH solutions, remove template, obtain g-CN nanometer pipe array electrodes, wherein, g-CN nanotubes are averaged
Caliber about 80nm, length is 600nm.
Embodiment 6
(1) ITO is cut into 2cm*2.5cm sizes, successively each ultrasonic 15min in isopropanol, acetone and ethanol,
Then dried up with nitrogen.
(2) clean ITO one end is stained with high temperature gummed tape, then sputters 10nm thick Ti, 50nm successively on ITO thick
W and the thick Al of 750nm, labeled as Al/Ti/W/ITO.
(3) silica gel packaging Al/Ti/W/ITO electrodes are used, 2-5 days is then stood, allows silica gel fully to solidify.
(4) 98wt% sulfuric acid mixes to (wherein, the volume ratio of water and alcohol is 1 with water and alcohol:1), make sulfuric acid water alcohol molten
The mass fraction of liquid is 5.5wt%.
(5) electrode for preparing step (3) is placed in 0.55M sulfuric acid water-alcohol solutions, and oxidation voltage is 20V, anodic oxidation
To electrode it is transparent when, terminate oxidation, be then immersed in 5wt%H3PO4In solution, reaming 35min obtains the sun of substrate support
Pole alumina formwork, labeled as AAO-S/Ti/W/ITO, wherein, the aperture of anodic oxidation aluminium formwork is about 30nm.
(6) silica gel of encapsulated electrode is removed, is put into the cyanamide solution of concentration that (the 50wt% cyanamide aqueous solution is at 50 DEG C
Placed 3 days in vacuum drying oven), the ultrasound 6min in ultrasonic cleaner, power is 100w.After ultrasound terminates, take out, remove table
The unnecessary cyanamide solution in face, then the sizes such as its surface cover lastblock sheet glass and encase sealing with tinfoil, then by it
It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible of the good seal in step (5) is placed in tube furnace, under the protection of helium, 550 DEG C of annealing 4h,
Heating rate is 2.5 DEG C/min, and the flow velocity of nitrogen is 120sccm.
(8) reaction terminates, after temperature is down to room temperature, closes gas, takes out sample.The sample that reaction is obtained is placed in
Soak 3h in 0.12M NaOH solutions, remove template, obtain g-CN nanometer pipe array electrodes, wherein, g-CN nanotubes are averaged
Caliber about 30nm, length is 750nm.
Embodiment 7
(1) ITO is cut into 2cm*2.5cm sizes, successively each ultrasonic 12min in isopropanol, acetone and ethanol,
Then dried up with nitrogen.
(2) clean ITO one end is stained with high temperature gummed tape, then sputters 8nm thick Ti, 60nm successively on ITO thick
W and the thick Al of 1100nm, labeled as Al/Ti/W/ITO.
(3) silica gel packaging Al/Ti/W/ITO electrodes are used, 2-5 days is then stood, allows silica gel fully to solidify.
(4) citric acid mixes to (wherein, the volume ratio of water and alcohol is 1 with water and alcohol:1) 0.15M citric acid water, is obtained
Alcoholic solution, then by 0.15M citric acid water alcoholic solution and 0.3M oxalic acid aqueous solution according to volume ratio 10:1 mixing, obtains lemon
The mixed solution of lemon sour water alcoholic solution and oxalic acid aqueous solution.
(5) electrode for preparing step (3) is placed in the mixed solution of citric acid water alcoholic solution and oxalic acid aqueous solution, is aoxidized
Voltage is 120V, anodic oxidation to electrode it is transparent when, terminate oxidation, be then immersed in 5wt%H3PO4In solution, reaming
250min, obtains the anodic oxidation aluminium formwork of substrate support, labeled as AAO- (O+C)/Ti/W/ITO, wherein, anodised aluminium
The aperture of template is about 170nm.
(6) silica gel of encapsulated electrode is removed, is put into the cyanamide solution of concentration that (the 50wt% cyanamide aqueous solution is at 50 DEG C
Placed 3 days in vacuum drying oven), the ultrasound 8min in ultrasonic cleaner, power is 100w.After ultrasound terminates, take out, remove table
The unnecessary cyanamide solution in face, then the sizes such as its surface cover lastblock sheet glass and encase sealing with tinfoil, then by it
It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible of the good seal in step (5) is placed in tube furnace, under the protection of helium, 550 DEG C of annealing 4h,
Heating rate is 2.5 DEG C/min, and the flow velocity of argon gas is 150sccm.
(8) reaction terminates, after temperature is down to room temperature, closes gas, takes out sample.The sample that reaction is obtained is placed in
Soak 8h in 0.12M NaOH solutions, remove template, obtain g-CN nanometer pipe array electrodes, wherein, g-CN nanotubes are averaged
Caliber about 170nm, length is 1100nm.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of graphite type carbon nitride nanotube array photoelectrode, it is characterised in that the graphite type carbon nitride nano-tube array
Graphite type carbon nitride nano-tube array of the optoelectronic pole by substrate and in the substrate is constituted, the graphite type carbon nitride nanometer
Pipe array is formed by graphite type carbon nitride Nanotube alignment.
2. graphite type carbon nitride nano-tube array according to claim 1, it is characterised in that the graphite type carbon nitride is received
A diameter of 20nm-170nm of mitron, preferably 70nm-150nm；
Preferably, the length of the graphite type carbon nitride nanotube is 400nm-2500nm, preferably 400nm-1600nm；
Preferably, the substrate is conductive substrates, preferably any one in ito glass, FTO glass or Si pieces.
3. the preparation method of graphite type carbon nitride nanotube array photoelectrode as claimed in claim 1 or 2, it is characterised in that
It the described method comprises the following steps：
(1) adhesion layer is sputtered in substrate；
(2) continue to sputter Al films, encapsulation on adhesion layer；
(3) step (2) is encapsulated to obtained electrode to be placed in electrolyte, anodic oxidation is carried out；
(4) electrode for obtaining step (3) anodic oxidation is placed in H3PO4Reaming in solution, obtains the anodised aluminium of substrate support
Template；
(5) remove in encapsulation, the anodic oxidation aluminium formwork of the substrate support obtained to step (4) and pour into cyanamide, obtain substrate branch
The template for pouring into cyanamide of support；
(6) encapsulation process is carried out, is then annealed under inert gas shielding；
(7) removing template is removed, graphite type carbon nitride nanotube array photoelectrode is obtained.
4. method according to claim 3, it is characterised in that step (1) described substrate is conductive substrates, preferably ITO
Any one in glass, FTO glass or Si pieces；
Preferably, the step of step (1) described substrate is first cleaned by ultrasonic and dried up before the use；
Preferably, the thickness of step (1) described adhesion layer is 5nm-70nm；
Preferably, step (1) described adhesion layer is TiO2Layer, or for by the Ti layers and W layers combination layer constituted；
Preferably, step (1) described adhesion layer is TiO2Layer, and the TiO2The thickness of layer is 20nm-50nm；
Preferably, step (1) described adhesion layer is the thick TiO of 30nm2Layer；
Preferably, step (1) described adhesion layer is the Ti layers by the Ti layers and W layers combination layer constituted, and in the combination layer
Thickness is 5nm-10nm, and described W layers thickness is 40nm-70nm；
Preferably, step (1) described adhesion layer is the combination layer being made up of the thick W layers of thick 10nm Ti layers and 60nm；
Preferably, when step (1) described adhesion layer is TiO2During layer, TiO has been sputtered in step (1)2After layer, step (2) sputtering
Before Al films, proceed as follows：To having sputtered TiO2The substrate of layer is made annealing treatment；
Preferably, to having sputtered TiO2During the substrate of layer is made annealing treatment, annealing temperature is 450 DEG C -550 DEG C, preferably
For 500 DEG C；
Preferably, to having sputtered TiO2During the substrate of layer is made annealing treatment, annealing time is 30min-4h, is preferably
2h；
Preferably, to having sputtered TiO2During the substrate of layer is made annealing treatment, the heating rate for being warming up to annealing temperature is
10 DEG C/min-20 DEG C/min, preferably 16 DEG C/min.
5. the method according to claim 3 or 4, it is characterised in that the thickness of step (2) the Al films is 400nm-
2500nm, preferably 400nm-1600nm；
Preferably, step (2) is described is encapsulated as：The electrode after sputtering Al films is packaged and solidified using silica gel.
6. the method according to claim any one of 3-5, it is characterised in that step (3) described electrolyte be oxalic acid solution,
In phosphoric acid solution, sulfuric acid solution or citric acid solution any one or at least two combination, preferably oxalic acid aqueous solution, phosphorus
The mixed solution of aqueous acid, sulfuric acid water-alcohol solution, or citric acid water alcoholic solution and oxalic acid aqueous solution, preferably 0.2M-0.4M
Oxalic acid aqueous solution, 5wt%-10wt% phosphate aqueous solution, 0.5M-1M sulfuric acid water-alcohol solution, or citric acid water alcoholic solution
With any one in the mixed solution of oxalic acid aqueous solution；
Preferably, the sulfuric acid water-alcohol solution of the 0.5M-1M is prepared via a method which to obtain：By 98wt% sulfuric acid and water and
Alcohol is mixed, and the molar concentration for making sulfuric acid water-alcohol solution is 0.5M-1M；
Preferably, during the sulfuric acid water-alcohol solution for preparing 0.5M-1M, the volume ratio of water and alcohol is 1:1；
Preferably, the mixed solution of the citric acid water alcoholic solution and oxalic acid aqueous solution is prepared via a method which to obtain：By lemon
Lemon acid is mixed with water and alcohol, 0.15M citric acid water alcoholic solution is obtained, then by 0.15M citric acid water alcoholic solution and 0.3M
Oxalic acid aqueous solution according to volume ratio 10:1-60:1 mixing；
Preferably, during the mixed solution for preparing citric acid water alcoholic solution and oxalic acid aqueous solution, the volume ratio of water and alcohol is
1:1；
Preferably, during step (3) carries out anodic oxidation, voltage is 10V-120V；
Preferably, when the electrolyte that step (3) is used is 0.2M-0.4M oxalic acid, during carrying out anodic oxidation, voltage
For 30V-60V, preferably 40V；
Preferably, when the electrolyte that step (3) is used is 5wt%-10wt% phosphoric acid solution, the process of anodic oxidation is carried out
In, voltage is 70V-100V, preferably 86V；
Preferably, when the electrolyte that step (3) is used is 0.5M-1M sulfuric acid water-alcohol solution, the process of anodic oxidation is carried out
In, voltage is 10V-25V, preferably 20V；
Preferably, when the electrolyte that step (3) is used is the mixed solution of citric acid water alcoholic solution and oxalic acid aqueous solution, carry out
During anodic oxidation, voltage is 90V-120V, preferably 120V.
7. the method according to claim any one of 3-6, it is characterised in that step (4) described H3PO4The quality of solution point
Number is 5wt%；
Preferably, the time of step (4) described reaming is 40min-300min, preferably 80min-140min；
Preferably, the process of cyanamide is poured into the anodic oxidation aluminium formwork of step (5) substrate support obtained to step (4)
For：By in the anodic oxidation aluminium formwork immersion cyanamide solution of substrate support, ultrasound obtains the mould for pouring into cyanamide of substrate support
Plate；
Preferably, the cyanamide solution is the cyanamide solution of concentration, and the concentration of the cyanamide solution of the concentration is 75wt%-
95wt%；
Preferably, the cyanamide solution of the concentration is obtained by the following method：By the cyanamide aqueous solution that mass fraction is 50wt%
Placed 3 days in 50 DEG C of vacuum drying ovens, the cyanamide solution concentrated；
Preferably, the ultrasonic time is 5min-10min.
8. the method according to claim any one of 3-8, it is characterised in that the process of step (6) described encapsulation process is：
In the glass of the sizes such as one piece of the template upper cover for pouring into cyanamide of substrate support, encased, be then placed in crucible with tinfoil, then
With tinfoil by sealed crucible；
Preferably, step (6) described inert gas is any one in helium, neon, argon gas, Krypton or xenon or at least two
The gaseous mixture planted, preferably argon gas；
Preferably, the speed that is passed through of step (6) described inert gas is 50sccm-200sccm, preferably 100sccm；
Preferably, during step (6) described annealing, annealing temperature is 480 DEG C -550 DEG C, preferably 550 DEG C；
Preferably, during step (6) described annealing, annealing time is 3h-6h, preferably 4h；
Preferably, step (6) is warming up to the heating rate of the annealing temperature for 2 DEG C/min-3 DEG C/min, preferably 2.5 DEG C/
min；
Preferably, step (7) it is described remove removing template process be：Electrode after step (7) is made annealing treatment immerses NaOH solution
In；
Preferably, during removing removing template described in step (7), the concentration of NaOH solution is 0.12M；
Preferably, during removing removing template described in step (7), the time of immersion is 3h-12h.
9. the method according to claim any one of 3-8, it is characterised in that methods described is additionally included in after step (5)
Step (5) ' is carried out before step (6)：Remove the cyanamide solution of the template surface for pouring into cyanamide of substrate support；
Preferably, step (7) carries out step (6) ' before after methods described is additionally included in step (6)：Cool and close and be passed through
Inert gas.
10. the purposes of graphite type carbon nitride nanotube array photoelectrode as claimed in claim 1 or 2, it is characterised in that described
Graphite type carbon nitride nanotube array photoelectrode is used for solar energy electrochemical decomposition aquatic products oxygen as light anode.
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| CN107986247A (en) * | 2017-12-26 | 2018-05-04 | 佛山科学技术学院 | A kind of preparation method of graphite phase carbon nitride nanotube |
| CN109811313A (en) * | 2019-02-28 | 2019-05-28 | 杭州电子科技大学 | The preparation method of porous alumina formwork in a kind of high resistivity substrate |
| CN115261901A (en) * | 2022-06-24 | 2022-11-01 | 华东理工常熟研究院有限公司 | Novel proton exchange membrane photoelectrolysis water hydrogen production electrolysis trough |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107986247A (en) * | 2017-12-26 | 2018-05-04 | 佛山科学技术学院 | A kind of preparation method of graphite phase carbon nitride nanotube |
| CN109811313A (en) * | 2019-02-28 | 2019-05-28 | 杭州电子科技大学 | The preparation method of porous alumina formwork in a kind of high resistivity substrate |
| CN109811313B (en) * | 2019-02-28 | 2020-12-08 | 杭州电子科技大学 | Preparation method of porous alumina template on high-resistivity substrate |
| CN115261901A (en) * | 2022-06-24 | 2022-11-01 | 华东理工常熟研究院有限公司 | Novel proton exchange membrane photoelectrolysis water hydrogen production electrolysis trough |
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